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WO2020095751A1 - Polyisocyanate de polyester, composition de polyisocyanate de polyester, adhésif, produit stratifié, et matériau d'emballage - Google Patents

Polyisocyanate de polyester, composition de polyisocyanate de polyester, adhésif, produit stratifié, et matériau d'emballage Download PDF

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Publication number
WO2020095751A1
WO2020095751A1 PCT/JP2019/042286 JP2019042286W WO2020095751A1 WO 2020095751 A1 WO2020095751 A1 WO 2020095751A1 JP 2019042286 W JP2019042286 W JP 2019042286W WO 2020095751 A1 WO2020095751 A1 WO 2020095751A1
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WO
WIPO (PCT)
Prior art keywords
acid
derivative
polyester
adhesive
film
Prior art date
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Ceased
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PCT/JP2019/042286
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English (en)
Japanese (ja)
Inventor
正光 新居
常行 手島
下口　睦弘
武田　博之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2020544301A priority Critical patent/JP6801828B2/ja
Priority to CN201980071853.5A priority patent/CN112969583B/zh
Publication of WO2020095751A1 publication Critical patent/WO2020095751A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a polyester polyisocyanate, a polyester polyisocyanate composition, an adhesive, a laminate, and a packaging material.
  • Packaging materials such as foods and beverages have various functions such as strength and resistance to cracking, retort resistance, and heat resistance in order to protect the contents from various distribution, storage such as refrigeration and treatment such as heat sterilization. A wide variety of functions are required, such as excellent transparency so that the contents can be confirmed.
  • an unstretched polyolefin film excellent in heat processability is essential, but the unstretched polyolefin film has many functions insufficient as a packaging material.
  • a composite flexible film in which different kinds of polymer materials are combined is widely used.
  • a composite flexible film is composed of a thermoplastic film layer or the like serving as an outer layer having product protection or various functions, and a thermoplastic film layer or the like serving as a sealant layer, and these are laminated with a thermoplastic resin for the outer layer.
  • a method of melt-extruding three layers of an adhesive and a thermoplastic resin for a sealant layer to form an unstretched laminated sheet and then stretching see, for example, Patent Document 1
  • a dry lamination method see, for example, Patent Document 2 for manufacturing a multi-layer film by adhesion is known.
  • PET polyester terephthalate
  • polyester resin polyamide resin
  • stretched polyolefin resin a film obtained by vapor deposition of silica, alumina, aluminum or the like.
  • vinylidene chloride which has a high oxygen barrier property and a high water vapor barrier property (that is, it is easy to impede mass transfer), has been widely used as a barrier coating material.
  • dioxin is generated during firing, and there is a problem that it turns yellow when exposed to light.
  • the polyvinyl alcohol resin or ethylene-polyvinyl alcohol copolymer having an oxygen barrier function has a problem that the barrier property is further deteriorated under high humidity where the resin swells.
  • the method of giving a gas barrier function to the adhesive used at the time of lamination is an advantage that a multilayer film for gas barrier can be produced without using a special film with a special gas barrier function by the process and the structure essential for producing a laminated film. have.
  • a flexible molecular structure, which is essential for adhesives generally has high gas permeability. Therefore, there is often a trade-off relationship between the adhesive ability and the gas barrier function, and the elimination of this raises the technical difficulty.
  • Patent Document 3 As a container using such a gas barrier barrier laminated film, for example, in Patent Document 3 or Patent Document 4, an epoxy resin is used between a thermoplastic film layer or the like which is an outer layer and a thermoplastic film layer which is a sealant layer.
  • a gas-barrier laminated film bonded with an epoxy resin composition comprising a resin and an epoxy resin curing agent is described.
  • the gas barrier property is not perfect even with the method that uses a film obtained by vapor deposition of silica, alumina, aluminum, etc., because the vapor deposition layer usually has vapor deposition defects. Further, since the vapor-deposited layer is an inorganic thin film, it has low flexibility, and in particular, there is a problem in that cracks occur due to twisting or bending of the film, and barrier performance deteriorates. Since vapor-deposited films are originally used for applications that require a high barrier, the unstable barrier function is a serious problem in terms of quality control of contents.
  • the present invention has been made in view of such circumstances, a packaging material centered on food, a solar cell, a transparent film that can be used as a transparent barrier film for electronic materials such as display elements, the gas barrier function
  • a packaging material centered on food, a solar cell, a transparent film that can be used as a transparent barrier film for electronic materials such as display elements, the gas barrier function
  • Another object of the present invention is to provide a gas barrier multilayer film and a packaging material which are excellent in bending resistance and are strong.
  • the present invention relates to a polyester polyisocyanate (B) which is a reaction product of a polyester which is a polycondensate of a polyvalent carboxylic acid or a derivative thereof (IB) and a polyhydric alcohol (II-B), and an isocyanate compound.
  • the polyvalent carboxylic acid or its derivative (IB) is an aliphatic polyvalent carboxylic acid or its derivative (IBi) having 8 or less carbon atoms in the portion excluding the carboxyl group
  • the polyhydric alcohol (II-B) containing an aromatic polyhydric carboxylic acid or a derivative thereof (IB-ii) is an aliphatic polyhydric alcohol (II-Bi) having 8 or less carbon atoms.
  • the present invention relates to a polyisocyanate composition containing the polyester polyisocyanate (B), an adhesive using the polyisocyanate composition, a laminate obtained by using the adhesive, and a packaging material obtained by using the laminate. ..
  • polyester polyisocyanate (B) of the present invention it is possible to provide an adhesive having excellent gas barrier properties, and further to provide a gas barrier multilayer film and a packaging material which are excellent in gas barrier function and strong in bending treatment. It will be possible.
  • the present invention relates to a polyester polyisocyanate (B) which is a reaction product of a polyester which is a polycondensate of a polyvalent carboxylic acid or a derivative thereof (IB) and a polyhydric alcohol (II-B), and an isocyanate compound.
  • the polyvalent carboxylic acid or its derivative (IB) is an aliphatic polyvalent carboxylic acid or its derivative (IBi) having 8 or less carbon atoms in the portion excluding the carboxyl group
  • the polyhydric alcohol (II-B) containing an aromatic polyhydric carboxylic acid or a derivative thereof (IB-ii) is an aliphatic polyhydric alcohol (II-Bi) having 8 or less carbon atoms.
  • the present invention is a polyisocyanate composition using a polyester polyisocyanate (B), an adhesive, a laminate, and a packaging material.
  • B polyester polyisocyanate
  • the configuration of the present invention will be described in detail.
  • polyol composition used in the present invention is one component of a two-component adhesive used together with the polyisocyanate composition.
  • polyol composition used in the present invention will be described in detail.
  • the polyol composition used in the present invention contains a resin (polyol) having substantially two or more hydroxyl groups. Since the time required for synthesis is short and the handling is easy, it is preferable to use a polyol having a number average molecular weight of 300 or more and 3000 or less, more preferably 350 or more and 1000 or less, and 350 or more and 950 or less. It is more preferable to use.
  • the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) under the following conditions.
  • HLC-8220GPC manufactured by Tosoh Corporation Column; Tosoh Corporation TSK-GUARDCOULUMN SuperHZ-L + Tosoh Corporation TSK-GEL SuperHZM-M x 4 Detector; RI (differential refractometer) Data processing; Multi-station GPC-8020 modelII manufactured by Tosoh Corporation Measurement conditions; Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene sample; Tetrahydrofuran solution of 0.2% by mass in terms of resin solid content filtered with a microfilter (100 ⁇ l)
  • the polyol examples include a polyol having a polyester skeleton, a polyol having a polyurethane skeleton, a polyol having a polyether skeleton, and a polyol having an acrylic skeleton.
  • the polyvalent carboxylic acid or its derivative (IA) is used. It is preferable to include a polyol (A) having a polyester skeleton which is a polycondensation product with a polyhydric alcohol (II-A).
  • the polyol (A) having a polyester skeleton is also simply referred to as a polyester polyol (A).
  • the polyester polyol (A) used in the present invention is A polyester polyol (which is obtained by using, as the polyvalent carboxylic acid or its derivative (IA), an aliphatic polyvalent carboxylic acid having a carbon atom number of 8 or less in the portion excluding the carboxyl group or its derivative (IAi) A); A polyester polyol (A) obtained by using an aromatic polyvalent carboxylic acid or its derivative (IA-ii) as the polyvalent carboxylic acid or its derivative (IA); Aliphatic polycarboxylic acid or its derivative (IA) having a carbon number of 8 or less in the portion excluding the carboxyl group as polycarboxylic acid or its derivative (IA), and aromatic polycarboxylic acid Or a polyester polyol (A) obtained in combination with a derivative thereof (IA-ii); However, the present invention is not limited to this.
  • the polyester polyol (A) used in the present invention preferably contains, as the polyhydric alcohol (II-A), an ali
  • an aliphatic polycarboxylic acid having 8 or less carbon atoms in the portion excluding a carboxyl group or a derivative thereof is also called a polycarboxylic acid (IAi), which is an aromatic polycarboxylic acid.
  • a carboxylic acid or its derivative (IA-ii) is also called a polycarboxylic acid (IA-ii)
  • an aliphatic polyhydric alcohol (II-Ai) having 8 or less carbon atoms is polyvalent. Also referred to as alcohol (II-A-i).
  • Polyvalent carboxylic acid or its derivative (IA) Polyvalent carboxylic acids (IAi)
  • polyvalent carboxylic acids (IAi) As the polyvalent carboxylic acids (IAi) used for synthesizing the polyester polyol (A), conventionally known ones can be used without particular limitation.
  • Polyvalent carboxylic acids (IA-ii)) As the polyvalent carboxylic acids (IA-ii) used for synthesizing the polyester polyol (A), conventionally known ones can be used without particular limitation. Specifically, orthophthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl Examples thereof include dicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, and their anhydrides and methyl ester compounds, and these can be used alone or in combination of two or more kinds.
  • orthophthalic acid terephthalic acid, isophthalic acid, and their anhydrides
  • orthophthalic acid or orthophthalic anhydride it is more preferable to use orthophthalic acid or orthophthalic anhydride in order to improve the gas barrier property and the adhesive property of the adhesive described later. ..
  • the reason why the gas barrier property of the adhesive is excellent by using orthophthalic acid or orthophthalic anhydride is that the rotation of the polyester chain obtained by using orthophthalic acid or its anhydride is suppressed.
  • the reason why the adhesiveness is excellent is that the polyester chain is asymmetric and thus exhibits non-crystallinity, and sufficient base material adhesion is imparted.
  • the polyvalent carboxylic acid or its derivative (IA) used in the synthesis of the polyester polyol (A) of the present invention includes polyvalent carboxylic acids (IAi) and polyvalent carboxylic acids (IA-ii). Other polyvalent carboxylic acids (IA-iii) may be included. Examples of the polyvalent carboxylic acids (IA-iii) include polyvalent carboxylic acids having more than 8 carbon atoms excluding the carboxyl group, such as dodecanedicarboxylic acid, which may be used alone or in combination of two or more. it can. When the polyvalent carboxylic acid (IA-iii) is used in combination, it is preferably 10% by mass or less and more preferably 5% by mass or less of the total amount of the polycarboxylic acid or its derivative (IA). ..
  • the proportion of the polyvalent carboxylic acid (IAi) in the polyvalent carboxylic acid or its derivative (IA) is 100 mol%. Is preferred.
  • the proportion of the polycarboxylic acid (IA-ii) in the polycarboxylic acid or its derivative (IA) is 100 mol%.
  • the combined use of the polycarboxylic acid (IAi) and the polycarboxylic acid (IA-ii) is preferable because the cured coating film of the adhesive described below has excellent gas barrier properties and flex resistance.
  • the compounding ratio (molar ratio) of the polyvalent carboxylic acids (IAi) and the polyvalent carboxylic acids (IA-ii) is, for example, 1: 9 to 9: 1, and more preferably 2: 8 to 8: 2.
  • Polyhydric alcohol (II-A) (Polyhydric alcohol (II-Ai))
  • polyhydric alcohol (II-Ai) As the polyhydric alcohol (II-Ai) used for synthesizing the polyester polyol (A), conventionally known ones can be used without particular limitation.
  • the polyhydric alcohol (II-A-ii) used for the synthesis of the polyester polyol (A) may contain a polyhydric alcohol (II-A-ii) other than the polyhydric alcohol (II-Ai).
  • examples of the polyhydric alcohol (II-A-ii) include tetraethylene glycol, tripropylene glycol, dipentaerythritol, hydroquinone, resorcinol, catechol, naphthalenediol, biphenol, bisphenol A, bisphenol F, tetramethylbiphenol, and the like. They can be used alone or in combination of two or more.
  • the polyhydric alcohol (II-A-ii) is used in combination, it is preferably 10% by mass or less and more preferably 5% by mass or less based on the total amount of the polyhydric alcohol (II-A).
  • polyester polyol (A) The number average molecular weight of the polyester polyol (A) is preferably 300 or more and 3000 or less, more preferably 350 or more and 1000 or less, and further preferably 350 or more and 950 or less. This makes it possible to obtain an adhesive having excellent adhesiveness and gas barrier properties.
  • the hydroxyl value of the polyester polyol (A) is preferably 20 mgKOH / g or more and 400 mgKOH / g or less. When the hydroxyl value is less than 20 mgKOH / g, the viscosity of the polyester polyol (A) becomes high, and good coating suitability may not be obtained. If the hydroxyl value exceeds 400 mgKOH / g, the crosslink density of the cured coating film may be too high, and good adhesive strength may not be obtained.
  • the hydroxyl value of the polyester polyol (A) can be measured by the hydroxyl value measuring method described in JIS-K0070.
  • the acid value of the polyester polyol (A) is preferably 200 mgKOH / g or less. When the acid value exceeds 200 mgKOH / g, the reaction with the polyisocyanate may be too fast, and good coating suitability may not be obtained.
  • the lower limit of the acid value of the polyester polyol (A) is not particularly limited and may be 0 mgKOH / g.
  • the acid value of the polyester polyol (A) can be measured by the acid value measuring method described in JIS-K0070.
  • the glass transition temperature of the polyester polyol (A) is preferably 10 ° C. or lower, and more preferably 5 ° C. or lower in order to improve the adhesiveness.
  • the lower limit of the glass transition temperature is not particularly limited, but as an example, it is ⁇ 60 ° C. or higher, and more preferably ⁇ 50 ° C. or higher.
  • the glass transition temperature of the polyester polyol (A) can be measured by a differential scanning calorimeter.
  • the polyester polyol (A) used in the present invention is preferably linear.
  • the polyester polyol (A) having a linear structure means that all the polyester polyol raw materials (polyvalent carboxylic acid or its derivative (IA) and polyhydric alcohol (II-A)) are 2 It is composed of a compound having one reactive group.
  • the polyhydric alcohol (II-A) a polyester polyol prepared by using a bifunctional alcohol having a branched alkyl group such as neopentyl glycol is linearly contained. As a result, an increase in the viscosity of the polyester polyol can be suppressed, and an adhesive having excellent coatability can be obtained.
  • the polyol composition used in the present invention contains a resin (polyol) having substantially two or more hydroxyl groups, preferably the above-mentioned polyester polyol (A). If necessary, other components such as low molecular weight alcohol, organic solvent, viscosity modifier, silane coupling agent, defoaming agent, tackifier and the like may be contained.
  • examples include propyl, castor oil, polyethylene glycol, polypropylene glycol and the like.
  • organic solvent examples include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluene, xylol, n-hexane and cyclohexane.
  • MEK methyl ethyl ketone
  • viscosity modifiers examples include dimethyl phthalate, dibutyl phthalate, dimethoxyethyl phthalate, dioctyl phthalate, diphenyl phthalate, triacetin, propyl dicaprylate, propylene carbonate and the like.
  • silane coupling agent examples include ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) - ⁇ -Aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, and other aminosilanes; ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -gly Epoxy silanes such as cidoxypropyltriethoxysilane and glycidoxyoctyltrimethoxysilane; vinyltris ( ⁇ -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrie
  • dimethylpolysiloxane a part of the methyl group of dimethylpolysiloxane is a carbinol group, a polyether group, or a carbon atom number of 2 or more.
  • examples thereof include a silicone-based defoaming agent modified with an alkyl group, an epoxy group, an amino group, a long-chain alcohol such as octyl alcohol, and a sorbitan derivative such as sorbitan monooleate.
  • tackifier examples include rosin-based or rosin ester-based tackifiers, terpene-based or terpene-phenol-based tackifiers, saturated hydrocarbon resins, coumarone-based tackifiers, coumarone-indene-based tackifiers, and styrene resin-based tackifiers.
  • tackifiers examples include tackifiers, xylene resin-based tackifiers, phenol resin-based tackifiers, petroleum resin-based tackifiers, and the like. These may be used alone or in combination of two or more.
  • the polyisocyanate composition of the present invention is one component of a two-component adhesive used with a polyol composition, and contains the polyester polyisocyanate (B) of the present invention as an essential component.
  • the polyester polyisocyanate (B) and the polyisocyanate composition of the present invention will be described in detail.
  • the polyester polyisocyanate (B) of the present invention is used as one component of a polyisocyanate composition of an adhesive containing a polyol composition and a polyisocyanate composition, and a polyvalent carboxylic acid or its derivative (IB) ) And a polycondensate of a polyhydric alcohol (II-B), and a polyester polyisocyanate (B) which is a reaction product of an isocyanate compound.
  • the polyester polyisocyanate (B) has two or more isocyanate groups in one molecule.
  • the polyvalent carboxylic acid or its derivative (IB) includes an aliphatic polycarboxylic acid or its derivative (IBi) having a carbon atom number of 8 or less in a portion excluding a carboxyl group, and an aromatic polycarboxylic acid. Acid or a derivative thereof (IB-ii), and the polyhydric alcohol (II-B) includes an aliphatic polyhydric alcohol (II-Bi) having 8 or less carbon atoms.
  • an aliphatic polycarboxylic acid having 8 or less carbon atoms in the portion excluding a carboxyl group or a derivative thereof is also referred to as a polycarboxylic acid (IBi), which is an aromatic polycarboxylic acid.
  • a carboxylic acid or its derivative (IB-ii) is also called a polycarboxylic acid (IB-ii)
  • an aliphatic polyhydric alcohol (II-Bi) having 8 or less carbon atoms is polyvalent. Also referred to as alcohol (II-Bi).
  • Polyvalent carboxylic acid or its derivative (IB) As the polyvalent carboxylic acids (IBi) used for the synthesis of the polyester polyisocyanate (B) of the present invention, conventionally known ones can be used without particular limitation. Specifically, the same as those exemplified as the polycarboxylic acid (IAi) can be used, and they can be used alone or in combination of two or more kinds.
  • Polycarboxylic acids (IB-ii)) As the polyvalent carboxylic acids (IB-ii) used in the synthesis of the polyester polyisocyanate (B) of the present invention, conventionally known ones can be used without particular limitation. Specifically, the same ones as exemplified as the polyvalent carboxylic acids (IA-ii) can be used, and they can be used alone or in combination of two or more kinds.
  • orthophthalic acid terephthalic acid, isophthalic acid, and their anhydrides
  • orthophthalic acid or orthophthalic anhydride it is more preferable to use orthophthalic acid or orthophthalic anhydride in order to improve the gas barrier property and the adhesive property of the adhesive described later. ..
  • the reason why the gas barrier property of the adhesive is excellent by using orthophthalic acid or orthophthalic anhydride is that the rotation of the polyester chain obtained by using orthophthalic acid or its anhydride is suppressed.
  • the reason why the adhesiveness is excellent is that the polyester chain is asymmetric and thus exhibits non-crystallinity, and sufficient base material adhesion is imparted.
  • polyvalent carboxylic acids (IB-iii) The polyvalent carboxylic acid or its derivative (IB) used for the synthesis of the polyester polyisocyanate (B) of the present invention is a polyvalent carboxylic acid (IBi) or a polyvalent carboxylic acid (IBi). Other than the above), polyvalent carboxylic acids (IB-iii) may be contained. Examples of the polyvalent carboxylic acids (IB-iii) include polyvalent carboxylic acids having more than 8 carbon atoms excluding the carboxyl group, such as dodecanedicarboxylic acid, which may be used alone or in combination of two or more kinds. it can.
  • the polyvalent carboxylic acid (IB-iii) is used in combination, it is preferably kept at 10% by mass or less, more preferably 5% by mass or less, based on the total amount of the polyvalent carboxylic acid or its derivative (IB). ..
  • the blending ratio of the polycarboxylic acid (IBi) and the polycarboxylic acid (IBi) may be appropriately adjusted according to the required gas barrier property and flex resistance.
  • the compounding ratio (molar ratio) of the polycarboxylic acid (IBi) and the polycarboxylic acid (IB-ii) is, for example, 1: 9 to 9: 1, and more preferably 2: 8 to 8: 2.
  • polyhydric alcohol (II-B) (Polyhydric alcohol (II-Bi))
  • polyhydric alcohol (II-Bi) As the polyhydric alcohol (II-Bi) used in the synthesis of the polyester polyisocyanate (B) of the present invention, conventionally known ones can be used without particular limitation. Specifically, the same as those exemplified as the polyhydric alcohol (II-Ai) can be used, and they can be used alone or in combination of two or more kinds. Among them, ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol and the like are preferable.
  • the polyhydric alcohol (II-B-ii) used in the synthesis of the polyester polyisocyanate (B) of the present invention contains a polyhydric alcohol (II-B-ii) other than the polyhydric alcohol (II-Bi). Good.
  • the polyhydric alcohol (II-B-ii) is used in combination, it is preferably 10% by mass or less, and more preferably 5% by mass or less of the total amount of the polyhydric alcohol (II-B).
  • isocyanate compound As the isocyanate compound used in the synthesis of the polyester polyisocyanate (B) of the present invention, known compounds can be used without particular limitation, and examples thereof include butane-1,4-diisocyanate, hexamethylene diisocyanate and 2,2,4-trimethyl. Aliphatic diisocyanates such as hexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate;
  • Cyclohexane-1,4-diisocyanate isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexanediisocyanate, isopropylidenedicyclohexyl-4,4′-diisocyanate, Alicyclic diisocyanates such as norbornane diisocyanate;
  • aromatic diisocyanate examples include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and tolylene diisocyanate.
  • oligomers of these diisocyanates may be used.
  • an isocyanate compound having an aromatic ring in the molecule it has excellent gas barrier properties and adhesiveness.
  • the isocyanate compound having an aromatic ring in the molecule conventionally known compounds can be used without particular limitation. Specifically, xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 1 Isocyanate monomers such as 1,5-naphthalene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, and tetramethyl xylene diisocyanate, compounds obtained by modifying a part of the isocyanate groups of these isocyanate monomers with carbodiimide, oligomers, and allophanate compounds, Nu
  • Examples of the compound having two or more active hydrogen groups include trimethylolpropane, glycerol, erythritol, pentaerythritol, sorbitol, diethanolamine, triethanolamine, and alkylene oxide adducts of these compounds.
  • At least one selected from the group consisting of xylylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate is preferable.
  • the proportion of the isocyanate compound having an aromatic ring is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass with respect to the total amount of the isocyanate compound used in the synthesis of the polyester polyisocyanate (B). It is more preferable that the above is satisfied.
  • the entire amount of the isocyanate compound used for the synthesis of the polyester polyisocyanate (B) may be an isocyanate compound having an aromatic ring.
  • the polyester which is an intermediate of the polyester polyisocyanate (B), is obtained by reacting the above-mentioned polyvalent carboxylic acid or its derivative (IB) with the polyhydric alcohol (II-B).
  • the intermediate polyester of polyester polyisocyanate (B) is preferably linear.
  • the intermediate polyester of the polyester polyisocyanate (B) is linear, that is, the raw material of the polyester polyol (polyhydric carboxylic acid or its derivative (II-A) or polyhydric alcohol (II-B). )) All consist of compounds with two reactive groups.
  • the polyhydric alcohol (II-B) a polyester polyol prepared by using a bifunctional alcohol having a branched alkyl group such as neopentyl glycol is included in a linear form. This makes it possible to suppress an increase in the viscosity of the final product, polyester polyisocyanate, and to provide an adhesive with excellent coatability.
  • polyester polyisocyanate (B) The polyester polyisocyanate (B) of the present invention is a polycondensation product of the above-mentioned polyvalent carboxylic acid or its derivative (IB) and polyhydric alcohol (II-B) with an isocyanate compound at the end. Obtained by reacting.
  • the polyisocyanate composition of the present invention contains the above-mentioned polyester polyisocyanate (B) as an essential component. Further, an isocyanate compound other than the polyester polyisocyanate (B) may be contained within a range not impairing the effects of the present invention.
  • isocyanate compound other than the polyester polyisocyanate (B) examples include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and xylyl.
  • Aliphatic diisocyanates such as diisocyanate and m-tetramethylxylylene diisocyanate;
  • Cyclohexane-1,4-diisocyanate isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, isopropylidenedicyclohexyl-4,4'-diisocyanate, Alicyclic diisocyanates such as norbornane diisocyanate;
  • aromatic diisocyanate examples include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate and tolylene diisocyanate.
  • oligomers of these diisocyanates may be used.
  • the content of the polyester polyisocyanate (B) is preferably 50% by mass or more based on the total amount thereof, and 60 It is preferably at least mass%.
  • an isocyanate compound other than the polyester polyisocyanate (B) is used, a polyisocyanate having an aromatic ring, more preferably xylylene diisocyanate, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane It is preferable to use at least one selected from the group consisting of diisocyanates.
  • the isocyanate compound other than the polyester polyisocyanate (B) the isocyanate compound remaining without reacting with the intermediate polyester may be used as it is when the polyester polyisocyanate (B) is adjusted, or the polyisocyanate composition is adjusted. You may add it at the time.
  • the polyisocyanate composition may further contain an organic solvent and a viscosity modifier.
  • the same organic solvent and viscosity modifier as those used for the polyol composition can be used.
  • Adhesive is a two-component adhesive containing a polyol composition and the polyisocyanate composition of the present invention, and is suitable for film laminating applications. Further, the adhesive of the present invention may be used in either a solvent type or a solventless type.
  • the solvent-type adhesive is a method of applying an adhesive to a base material, heating it in an oven or the like to volatilize the organic solvent in the coating film, and then bonding it to another base material, so-called dry It refers to the form used in the laminating method.
  • Either one or both of the polyol composition and the polyisocyanate composition contains the above-mentioned organic solvent.
  • the solvent used as a reaction medium during the production of the constituents of the polyol composition or the polyisocyanate composition may be used as a diluent during coating.
  • the solventless adhesive is used in a so-called non-solvent laminating method in which an adhesive is applied to a base material and then bonded to another base material without passing through a step of heating in an oven or the like to volatilize the solvent. It is a form that can be used.
  • the polyol composition nor the polyisocyanate composition is substantially free of the above-mentioned organic solvent. Constituent components of the polyol composition or polyisocyanate composition, or the organic solvent used as the reaction medium during the production of the raw material cannot be completely removed, and a trace amount of the organic solvent remains in the polyol composition or the polyisocyanate composition. If so, it is understood to be substantially free of organic solvents.
  • the polyol composition contains a low molecular weight alcohol
  • the low molecular weight alcohol reacts with the isocyanate composition to form a part of the coating film, and therefore it is not necessary to volatilize it after coating. Therefore, such a form is also treated as a solventless adhesive.
  • the adhesive of the present invention is used by mixing a polyol composition and a polyisocyanate composition immediately before coating on a substrate.
  • the polyol composition and the polyisocyanate composition are blended so that the equivalent ratio [NCO] / [OH] of the hydroxyl group contained in the polyol composition and the isocyanate group contained in the polyisocyanate composition is 0.5 to 4.
  • [NCO] / [OH] exceeds 4
  • excess isocyanate groups may bleed out from the cured coating film of the adhesive, and if it is less than 0.5, adhesive strength may be insufficient.
  • the adhesive of the present invention is an inorganic filler such as silica, alumina, aluminum flakes, glass flakes, a coupling agent such as a silane coupling agent or a titanium coupling agent, an antioxidant, a heat stabilizer, an ultraviolet absorber, an electrostatic charge. It may contain various additives such as an inhibitor, a lubricant, an antiblocking agent, a coloring agent, and a crystal nucleating agent.
  • various thermoplastic resins such as acrylic resin, ketone resin, epoxy resin and polyester resin may be blended. These various additives and thermoplastic resins may be added in advance to either one or both of the polyol composition and the polyisocyanate composition, or when mixing the polyol composition and the polyisocyanate composition. You may add.
  • the laminated body of the present invention can be obtained, for example, by laminating a plurality of films using the adhesive of the present invention by a dry laminating method or a non-solvent laminating method.
  • the laminated laminate has excellent gas barrier properties and can be used as a gas barrier laminate.
  • the film to be used is not particularly limited, and a film suitable for the application can be selected appropriately.
  • a film suitable for the application can be selected appropriately.
  • PET polyethylene terephthalate
  • polystyrene film polyamide film, polyacrylonitrile film
  • polyethylene film LLDPE: low density polyethylene film
  • HDPE high density polyethylene film
  • CPP unstretched
  • examples thereof include polypropylene films, polyolefin films such as OPP: biaxially oriented polypropylene film), polyvinyl alcohol films, ethylene-vinyl alcohol copolymer films, and the like.
  • the film may be stretched.
  • a stretching treatment method a resin is melt-extruded by an extrusion film-forming method or the like to form a sheet, and then simultaneous biaxial stretching or sequential biaxial stretching is performed.
  • sequential biaxial stretching it is general to first carry out a longitudinal stretching treatment and then a transverse stretching. Specifically, a method of combining longitudinal stretching using a speed difference between rolls and lateral stretching using a tenter is often used.
  • a barrier film containing a metal such as aluminum, a vapor-deposited layer of a metal oxide such as silica or alumina, a polyvinyl alcohol, an ethylene / vinyl alcohol copolymer, a gas barrier layer such as vinylidene chloride is used together. Good.
  • a laminate having a barrier property against water vapor, oxygen, alcohol, inert gas, volatile organic substances (fragrance), and the like can be obtained.
  • various surface treatments such as flame treatment and corona discharge treatment may be performed on the film surface so that an adhesive layer without defects such as film breakage and cissing is formed.
  • the laminate of the present invention can be obtained by applying the adhesive of the present invention as an adhesion aid (anchor coating agent) to a film by a laminator, carrying out a curing reaction, and then laminating a polymer material melted by an extruder. Can be obtained (extrusion lamination method).
  • the film the same films as those used in the dry laminating method and the non-solvent laminating method described above can be used.
  • a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin or an ethylene-vinyl acetate copolymer resin is preferable.
  • Substrate film 1 / adhesive layer 1 / sealant film (2) Substrate film 1 / adhesive layer 1 / metal-deposited unstretched film (3) Substrate film 1 / adhesive layer 1 / metal-deposited stretched film (4) Transparent vapor-deposited stretched film / adhesive layer 1 / sealant film (5) substrate film 1 / adhesive layer 1 / substrate film 2 / adhesive layer 2 / sealant film (6) substrate film 1 / adhesive layer 1 / metal vapor-deposited stretched film / Adhesive layer 2 / Sealant film (7) Substrate film 1 / Adhesive layer 1 / Transparent vapor deposition stretched film / Adhesive layer 2 / Sealant film (8) Substrate film 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Sealant Film (9) Substrate film 1 / Adhesive layer 1 / Substrate film 2 / Adhesive layer 2 / Metal layer
  • the base film 1 used in the configuration (1) OPP film, PET film, nylon film and the like can be mentioned. Further, as the base film 1, a film coated for the purpose of improving gas barrier properties and ink receptivity when a printing layer described later is provided may be used. Examples of commercially available coated base film 1 include K-OPP film and K-PET film.
  • the adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include CPP film and LLDPE film.
  • a print layer may be provided on the surface of the base film 1 on the adhesive layer 1 side (when the coated base film 1 is used, the surface of the coating layer on the adhesive layer 1 side).
  • the printing layer is formed by various printing inks such as gravure ink, flexographic ink, offset ink, stencil ink, and inkjet ink, which are generally used for printing on polymer films.
  • the adhesive layer 1 is a cured coating film of the adhesive of the present invention.
  • the metal vapor-deposited unstretched film use a VM-CPP film obtained by vapor-depositing a metal such as aluminum on a CPP film, and use the VM-OPP film obtained by vapor-depositing a metal such as aluminum on an OPP film as the metal vapor-deposited stretched film.
  • a printing layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1 in the same manner as the configuration (1).
  • the transparent vapor-deposited stretched film used in the constitution (4) includes a film obtained by vapor-depositing silica or alumina on an OPP film, a PET film, a nylon film or the like.
  • a film coated on the vapor deposition layer may be used.
  • the adhesive layer 1 is a cured coating film of the adhesive of the present invention.
  • the sealant film the same one as the constitution (1) can be mentioned.
  • a printing layer may be provided on the surface of the transparent vapor-deposited stretched film on the side of the adhesive layer 1 (the surface of the coating layer on the side of the adhesive layer 1 when a coating is applied on the inorganic vapor-deposited layer).
  • the method of forming the print layer is the same as that of the configuration (1).
  • the base film 1 used in the configuration (5) a PET film and the like can be mentioned.
  • the base film 2 include a nylon film and the like.
  • At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention.
  • the sealant film the same one as the constitution (1) can be mentioned.
  • a printing layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1 in the same manner as the configuration (1).
  • the base film 1 having the configuration (6) the same ones as the configurations (2) and (3) can be mentioned.
  • the metal vapor deposition stretched film include a VM-OPP film and a VM-PET film obtained by vapor deposition of a metal such as aluminum on an OPP film or PET film.
  • At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention.
  • the sealant film the same one as the constitution (1) can be mentioned.
  • a printing layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1 in the same manner as the configuration (1).
  • the base film 1 having the configuration (7) a PET film or the like can be used.
  • the transparent vapor-deposited stretched film the same as the constitution (4) can be mentioned.
  • At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention.
  • the sealant film the same one as the constitution (1) can be mentioned.
  • a printing layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1 in the same manner as the configuration (1).
  • the base film 1 having the structure (8) a PET film or the like can be used.
  • Aluminum foil etc. are mentioned as a metal layer.
  • At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention.
  • As the sealant film the same one as the constitution (1) can be mentioned.
  • a printing layer may be provided on the surface of the base film 1 on the side of the adhesive layer 1 in the same manner as the configuration (1).
  • Examples of the base film 1 having the configurations (9) and (10) include PET films.
  • Examples of the base film 2 include a nylon film and the like. Aluminum foil etc. are mentioned as a metal layer.
  • At least one layer of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention.
  • As the sealant film the same one as the constitution (1) can be mentioned.
  • a printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as the configuration (1).
  • the laminate of the present invention includes at least one of a metal vapor deposition film, a transparent vapor deposition film, and a metal layer
  • the metal vapor deposition layer, the transparent vapor deposition layer, the adhesive layer in contact with the metal layer is a cured coating film of the adhesive of the present invention. Is preferred.
  • the adhesive of the present invention is a solvent type
  • the adhesive of the present invention is applied to a film material serving as a substrate using a roll such as a gravure roll, and after evaporating the organic solvent by heating in an oven or the like, The other base material is attached to obtain the laminate of the present invention.
  • aging treatment is preferably performed.
  • the aging temperature is preferably room temperature to 80 ° C.
  • the aging time is preferably 12 to 240 hours.
  • the adhesive of the present invention is a solventless type
  • the adhesive of the present invention after applying the adhesive of the present invention which has been heated to about 40 ° C to 100 ° C in advance to a film material as a base material using a roll such as a gravure roll Immediately, the other base material is attached to obtain the laminate of the present invention.
  • aging treatment is preferably performed.
  • the aging temperature is preferably room temperature to 70 ° C.
  • the aging time is preferably 6 to 240 hours.
  • the adhesive auxiliary of the present invention is applied to a film material as a base material by using a roll such as a gravure roll and the organic solvent is volatilized by heating in an oven or the like. Then, the polymer material melted by an extruder is laminated to obtain the laminate of the present invention.
  • the amount of adhesive applied is adjusted appropriately.
  • the solid content is adjusted to 1 g / m 2 or more and 10 g / m 2 or less, preferably 1 g / m 2 or more and 5 g / m 2 or less.
  • the amount of the adhesive applied is, for example, 1 g / m 2 or more and 10 g / m 2 or less, preferably 1 g / m 2 or more and 5 g / m 2 or less.
  • the coating amount is, for example, 0.03 g / m 2 or more and 0.09 g / m 2 or less (solid content).
  • the laminated body of the present invention may further include other films and base materials in addition to the above-mentioned constitutions (1) to (10).
  • the other base material in addition to the above-mentioned stretched film, unstretched film and transparent vapor deposition film, a porous base material such as paper, wood and leather can be used.
  • the adhesive used for laminating other base materials may or may not be the adhesive of the present invention.
  • the laminate of the present invention can be used as a multilayer packaging material for protecting foods, pharmaceuticals and the like. When it is used as a multi-layer packaging material, its layer structure may change depending on the contents, environment of use, and form of use.
  • the packaging material of the present invention is obtained by using the laminate of the present invention, stacking the surfaces of the sealant films of the laminate so as to face each other, and then heat-sealing the peripheral edges thereof.
  • the laminate of the present invention is folded, or the surfaces of the inner layers of the laminate are opposed to each other (the surface of the sealant film), and the peripheral edges thereof are, for example, a side seal type, a two-side seal type.
  • Examples include heat sealing methods such as three-sided seal type, four-sided seal type, envelope-attached seal type, joint-sealed seal type, pleated seal type, flat bottom seal type, square bottom seal type, gusset type, and other heat seal types. Be done.
  • the packaging material of the present invention can take various forms depending on the contents, the use environment, and the use form. Self-supporting packaging materials (standing pouches) are also possible.
  • As the heat sealing method known methods such as bar sealing, rotating roll sealing, belt sealing, impulse sealing, high frequency sealing, and ultrasonic sealing can be used.
  • the opening After filling the packaging material of the present invention with the contents from the opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention.
  • the contents to be filled include rice cakes, bean cakes, nuts, biscuits and cookies, wafer cakes, confectionery such as marshmallows, pies, half-cakes, candy, snacks, bread, snack noodles, instant noodles, dried noodles, pasta.
  • Aseptic packed rice, elephant, rice porridge, rice cake, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, nameko mushrooms, konjac, processed wild vegetables, jams, peanut cream, salads, frozen Vegetables, processed agricultural products such as potato products, hams, bacon, sausages, processed chicken products, livestock processed products such as corned beef, fish ham and sausages, fish paste products, kamaboko, paste, boiled fish, bonito, salted fish, Smoked salmon, seafood products such as mentaiko, peach, mandarin orange, pineapple, apple, pear, Cooking flesh such as cherries, corn, asparagus, mushrooms, onions, carrots, vegetables such as radish and potatoes, hamburger, meatballs, fried seafood, gyoza, croquette, etc.
  • the packaging material of the present invention can be used as a packaging material for medicines such as cigarettes, disposable body warmers, infusion packs, cosmetics, and vacuum heat insulating materials.
  • Polyol composition A1 A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser was charged with 80.12 parts of ethylene glycol, 148.12 parts of phthalic anhydride, and 0.02 part of titanium tetraisopropoxide, and a rectification tube. The inner temperature was maintained at 220 ° C by gradually heating so that the upper temperature did not exceed 100 ° C. When the acid value was 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of 900.
  • the hydroxyl value was 124.7 mgKOH / g, and the glass transition temperature was 10 ° C or lower. Further, while heating to 60 ° C., 310.13 parts of ethyl acetate was added as a diluting solvent and stirred for 1 hour to obtain a polyol composition A1.
  • Polyol composition A2 A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser was charged with 100.12 parts of ethylene glycol, 148.12 parts of phthalic anhydride, and 0.02 part of titanium tetraisopropoxide, and a rectification tube. The inner temperature was maintained at 220 ° C by gradually heating so that the upper temperature did not exceed 100 ° C. When the acid value was 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of 400. The hydroxyl value was 280.5 mgKOH / g, and the glass transition temperature was 10 ° C or lower. The obtained polyester polyol was used as a polyol composition A2.
  • Polyol composition A3 In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser, 79.10 parts of ethylene glycol, 74.06 parts of phthalic anhydride, 73.07 parts of adipic acid and 0.01 parts of titanium tetraisopropoxide were placed. Was charged and gradually heated so that the upper temperature of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C. When the acid value was 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester polyol having a number average molecular weight of 800. The hydroxyl value was 143.2 mgKOH / g, and the glass transition temperature was 10 ° C or lower. The obtained polyester polyol was used as a polyol composition A3.
  • Polyol composition A4 A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser was charged with 91.05 parts of diethylene glycol, 34.65 parts of 2-methyl-1,3-propanediol, 143.67 parts of adipic acid, and trimethylolproban. 15.79 parts and 0.01 parts of titanium tetraisopropoxide were charged and gradually heated so that the upper temperature of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C.
  • polyester polyol having a number average molecular weight of 750.
  • the hydroxyl value was 185.1 mgKOH / g, and the glass transition temperature was 10 ° C or lower.
  • the obtained polyester polyol was used as a polyol composition A4.
  • Polyisocyanate composition B1 A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser was charged with 92.00 parts of ethylene glycol, 118.50 parts of phthalic anhydride, 29.23 parts of adipic acid and 0.01 parts of titanium tetraisopropoxide. was charged and gradually heated so that the upper temperature of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester intermediate B1 ′ having a number average molecular weight of 500.
  • Polyisocyanate composition B2 In a polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser, 79.27 parts of ethylene glycol, 59.25 parts of phthalic anhydride, 87.68 parts of adipic acid and 0.02 part of titanium tetraisopropoxide were placed. Was charged and gradually heated so that the upper temperature of the rectification tube did not exceed 100 ° C. to maintain the internal temperature at 220 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester intermediate B2 ′ having a number average molecular weight of 850.
  • xylylene diisocyanate a mixture of xylylene diisocyanate (4,4'-diphenylmethane diisocyanate and 2,4'-diphenylmethane diisocyanate) was placed in a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snyder tube, a cooling condenser and a dropping funnel.
  • 30.61 parts was added and stirred while heating to 70 ° C.
  • polyester intermediate B2′100.33 parts was added dropwise using a dropping funnel over 2 hours, and further stirred for 4 hours to obtain a polyisocyanate composition.
  • B2 was obtained.
  • the NCO% measured according to JIS-K1603 was 15.4%.
  • Polyisocyanate composition B3 A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser was charged with 100.12 parts of ethylene glycol, 148.12 parts of phthalic anhydride, and 0.02 part of titanium tetraisopropoxide, and a rectification tube. The inner temperature was maintained at 220 ° C by gradually heating so that the upper temperature did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester intermediate B3 ′ having a number average molecular weight of 400.
  • Polyisocyanate composition B4 A polyester reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snider tube, and a condenser was charged with 48.16 parts of ethylene glycol, 62.98 parts of 2-methyl-1,3-propanediol, and 129.69 parts of adipic acid. The inner temperature was maintained at 220 ° C by gradually heating so that the upper temperature of the rectification tube did not exceed 100 ° C. When the acid value became 1 mgKOH / g or less, the esterification reaction was terminated to obtain a polyester intermediate B4 ′ having a number average molecular weight of 600.
  • luplanate MI a mixture of 4,4′-diphenylmethane diisocyanate and 2,4′-diphenylmethane diisocyanate
  • a reaction vessel equipped with a stirrer, a nitrogen gas introduction tube, a snyder tube, a cooling condenser, and a dropping funnel.
  • polyester intermediate B4′81.63 parts was added dropwise using a dropping funnel over 2 hours, and further stirred for 4 hours to obtain polyisocyanate composition B4.
  • the NCO% measured according to JIS-K1603 was 14.5%.
  • Example 1 Using the bar coater, the adhesive surface of Example 1 was printed on a printed surface of an OPP film (“P2161” manufactured by Toyobo Co., Ltd.) having a thickness of 20 ⁇ m so that the coating amount was 3.0 g / m 2 (solid content). It was applied to and dried by evaporating the diluting solvent with a dryer set at a temperature of 70 ° C. Next, the adhesive surface of the OPP film coated with the adhesive was bonded to the vapor deposition surface of a 25 ⁇ m thick aluminum vapor-deposited CPP film (“2203” manufactured by Toray Film Machinery Co., Ltd.). Aging was performed at 40 ° C. for 2 days to obtain the laminated body of Example 1.
  • OPP film P2161” manufactured by Toyobo Co., Ltd.
  • Example 2 (Comparative Example 1), (Comparative Example 2) Laminated bodies of Example 2 and Comparative Examples 1 and 2 were obtained in the same manner as in Example 1 except that the adhesive was changed.
  • Example 3 The adhesive of Example 3 was heated to about 70 ° C., and a 20 ⁇ m thick OPP film (“P2161” manufactured by Toyobo Co., Ltd.) was coated with a solvent-free test coater to give a coating amount of 2.0 g / m 2 (solid content) was applied, and then the vapor-deposited surface of an aluminum vapor-deposited CPP film (“2203” manufactured by Toray Film Machinery Co., Ltd.) having a thickness of 25 ⁇ m was attached to the adhesive-coated surface. Aging was performed at 40 ° C. for 2 days to obtain a laminate of Example 3.
  • OPP film P2161” manufactured by Toyobo Co., Ltd.
  • a solvent-free test coater to give a coating amount of 2.0 g / m 2 (solid content) was applied, and then the vapor-deposited surface of an aluminum vapor-deposited CPP film (“2203” manufactured by Toray Film Machinery Co., Ltd.) having a thickness of 25 ⁇ m was attached to the adhesive
  • Example 4 (Example 4)-(Example 8), (Comparative Example 3)-(Comparative Example 8) Laminates of Examples 4-8 and Comparative Examples 3-8 were obtained in the same manner as in Example 3 except that the adhesive was changed.
  • Example 9 The adhesive of Example 9 was heated to about 70 ° C., and a coating amount was applied to the vapor-deposited surface of a 25 ⁇ m-thick aluminum vapor-deposited CPP film (“2203” manufactured by Toray Film Processing Co., Ltd.) using a solventless test coater. It was applied so as to have a concentration of 2.0 g / m 2 (solid content), and then the printing surface of a PET film having a thickness of 12 ⁇ m (“P5102” manufactured by Toyobo Co., Ltd.) and the application surface of the adhesive were bonded together. Aging was performed at 40 ° C. for 2 days to obtain a laminate of Example 9.
  • a coating amount was applied to the vapor-deposited surface of a 25 ⁇ m-thick aluminum vapor-deposited CPP film (“2203” manufactured by Toray Film Processing Co., Ltd.) using a solventless test coater. It was applied so as to have a concentration of 2.0 g / m 2 (solid content), and then the printing surface of
  • the laminate obtained using the adhesive of the present invention has excellent gas barrier properties and flex resistance.
  • the laminate obtained by using the adhesive of Comparative Example could not satisfy both the gas barrier property and the flex resistance at a level satisfying both.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Wrappers (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne un film stratifié de barrière aux gaz et un matériau d'emballage qui sont un film transparent utilisable en tant que film barrière transparent pour des matériaux d'emballage principalement pour des aliments, et des matériaux électroniques pour des cellules solaires, des éléments d'affichage, etc., et qui ont une excellente fonction de barrière aux gaz et sont résistants à la flexion. Le présent polyisocyanate de polyester (B) est un produit de réaction d'un polyester qui est un produit de polycondensation d'un acide polycarboxylique ou d'un dérivé de celui-ci (I-B) et d'un alcool polyhydrique (II-B), avec un composé isocyanate, l'acide polycarboxylique ou un dérivé de celui-ci (I-B) contient un acide polycarboxylique aliphatique ayant huit atomes de carbone ou moins au niveau d'une partie à l'exclusion d'un groupe carboxyle, ou un dérivé de celui-ci (I-B-i), et un acide polycarboxylique aromatique ou un dérivé de celui-ci (I-B-ii), et l'alcool polyhydrique (II-B) contient un alcool polyhydrique aliphatique (II-B-i) ayant huit atomes de carbone ou moins.
PCT/JP2019/042286 2018-11-06 2019-10-29 Polyisocyanate de polyester, composition de polyisocyanate de polyester, adhésif, produit stratifié, et matériau d'emballage Ceased WO2020095751A1 (fr)

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JP2020544301A JP6801828B2 (ja) 2018-11-06 2019-10-29 ポリエステルポリイソシアネート、ポリエステルポリイソシアネート組成物、接着剤、積層体、包装材
CN201980071853.5A CN112969583B (zh) 2018-11-06 2019-10-29 聚酯多异氰酸酯、聚酯多异氰酸酯组合物、粘接剂、层叠体、包装材料

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JP2022075483A (ja) * 2020-11-04 2022-05-18 斎藤塗料株式会社 ポリウレタン樹脂組成物
US12319035B2 (en) 2022-02-14 2025-06-03 Toppan Holdings Inc. Laminated film and packaging bag

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Publication number Priority date Publication date Assignee Title
JP2022075483A (ja) * 2020-11-04 2022-05-18 斎藤塗料株式会社 ポリウレタン樹脂組成物
JP7742096B2 (ja) 2020-11-04 2025-09-19 斎藤塗料株式会社 ポリウレタン樹脂組成物
US12319035B2 (en) 2022-02-14 2025-06-03 Toppan Holdings Inc. Laminated film and packaging bag

Also Published As

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JPWO2020095751A1 (ja) 2021-02-15
JP6801828B2 (ja) 2020-12-16
CN112969583A (zh) 2021-06-15
CN112969583B (zh) 2023-04-07

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