WO2022172841A1 - 二液硬化型接着剤、積層フィルム、積層フィルム製造装置、積層フィルムの製造方法 - Google Patents

二液硬化型接着剤、積層フィルム、積層フィルム製造装置、積層フィルムの製造方法 Download PDF

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WO2022172841A1
WO2022172841A1 PCT/JP2022/004166 JP2022004166W WO2022172841A1 WO 2022172841 A1 WO2022172841 A1 WO 2022172841A1 JP 2022004166 W JP2022004166 W JP 2022004166W WO 2022172841 A1 WO2022172841 A1 WO 2022172841A1
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Prior art keywords
film
polyol
polyisocyanate
composition
laminated film
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PCT/JP2022/004166
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English (en)
French (fr)
Japanese (ja)
Inventor
健二 中村
厚美 佐野
智雄 大久保
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • 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
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition

Definitions

  • the present invention relates to a two-component curing adhesive, a laminated film, a laminated film manufacturing apparatus, and a laminated film manufacturing method.
  • a laminate film in which two films are bonded together using an adhesive, and a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition is used as the adhesive.
  • a method for producing a laminated film using a two-component curing adhesive there are a method having a two-component mixed coating process that has been used for a long time and a method having a two-component separate coating process that has been attracting attention in recent years.
  • the polyisocyanate composition and the polyol composition are mixed to form a mixed liquid, and the two-liquid mixing coating step of applying this on the film, and the coating film formed on the film. and a step of forming an adhesive layer in which another film is laminated and cured.
  • a two-component separated coating comprising a first coating step of coating the polyisocyanate composition on the first film and a second coating step of coating the polyol composition on the second film.
  • Patent Documents 1 to 3 disclose solvent-free agent A that is liquid at room temperature applied to one adherend and solvent-free agent B that is liquid at room temperature and applied to the other adherend.
  • a two-part split-coat adhesive is described that initiates a curing reaction when it comes into contact with the adhesive.
  • the above agent A is mainly composed of a compound having an isocyanate group at both ends of the molecule
  • the above agent B is a compound having an amino group at both ends of the molecule and a compound having a tertiary amine in the molecule. and a tackifying resin are described.
  • the A agent is mainly composed of a compound having an isocyanate group at both molecular ends
  • the B agent is a two-component separate application type mainly composed of a compound having an amino group at both molecular ends.
  • a urethane adhesive is described.
  • the A agent is mainly composed of a compound having an isocyanate group at both ends of the molecule
  • the B agent is a two-liquid separate application type urethane system mainly composed of a compound having a hydroxyl group in the molecule. Adhesives are mentioned.
  • a laminated film in which an adhesive layer is formed between a first film and a second film using a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition Alternatively, the laminated film and another film are often heat-sealed (melt-adhered). For example, by heat-sealing the ends of the laminated film to form a bag, it can be used as a packaging material for foods and daily necessities (detergents, medicines, etc.). Such packaging materials are required to exhibit high bonding strength by heat sealing so as to maintain excellent bag-making properties. However, there is still room for improvement in the heat seal strength of laminated films formed using conventional two-component curing adhesives.
  • the present invention has been made in view of the above circumstances, and provides a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, and uses the same to form a first film and a second film.
  • a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, and uses the same to form a first film and a second film.
  • a laminated film with good heat sealability is obtained, and a two-component curing adhesive with good reactivity between a polyisocyanate composition and a polyol composition is provided.
  • the present invention uses a two-component curable adhesive with good reactivity between a polyisocyanate composition and a polyol composition, can be efficiently manufactured with a small amount of energy, and can obtain excellent bonding strength by heat sealing.
  • An object of the present invention is to provide a laminated film having good heat sealability.
  • the present invention uses a two-component curable adhesive with good reactivity between a polyisocyanate composition and a polyol composition, and a production method having a two-component separate coating process to produce a laminated film with good heat sealability.
  • An object of the present invention is to provide a laminated film manufacturing apparatus that can be suitably used when manufacturing.
  • the present invention provides a laminated film that can efficiently produce a laminated film with good heat sealability with a small amount of energy by using a two-component curing adhesive that has good reactivity between a polyisocyanate composition and a polyol composition.
  • the object is to provide a manufacturing method.
  • the present inventors have developed a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition, in which the polyisocyanate composition and the polyol composition are heated at room temperature (25 ° C.).
  • room temperature 25 ° C.
  • a two-component curing adhesive having a shear viscosity or complex viscosity of 10 Pa s or more within 1 minute from the start of the curing reaction.
  • the two-component curing adhesive has good reactivity and can be efficiently cured with a small amount of energy, and the laminated film obtained using the two-component curing adhesive has excellent heat-sealing properties.
  • the present invention relates to the following matters.
  • the polyisocyanate composition (X) and the polyol composition (Y) are subjected to a curing reaction at 25° C., so that the shear viscosity or the complex viscosity becomes 10 Pa s or more within 1 minute from the start of the curing reaction.
  • Hardening adhesive
  • [2] having an adhesive layer between the first film and the second film; A laminated film, wherein the adhesive layer is a cured product of the two-component curing adhesive according to [1].
  • the two-component curable adhesive of the present invention is such that the polyisocyanate composition (X) and the polyol composition (Y) undergo a curing reaction at 25° C., and the shear viscosity or complex viscosity increases within 1 minute from the start of the curing reaction. 10 Pa ⁇ s or more. Therefore, the two-component curing adhesive of the present invention has good reactivity and can be efficiently cured with a small amount of energy.
  • the laminated film in which the adhesive layer is formed between the first film and the second film using the two-component curing adhesive of the present invention can obtain excellent bonding strength by heat sealing.
  • the laminated film of the present invention has an adhesive layer between the first film and the second film, and the adhesive layer is made of the cured two-component curable adhesive of the present invention. Therefore, the laminated film of the present invention can be produced efficiently with a small amount of energy by using the two-component curing adhesive of the present invention having good reactivity between the polyisocyanate composition (X) and the polyol composition (Y). can be manufactured. In addition, the laminate film has good heat-sealing properties, and excellent bonding strength can be obtained by heat-sealing.
  • the laminated film manufacturing apparatus of the present invention uses the two-component curing adhesive of the present invention, which has good reactivity between the polyisocyanate composition (X) and the polyol composition (Y), in a two-component separate application step. It can be suitably used when producing a laminated film having good heat-sealing properties by a production method having
  • the two-component curable adhesive of the present invention having good reactivity between the polyisocyanate composition (X) and the polyol composition (Y) is used to form the first film and the second film.
  • a laminated film is manufactured by laminating a film. Therefore, a laminated film having good heat-sealing properties can be produced efficiently with a small amount of energy.
  • FIG. 1 is a cross-sectional view showing an example of the laminated film according to this embodiment.
  • FIG. 2 is a front view of the laminated film manufacturing apparatus according to the present embodiment.
  • 3 is a front view showing a main part of a polyisocyanate coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • FIG. 4 is a front view showing a main part of a polyol coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • FIG. FIG. 5 is a front view for explaining another example of the manufacturing apparatus used for manufacturing the laminated film of this embodiment.
  • the two-component curable adhesive of the present embodiment is a two-component curable adhesive using a curing reaction between the polyisocyanate composition (X) and the polyol composition (Y).
  • the polyisocyanate composition (X) in the two-component curing adhesive of the present embodiment contains polyisocyanate (A).
  • Polyol composition (Y) contains polyol (B).
  • the polyisocyanate composition (X) may contain part of the polyol (B) contained in the two-component curing adhesive, if necessary.
  • the two-component curable adhesive of this embodiment cures through a chemical reaction between the isocyanate groups in the polyisocyanate composition (X) and the hydroxyl groups (or hydroxyl groups and amino groups) in the polyol composition (Y).
  • the two-component curable adhesive of the present embodiment is obtained by curing the polyisocyanate composition (X) and the polyol composition (Y) at 25° C., thereby reducing the shear viscosity or complex viscosity within 1 minute from the start of the curing reaction. is 10 Pa ⁇ s or more. Therefore, the two-component curing adhesive of the present embodiment has good reactivity and can be efficiently cured with a small amount of energy. Specifically, there is no need to heat the two-component curable adhesive in order to cure the two-component curable adhesive, so aging can be performed at room temperature (25° C.) and the aging time can be shortened.
  • the two-component curable adhesive of the present embodiment is used to form an adhesive layer between the first film and the second film, so that excellent bonding strength can be obtained by heat sealing. Can form films.
  • the shear viscosity or The complex viscosity is preferably 20 Pa s or more, more preferably 30 Pa s or more, still more preferably 40 Pa s or more, and particularly preferably 50 Pa s or more, Most preferably, it is 60 Pa ⁇ s or more.
  • the shear viscosity or complex viscosity within 1 minute from the start of the curing reaction is preferably 1000 Pa s or less, more preferably 200 Pa s or less. . This is because if the viscosity of the two-component curable adhesive rises sharply in a short period of time, diffusion of the adhesive component molecules is suppressed and a uniform adhesive coating film cannot be formed.
  • the curing reaction is usually initiated by mixing two components consisting of a main agent and a curing agent.
  • the viscosity of the adhesive increases as the curing reaction progresses until the adhesive finally cures.
  • the viscosity of the two-component curing adhesive increases with time after the curing reaction has started.
  • the viscosity of the two-component curing adhesive is measured continuously or at predetermined time intervals from the start of the curing reaction, and the predetermined shear viscosity or complex viscosity is reached within 1 minute from the start of the curing reaction. It is preferable to check
  • the numerical value of adhesive viscosity is usually expressed as the measured value of shear viscosity. However, if the curing speed of the adhesive is too fast, it may not be possible to measure the shear viscosity one minute after the initiation of the curing reaction. In that case, the complex viscosity measurement can be used as a numerical value for the viscosity of the adhesive. There is basically no difference in the numerical value of the viscosity of the adhesive, whether it is the shear viscosity or the complex viscosity.
  • the shear viscosity of the two-component curing adhesive was continuously measured at a shear rate of 10 s ⁇ 1 in accordance with JIS-Z8803 (2011) after the curing reaction started. Then, when the shear viscosity of the two-component curing adhesive during measurement exceeds 8 Pa s, the vibration measurement conforms to JIS-K7244-10 (2005), and the curing reaction is performed at an angular frequency of 10 / s. The complex viscosity of the two-component curable adhesive was measured 1 minute after the start.
  • the viscosity of the two-component curable adhesive that should transition from shear viscosity to complex viscosity can be, for example, within the range of 4 to 9 Pa ⁇ s, and is not limited to 8 Pa ⁇ s.
  • the viscosity of the two-component curable adhesive, which should be changed from shear viscosity to complex viscosity can be determined as appropriate, as long as the viscosity can be measured correctly, in consideration of the measuring device and the like to be used.
  • the shear viscosity or complex viscosity within 1 minute from the start of the curing reaction when the polyisocyanate composition (X) and the polyol composition (Y) are cured at 25° C. can be adjusted by adjusting the content of the curing accelerator. can be controlled by It should be noted that those skilled in the art can obtain the polyisocyanate composition (X) and the polyol composition (Y) based on known techniques within the scope of ordinary experiments by appropriately adjusting the content of the curing accelerator. When the curing reaction is performed at 25° C., the shear viscosity or complex viscosity within 1 minute from the start of the curing reaction is within the desired range.
  • Polyisocyanate (A) As the polyisocyanate (A), known ones can be used without particular limitation.
  • Examples of the polyisocyanate (A) include tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate may be simply referred to as "MDI"), 2,2'-MDI, 4,4'-MDI, 1,5-naphthalene diisocyanate , aromatic polyisocyanates such as triphenylmethane triisocyanate; Aliphatic polyisocyanates such as xylylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate ; Compounds in which
  • polystyrene resin examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1 ,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol , dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, and other chain aliphatic glycols; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and other alicyclic glycols; g
  • a polyester polyol (2) obtained by reacting a polyol such as the linear aliphatic glycol, alicyclic glycol, dimer diol, bisphenol, or polyether polyol with a polyvalent carboxylic acid; polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; A polyester obtained by reacting a polyol such as the chain aliphatic glycol, alicyclic glycol, dimer diol, bisphenol, or polyether polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polycarboxylic acid.
  • Polyester polyol (5) which is a polymer of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acid; Castor oil, dehydrated castor oil, hydrogenated castor oil, castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil, and mixtures thereof.
  • Examples of the polyvalent carboxylic acid used for producing the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid.
  • non-cyclic aliphatic dicarboxylic acids such as; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; Anhydrides or ester-forming derivatives of aromatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, polybasic acids such as dimer acid is mentioned.
  • the polyisocyanate (A1) is preferred, and the polyisocyanate obtained by reacting the polyether polyol and the polyisocyanate is particularly preferred from the viewpoint of wettability. Furthermore, it is preferable to use a polyol having a polypropylene skeleton as the polyol component to be reacted with the polyisocyanate, since the polyisocyanate (A1) has a low viscosity and is easy to handle at low temperatures.
  • the polyol component to be reacted with the polyisocyanate has a number average molecular weight (Mn) of 300 to 5,000, more preferably 350 to 3,000.
  • Ether polyols are preferably used.
  • the proportion of polyether polyol having a number average molecular weight (Mn) of 300 to 5,000 in the polyol component is preferably 50% by mass or more.
  • the total polyol component may be a polyether polyol having a number average molecular weight (Mn) of 300-5,000.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device HLC-8320GPC manufactured by Tosoh Corporation Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation Detector; RI (differential refractometer) Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation Measurement conditions; column temperature 40°C Solvent; tetrahydrofuran flow rate; 0.35 ml/min standard; monodisperse polystyrene sample; 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 ⁇ l)
  • the polyisocyanate to be reacted with the polyol component preferably contains an aromatic polyisocyanate because of its excellent reactivity with the polyamine (C) described later.
  • the amount of the aromatic polyisocyanate to be blended is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, for 100 parts by mass of the total charged amount for synthesizing the polyisocyanate (A1).
  • the upper limit of the amount of the aromatic polyisocyanate compounded is preferably 60 parts by mass or less, more preferably 55 parts by mass or less.
  • polyisocyanate to be reacted with the polyol component, it is preferable to use at least one of aliphatic polyisocyanate and aliphatic polyisocyanate derivative together with aromatic polyisocyanate from the viewpoint of storage stability.
  • the reaction ratio of the polyisocyanate and the polyol component in the polyisocyanate (A1) is such that the equivalent ratio [isocyanate group/hydroxyl group] between the isocyanate group in the polyisocyanate and the hydroxyl group in the polyol component is 1.5 to 5.0. A range is preferred.
  • the polyisocyanate (A) employing such a polyisocyanate (A1) has an appropriate viscosity of the polyisocyanate composition (X) containing it, and the coating property is improved, and the polyisocyanate (A ) is preferable because the cohesive force of the coating film made of the two-component curing adhesive containing is improved.
  • the polyisocyanate (A) preferably has a weight average molecular weight (Mw) in the range of 100 to 10,000 from the viewpoint of shortening the aging time and ensuring proper packaging properties. A range is more preferred.
  • Mw weight average molecular weight
  • the polyisocyanate (A) is the polyisocyanate (A1), it preferably has a weight average molecular weight (Mw) in the range of 300 to 10,000.
  • the polyisocyanate (A) preferably has an isocyanate content of 5 to 20% by mass.
  • the polyisocyanate composition (X) containing such a polyisocyanate (A) is preferable because it has an appropriate resin viscosity and is excellent in coatability.
  • the isocyanate content of polyisocyanate (A) is a value determined by a titration method using di-n-butylamine.
  • polyol (B) examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6 - hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol , 1,4-cyclohexanedimethanol, glycols such as triethylene glycol;
  • trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, and pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diols;
  • polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polyvalent carboxylic acid
  • polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid
  • a polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid
  • Polyester polyol (5) which is a polymer of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acid
  • Polyester polyether polyols obtained by reacting the polyester polyols (1) to (5), the polyether polyols, and an aromatic or aliphatic polyisocyanate
  • polyester polyurethane polyols obtained by polymerizing the polyester polyols (1) to (5) with aromatic or aliphatic polyisocyanates
  • Castor oil dehydrated castor oil, hydrogenated castor oil,
  • Examples of the polyvalent carboxylic acid used for producing the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid.
  • a tertiary amine compound having a plurality of hydroxyl groups may be used as the polyol (B).
  • a tertiary amine compound having a plurality of hydroxyl groups not only cures when the hydroxyl groups react with the polyisocyanate (A), but also functions as a curing accelerator because the amine structure accelerates the curing reaction.
  • the number of hydroxyl groups is 2 or more, preferably 2 to 6.
  • a tertiary amine compound having a plurality of hydroxyl groups may have one or more tertiary amino groups, preferably one or two.
  • tertiary amine compounds having a plurality of hydroxyl groups include polypropylene glycol ethylene diamine ether, tri(1,2-polypropylene glycol) amine, N-ethyldiethanolamine, N-methyl-N-hydroxyethyl-N-hydroxy ethoxyethylamine, pentakishydroxypropyldiethylenetriamine, tetrakishydroxypropylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, triethanolamine and the like.
  • a commercially available product may be used as the tertiary amine compound having multiple hydroxyl groups.
  • Examples of commercially available products include EDP-300 manufactured by ADEKA Corporation, ED-500 and TE-360 manufactured by Kokuto Kako, and VORANOL TM800 Polyol manufactured by DOW.
  • the mixing ratio of the polyol other than the tertiary amine compound in the polyol (B) and the tertiary amine compound (polyol other than the tertiary amine compound/ The tertiary amine compound (mass ratio)) is preferably from 100/5 to 100/70, more preferably from 100/10 to 100/70.
  • Polyol (B) preferably contains a polyol having a polyether skeleton, and more preferably contains a polyol having a polypropylene skeleton.
  • a polyol (B) has a viscosity that enables coating at a temperature of 25° C. to 60° C. even if it is a non-solvent type.
  • the two-component curing adhesive containing such a polyol (B) is preferable because it exhibits excellent adhesion strength to metal oxides such as silica and/or alumina, metals such as aluminum, and resin films.
  • the content of the polyol having a polyether skeleton is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass, based on the total amount of the polyol (B) from the viewpoint of coatability. It is more preferable to be above.
  • the upper limit of the content of the polyol having a polyether skeleton is not particularly limited, and the total amount of the polyol (B) may be a polyol having a polyether skeleton. From the viewpoint, it is preferably 95% by mass or less.
  • Polyol (B) is castor oil, dehydrated castor oil, hydrogenated castor oil that is a hydrogenated product of castor oil, and 5 to 50 moles of alkylene oxide added to castor oil, from the viewpoint of the initial cohesive strength and coatability of the two-component curing adhesive. It preferably contains at least one castor oil-based compound selected from the group consisting of castor oil-based polyols such as castor oil-based polyols. These castor oil-based compounds are preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass of the total amount of polyol (B). It is more preferable to be above. Also, the upper limit of the castor oil-based compound is not particularly limited, and the total amount of the polyol (B) may be a castor oil-based compound, but from the viewpoint of coatability, it is preferably 95% by mass or less.
  • the polyol (B) may contain a highly reactive low-molecular-weight polyol (liquid at room temperature and having a molecular weight of about 150 or less). By containing such a low-molecular-weight polyol, the reaction with the polyisocyanate (A) can be accelerated. On the other hand, if the amount of the low-molecular-weight polyol is too large, the reaction with the polyisocyanate (A) may be too fast. Therefore, the content of the low-molecular-weight polyol is preferably 5% by mass or less, more preferably 3% by mass or less, of the polyol (B).
  • the viscosity of the polyol (B) is 400 to 5000, so the coatability is improved, and the cohesive force of the two-component curing adhesive is improved, which is preferable. .
  • the hydroxyl value of the polyol (B) is preferably 50 mgKOH/g or more and 300 mgKOH/g or less, more preferably 100 mgKOH/g or more and 250 mgKOH/g or less.
  • the hydroxyl value of the polyol (B) can be measured by the hydroxyl value measuring method described in JIS-K0070.
  • the polyol composition (Y) preferably contains a polyamine (C).
  • Polyamine (C) functions as a curing accelerator.
  • the polyamine (C) known ones can be used without particular limitation.
  • Polyamine (C) has two amino groups ( NH2 group, NHR group (R represents an alkyl group)) in the molecule in order to maintain the toughness of the coating film made of a two-component curing adhesive. It is desirable that the compound has the above.
  • Polyamines (C) include, for example, methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxaspironedecane, lysine, phenylenediamine, 2,2,4-trimethyl Hexamethylenediamine, tolylenediamine, hydrazine, piperazine, hexamethylenediamine, propylenediamine, dicyclohexylmethane-4,4-diamine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine , 2-hydroxypropylethylenediamine, or di-2-hydroxypropylethylenediamine, poly(propylene glycol) diamine, poly(propylene glycol) triamine, poly(propylene glycol) tetraamine, 1,2-diaminopropane, 1,3-diaminoprop
  • 1,4-diaminobutane 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, etc.
  • benzyl amine diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, etc., tetra(aminomethyl)methane, tetrakis ( 2-aminoethylaminomethyl)methane, 1,3-bis(2′-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethy
  • polyamine (C) it is preferable to use a polyetheramine having a polyether structure in the main chain in order to maintain the flexibility of the coating film composed of the two-component curing adhesive.
  • These polyamines (C) may be used alone or in combination of two or more.
  • a commercially available product may be used as the polyamine (C).
  • Commercially available products include EC-310 and EC-303 manufactured by BASF.
  • the functional group in the polyisocyanate composition (X) (the isocyanate group of the polyisocyanate (A)) and the functional group in the polyol composition (Y) (the hydroxyl group of the polyol (B), the amino group of the polyamine (C), group) molar ratio [isocyanate group / (hydroxyl group + amino group)] is preferably 0.5 to 5.0, and from the viewpoint of the adhesive performance of the two-component curing adhesive, 1.0 to 3.0 is more desirable.
  • the ratio of the polyol (B) and the polyamine (C) in the polyol composition (Y) is such that the molar ratio [amino group/hydroxyl group] of the amino group derived from the polyamine (C) and the hydroxyl group derived from the polyol (B) is 0. .001 to 2.0 is desirable, and from the viewpoint of achieving both the adhesive strength of the two-part curing adhesive, the processed appearance, and the practicality of workability, the range of 0.1 to 1.0 is more preferable. preferable.
  • the above molar ratio is 0.001 or more, the workability of the laminated film produced using the two-component curing adhesive becomes favorable.
  • the molar ratio is 2.0 or less, the adhesion strength of the two-component curing adhesive becomes good.
  • the two-component curing adhesive of this embodiment can be used as a non-solvent adhesive.
  • the two-component curing adhesive of this embodiment may contain a solvent, if necessary.
  • the "solvent” refers to a highly soluble organic solvent capable of dissolving the polyisocyanate composition (X) and/or the polyol composition (Y).
  • solvent-free refers to not containing these highly soluble organic solvents.
  • solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, and methyl ethyl ketone (MEK). , cyclohexanone, n-hexane, cyclohexane, and the like.
  • solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are particularly highly soluble organic solvents.
  • the two-component curable adhesive of this embodiment can be used by diluting it with a solvent so as to obtain the desired viscosity when it is required to lower the viscosity.
  • a solvent may be used to dilute either one of the polyisocyanate composition (X) or the polyol composition (Y), or both.
  • organic solvents examples include methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, Examples include toluene, xylene, n-hexane, cyclohexane and the like.
  • ethyl acetate and/or methyl ethyl ketone (MEK) it is preferable to use ethyl acetate, from the viewpoint of the solubility of the polyisocyanate composition (X) and the polyol composition (Y).
  • MEK methyl ethyl ketone
  • the content of the organic solvent in the two-component curing adhesive of the present embodiment can be appropriately determined according to the required viscosity, and can be, for example, 20 to 50% by mass.
  • the two-component curing adhesive of this embodiment may contain a catalyst.
  • the catalyst may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both.
  • the catalyst generally has a high reactivity with the polyisocyanate composition, and after the polyisocyanate composition (X) and the polyol composition (Y) are brought into contact with each other, the catalyst is effectively activated. It is preferably contained only in (Y).
  • the catalyst may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • the two-component curing adhesive contains a catalyst
  • the curing of the two-component curing adhesive is accelerated, and the laminate film produced using the two-component curing adhesive is exposed to harmful low-grade compounds such as aromatic amines. Elution of molecular chemicals can be suppressed. That is, the catalyst also works as a curing accelerator like polyamine (C) and the like.
  • the catalyst is not particularly limited as long as it promotes the urethanization reaction between the polyisocyanate composition (X) and the polyol composition (Y).
  • catalysts that can be used include metal-based catalysts, amine-based catalysts, diazabicycloundecene (DBU), aliphatic cyclic amide compounds, and titanium chelate complexes.
  • Metal-based catalysts include metal complex-based catalysts, inorganic metal-based catalysts, and organic metal-based catalysts.
  • the metal complex catalyst from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum) and Co (cobalt) Acetylacetonate salts of selected metals and the like are included. Specific examples include iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.
  • iron acetylacetonate Fe(acac) 3
  • manganese acetylacetonate Mn(acac) 2
  • Organometallic catalysts include stannus diacetate, stannus dioctoate, stannus dioleate, stannus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, bismuth neodecanoate, zinc neodecanoate and the like.
  • preferred organometallic catalysts are stannous dioctoate, dibutyltin dilaurate, bismuth neodecanoate, zinc neodecanoate, or mixtures thereof.
  • amine-based catalysts examples include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine.
  • triethylenediamine and/or 2-methyltriethylenediamine are preferably used as the amine-based catalyst because of their excellent catalytic activity and industrial availability.
  • tertiary amine catalysts include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'',N ′′-pentamethyldiethylenetriamine, N,N,N′,N′′,N′′-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N′,N′′,N′′-pentamethyldipropylenetriamine, N, N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxy ethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminoprop
  • aliphatic cyclic amide compounds used as catalysts include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthrolactam, ⁇ -capryllactam and ⁇ -propiolactam.
  • ⁇ -caprolactam can more effectively accelerate the curing of two-component curing adhesives.
  • the content of the catalyst in the two-component curing adhesive of this embodiment is not particularly limited, and can be a known amount.
  • the content of the catalyst can be, for example, 0.001 to 5.0% by mass with respect to the total solid content of the two-component curing adhesive.
  • the two-component curing adhesive of this embodiment may contain an adhesion promoter.
  • the adhesion promoter may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both. Since the adhesion promoter has high reactivity with the polyisocyanate composition (X), it is preferred to act after the polyisocyanate composition (X) and the polyol composition (Y) are brought into contact with each other. Therefore, the adhesion promoter is preferably contained only in the polyol composition (Y).
  • the adhesion promoter may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • Adhesion promoters include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, epoxy resins, and the like.
  • Silane coupling agents include, for example, ⁇ -aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, Aminosilanes such as N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycides epoxysilanes such as xypropyltrimethoxysilane and ⁇ -glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris( ⁇ -methoxyethoxy)silane, vinyltrie
  • titanate-based coupling agents examples include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, tetrastearoxytitanium, and the like. can be mentioned.
  • aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.
  • epoxy resin generally commercially available epi-bis type, novolac type, ⁇ -methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polyvalent carboxylic acid ester type, aminoglycidyl type, resorcinol type, and other epoxy resins.
  • the content of the adhesion promoter in the two-component curing adhesive of this embodiment is not particularly limited, and can be a known amount.
  • the content of the adhesion promoter can be, for example, 0 to 50% by mass with respect to the total solid content of the two-component curing adhesive.
  • the two-component curing adhesive of the present embodiment may be used in combination with a pigment, if necessary.
  • the pigment may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both.
  • the pigment may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • the pigment is not particularly limited, and includes various pigments.
  • pigments include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, and metal powders described in the 1970 edition of Handbook of Paint Materials (edited by the Japan Paint Manufacturers Association).
  • organic pigments such as pigments, luminescent pigments and pearlescent pigments, inorganic pigments, and plastic pigments.
  • organic pigments examples include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.
  • insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R
  • soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10
  • various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.
  • Pigments various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; various vat dyes such as anthraquinone pigments, thioindigo pigments and perinone pigments dye-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophtal;
  • inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanic compounds such as Prussian blue; titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, and chromium oxide.
  • various metal oxides such as green and zirconium oxide; various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder. pigments; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and mica-like iron oxide pigments; graphite, carbon black and the like.
  • Extender pigments include, for example, precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, Kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.
  • plastic pigments include "Glandole PP-1000" and "PP-2000S” manufactured by DIC Corporation.
  • inorganic oxides such as titanium oxide and zinc oxide as white pigments, and carbon black as black pigments, since they are excellent in durability, weather resistance, and design.
  • the content of the pigment in the two-component curing adhesive of the present embodiment is 1 to 400 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate composition (X) and the polyol composition (Y). is preferred, and 10 to 300 parts by mass is more preferred.
  • the content of the pigment is 1 to 400 parts by mass, a two-part curing adhesive having excellent adhesion and anti-blocking properties can be obtained.
  • the two-component curing adhesive of the present invention may contain other additives in addition to the components described above, if necessary.
  • the additive may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both.
  • the additive may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • Additives include, for example, leveling agents; inorganic fine particles such as colloidal silica and alumina sol; polymethylmethacrylate-based organic fine particles; antifoaming agents; Deactivator; peroxide decomposer; flame retardant; reinforcing agent; plasticizer; lubricant; rust inhibitor; fluorescent whitening agent; is mentioned.
  • the two-component curing adhesive of the present embodiment is a two-component curing type using a curing reaction between a polyisocyanate composition (X) containing a polyisocyanate (A) and a polyol composition (Y) containing a polyol (B).
  • the polyisocyanate composition (X) and the polyol composition (Y) are subjected to a curing reaction at 25° C., so that the shear viscosity or the complex viscosity is 10 Pa s or more within 1 minute from the start of the curing reaction.
  • the two-component curing adhesive of this embodiment has good reactivity and can be efficiently cured with a small amount of energy.
  • the laminated film in which the adhesive layer is formed between the first film and the second film using the two-component curing adhesive of the present embodiment can obtain excellent bonding strength by heat sealing.
  • FIG. 1 is a cross-sectional view showing an example of the laminated film according to this embodiment.
  • the laminated film 11a of this embodiment has an adhesive layer 10 between the first film W1 and the second film W2.
  • the adhesive layer 10 is made of the cured two-component curing adhesive of the above embodiment.
  • the film In the laminated film 11a of the present embodiment, it is preferable to use plastic films used for known laminated films for the films used as the first film W1 and the second film W2.
  • the first film W1 include base films such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") film, nylon (OPA) film, biaxially oriented polypropylene (OPP) film, various vapor deposition films, Aluminum foil or the like can be used.
  • PET polyethylene terephthalate
  • OPA nylon
  • OPP biaxially oriented polypropylene
  • various vapor deposition films Aluminum foil or the like
  • Aluminum foil or the like can be used.
  • a sealant film such as an unstretched polypropylene (CPP) film or a linear low density polyethylene (LLDPE) film can be used.
  • CPP unstretched polypropylene
  • LLDPE linear low density polyethylene
  • Paper such as natural paper, synthetic paper, and coated paper may be used as the first film W1 and the second film W2.
  • a printed layer may be provided on the outer surface or inner surface side of the first film W1 and/or the second film W2, if necessary.
  • the laminated film 11a of the present embodiment is industrially used as a flexible packaging film, a flexible packaging (package whose shape is formed by putting contents in it) material, a packaging material for filling detergents, medicines, foods, beverages, etc. can be used as intended.
  • Specific examples of detergents and chemicals include liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, and liquid conditioners. Foods and beverages are not particularly limited.
  • the laminated film 11a of this embodiment can be used as a package by forming it into a bag shape.
  • the laminated film 11a of the present embodiment has an adhesive layer 10 between the first film W1 and the second film W2, and the adhesive layer 10 is formed from the cured two-component curable adhesive of the above embodiment.
  • the laminated film 11a of the present embodiment uses the two-component curing adhesive of the present embodiment, which has good reactivity between the polyisocyanate composition (X) and the polyol composition (Y), and uses less energy. It can be produced efficiently in large quantities. Specifically, there is no need to heat the two-component curable adhesive in order to cure it, so the aging temperature can be set to room temperature (25°C), and the aging time can be shortened. can. Moreover, the laminated film 11a of the present embodiment has good heat-sealing properties such that excellent bonding strength can be obtained by heat-sealing.
  • FIG. 2 is a front view of the laminated film manufacturing apparatus according to the present embodiment.
  • 3 is a front view showing a main part of a polyisocyanate coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • FIG. 4 is a front view showing a main part of a polyol coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • the laminated film manufacturing apparatus 1 shown in FIG. 2 uses the two-component curing adhesive of the present embodiment described above to separate the first film W1 unwound from the roll and the second film W2 unwound from the roll.
  • This apparatus forms the adhesive layer 10 between the first film W1 and the second film W2 by sticking them together, and manufactures the above-described laminated film 11a of the present embodiment wound into a roll.
  • the laminated film manufacturing apparatus 1 of the present embodiment includes a first unwinding section 11, a polyisocyanate coating section 12 (first coating section), a second unwinding section 13, A polyol coating unit 14 (second coating unit) and a bonding device 15 are provided.
  • the first unwinding section 11 delivers the first film W1 to the polyisocyanate coating section 12 .
  • the first film W1 is rotatably mounted on the film mounting portion 111 of the first unwinding portion 11 .
  • the polyisocyanate coating section 12 applies the polyisocyanate composition (X) of the two-component curing adhesive of the present embodiment to the first film W1 delivered from the first unwinding section 11 .
  • the polyisocyanate coating section 12 is a four-roll squeeze roll coater.
  • the polyisocyanate coating section 12 includes an application roll 121 , a doctor roll 122 , a metering roll 123 , a coating roll 124 and a backing roll 125 .
  • a liquid reservoir 120 is provided at a portion where the application roll 121 and the doctor roll 122 face each other.
  • the application roll 121 is a roll having an outer peripheral surface made of an elastic material such as rubber.
  • the doctor roll 122 is a roll having an outer peripheral surface made of metal (inelastic material). As shown in FIG. 3, the application roll 121 and the doctor roll 122 are rotatably supported by the polyisocyanate coating section 12 so that their rotation axes are parallel to each other. The outer peripheral surface of the application roll 121 and the outer peripheral surface of the doctor roll 122 face each other with a minute gap therebetween.
  • a pair of barrier plates 126 is installed at a predetermined interval in the direction of the rotation axis of the application roll 121 and the doctor roll 122 above the portion where the application roll 121 and the doctor roll 122 face each other.
  • a liquid reservoir 120 is formed by the pair of barrier plates 126 , the outer peripheral surface of the application roll 121 , and the outer peripheral surface of the doctor roll 122 .
  • the liquid reservoir 120 temporarily stores the polyisocyanate composition (X).
  • the polyisocyanate composition (X) is supplied to the liquid reservoir 120 from a polyisocyanate supply section (not shown). Thereby, the polyisocyanate composition (X) stored in the liquid reservoir 120 is held at a constant amount.
  • the doctor roll 122 preferably has a temperature control section (not shown).
  • the temperature control section keeps the polyisocyanate composition (X) stored in the liquid reservoir section 120 at a constant temperature and stabilizes the viscosity of the polyisocyanate composition (X). Thereby, the outer peripheral surface of the doctor roll 122 is kept at a constant temperature.
  • the application roll 121 and doctor roll 122 rotate downward in the liquid reservoir 120 .
  • the outer peripheral surface of the doctor roll 122 is coated with the polyisocyanate composition (X) that has passed through the minute gaps.
  • the polyisocyanate coating section 12 rotatably supports a metering roll 123, a coating roll 124, and a backing roll 125.
  • the polyisocyanate composition (X) applied to the outer peripheral surface of the doctor roll 122 is transferred to the metering roll 123 .
  • the rotating shaft of the metering roll 123 is arranged parallel to the rotating shaft of the doctor roll 122 .
  • the outer peripheral surface of the metering roll 123 is made of an elastic material such as rubber. The outer peripheral surface of the metering roll 123 is pressed against the outer peripheral surface of the doctor roll 122 .
  • the polyisocyanate composition (X) applied to the outer peripheral surface of the metering roll 123 is transferred to the coating roll 124 .
  • the rotation axis of the coating roll 124 is arranged parallel to the rotation axis of the metering roll 123 .
  • the outer peripheral surface of the coating roll 124 is formed of a metal material. The outer peripheral surface of the coating roll 124 is pressed against the outer peripheral surface of the metering roll 123 .
  • the backing roll 125 is arranged so that the rotating shafts of the coating roll 124 are parallel to each other.
  • the backing roll 125 sandwiches the first film W1 between itself and the coating roll 124, and conveys the first film W1.
  • the backing roll 125 assists the transfer of the polyisocyanate composition (X) applied to the outer peripheral surface of the coating roll 124 to the first film W1.
  • the outer peripheral surface of the backing roll 125 is made of an elastic material such as rubber.
  • the coating roll 124 preferably has a constant temperature of the outer peripheral surface by a temperature control unit (not shown). This stabilizes the viscosity of the polyisocyanate composition (X) applied to the first film W1.
  • the second unwinding section 13 delivers the second film W2 to the polyol coating section 14 .
  • the second film W2 is rotatably mounted on the film mounting portion 131 of the second unwinding portion 13 .
  • the polyol coating section 14 applies the polyol composition (Y) of the two-component curing adhesive of the present embodiment to the second film W2 delivered from the second unwinding section 13 .
  • the polyol coating unit 14, as shown in FIG. 4, is a gravure coating machine (gravure coater) that applies the polyol composition (Y) by gravure printing.
  • the polyol coating section 14 includes a gravure roll 141 , a chamber 142 , an impression cylinder 143 , a coating liquid tank 144 , a pump 145 and a temperature controller 146 .
  • the gravure roll 141 is a metal roll rotatably supported by the polyol coating section 14 .
  • a plurality of recesses are formed on the surface of the gravure roll 141 by, for example, laser engraving. By changing the volume, opening ratio, depth, etc. of the recesses, the amount of the coating liquid applied to the surface of the gravure roll 141 can be adjusted.
  • the gravure pattern applied to the surface of the gravure roll 141 is not particularly limited, and may be, for example, a honeycomb pattern.
  • the chamber 142 is a container that stores the polyol composition (Y).
  • the chamber 142 is arranged on one radial side of the gravure roll 141 .
  • the chamber 142 has a storage part 142a that stores the polyol composition (Y).
  • the storage part 142a is open to the gravure roll 141 side. A part of the outer peripheral surface of the gravure roll 141 is immersed in the polyol composition (Y) stored in the storage part 142a.
  • the reservoir 142a is sealed by a doctor blade 142b, a seal plate 142c and a pair of side plates 142d.
  • the chamber 142 has a plate-like doctor blade 142b.
  • the doctor blade 142b protrudes toward the gravure roll 141 from the upper end of the opening of the reservoir 142a.
  • the material of the doctor blade 142b is not particularly limited, and may be metal or resin, for example, stainless steel.
  • the tip of the doctor blade 142 b is pressed against the outer peripheral surface of the gravure roll 141 .
  • the tip of the doctor blade 142b seals the downstream side of the reservoir 142a in the roll rotation direction.
  • the doctor blade 142b scrapes off excess polyol composition (Y) adhering to the outer peripheral surface of the gravure roll 141 by rotating the gravure roll 141 and weighs it.
  • the chamber 142 has a plate-like seal plate 142c.
  • the seal plate 142c is made of resin.
  • the seal plate 142c protrudes toward the gravure roll 141 from the lower end of the opening of the reservoir 142a.
  • the tip of the seal plate 142 c is pressed against the outer peripheral surface of the gravure roll 141 .
  • the tip of the seal plate 142c seals the upstream side of the reservoir 142a in the roll rotation direction.
  • the chamber 142 has a side plate 142d made of resin.
  • the side plates 142d are attached to both side surfaces of the chamber 142, that is, both ends of the gravure roll 141 in the rotation axis direction.
  • the side surface of the side plate 142 d on the side of the gravure roll 141 has an arc shape along the shape of the gravure roll 141 and is pressed against the gravure roll 141 .
  • the impression cylinder 143 holds the second film W2 between itself and the gravure roll 141, and conveys the second film W2.
  • the impression cylinder 143 presses the second film W2 against the gravure roll 141 to transfer the polyol composition (Y) applied to the outer peripheral surface of the gravure roll 141 to the second film W2.
  • the coating liquid tank 144 is a container that stores the polyol composition (Y). As shown in FIG. 4, the coating liquid tank 144 is connected via a pipe to a pump 145 for flowing the polyol composition (Y) into the chamber 142 . Also, the coating liquid tank 144 is connected to the chamber 142 via a pipe. As a result, the polyol composition (Y) overflowing from the reservoir 142 a of the chamber 142 is recovered in the coating liquid tank 144 .
  • the pump 145 is connected to the coating liquid tank 144 and the chamber 142 via piping.
  • the pump 145 supplies the polyol composition (Y) stored in the coating liquid tank 144 to the reservoir 142 a of the chamber 142 .
  • a sine pump for example, can be used as the pump 145 .
  • the temperature controller 146 adjusts the temperature of the polyol composition (Y) stored in the coating liquid tank 144. This keeps the temperature of the polyol composition (Y) constant and stabilizes the viscosity of the polyol composition (Y).
  • the temperature controller 146 is, for example, a water temperature controller that heats water, which is a heat medium, with a heater and circulates around the polyol composition (Y) stored in the coating liquid tank 144 .
  • the bonding device 15 includes a bonding section 151 and a winding section 152, as shown in FIG.
  • the bonding portion 151 is a surface coated with the polyisocyanate composition (X) in the first film W1 delivered from the polyisocyanate coating portion 12 and a polyol composition in the second film W2 delivered from the polyol coating portion 14.
  • the coated surface of (Y) is pasted together.
  • the winding section 152 winds up the laminated film 11 a bonded by the bonding section 151 .
  • the lamination section 151 has a pair of lamination rolls R1 and R2, as shown in FIG.
  • the lamination rolls R1 and R2 sandwich and bond the first film W1 and the second film W2, and convey them.
  • the two laminate rolls R1 and R2 are kept at a constant temperature on the outer peripheral surface by a temperature control unit (not shown). This stabilizes the curing of the two-component curing adhesive.
  • the lamination unit 151 passes the first film W1 and the second film W2 between two laminate rolls R1 and R2 arranged opposite to each other, and sends them out from the polyisocyanate coating unit 12.
  • the coated surface of the first film W1 fed from the first film W1 and the coated surface of the second film W2 delivered from the polyol coating unit 14 are brought into contact with each other and bonded together.
  • the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2 are mixed to form a two-component curing adhesive. Curing of the agent is started, and the first film W1 and the second film W2 are attached and fixed.
  • the winding section 152 winds up the laminated film 11a formed by bonding the first film W1 and the second film W2 together in the bonding section 151 .
  • the method for manufacturing the laminated film 11a of the present embodiment includes a two-liquid separate coating process and an adhesive layer forming process. In this embodiment, the two-liquid separate application step and the adhesive layer forming step are performed continuously.
  • the two-liquid separate application step includes a first application step of applying the polyisocyanate composition (X) containing the polyisocyanate (A) to the first film W1, and a second application of the polyol composition (Y) containing the polyol (B). and a second coating step of coating the film W2.
  • the first coating process and the second coating process are performed simultaneously.
  • first coating process A method of performing the first coating step using the laminated film manufacturing apparatus 1 shown in FIGS. 2 to 4 will be described.
  • the first film W1 is delivered from the first unwinding section 11 to the polyisocyanate coating section 12 .
  • each roll is rotated in the direction indicated by the arrow in FIG.
  • the polyisocyanate composition (X) stored in the liquid reservoir 120 is applied to the surface of the doctor roll 122 .
  • the temperature of the polyisocyanate composition (X) stored in the liquid reservoir 120 is preferably adjusted to 25° C. to 80° C., preferably 25° C. to 40° C., by a temperature control unit (not shown). is more preferable.
  • the viscosity of the polyisocyanate composition (X) at 40° C. is preferably 3000 mPa s or less, more preferably 2000 mPa s or less, and further preferably 1000 mPa s or less. preferable.
  • the polyisocyanate composition (X) applied to the doctor roll 122 is sequentially transferred to the metering roll 123 and the coating roll 124 .
  • Each roll of the polyisocyanate coating section 12 is set so that the rotational speed increases sequentially.
  • the coating thickness of the polyisocyanate composition (X) gradually decreases, and the coating roll 124 adjusts the coating thickness (coating amount) to a predetermined level.
  • the polyisocyanate composition (X) transferred to the coating roll 124 is transferred to the first film W ⁇ b>1 conveyed between the coating roll 124 and the backing roll 125 . Thereby, the polyisocyanate composition (X) is applied to the first film W1.
  • the coating amount of the polyisocyanate composition (X) applied to the first film W1 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2 .0 g/ m2 .
  • the first film W ⁇ b>1 coated with the polyisocyanate composition (X) is delivered to the bonding device 15 .
  • the second film W2 is delivered from the second unwinding section 13 to the polyol coating section .
  • the gravure roll 141 and impression cylinder 143 are rotated in the directions indicated by the arrows in FIG.
  • the rotation of the gravure roll 141 causes the polyol composition (Y) in the chamber 142 to be applied to the second film W2 through the surface of the gravure roll 141 .
  • the coating amount of the polyol composition (Y) applied to the second film W2 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2.0 g / m2 .
  • the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is preferably adjusted to 25° C. to 80° C., preferably 25° C. to 40° C., by the temperature controller 146. is more preferable.
  • the viscosity of the polyol composition (Y) is set to a viscosity suitable for a gravure coating machine.
  • the rotation direction of the gravure roll 141 may be forward rotation, which is the same direction as the transport direction of the second film W2, or reverse rotation, which is the opposite direction to the transport direction of the second film W2.
  • the gravure roll 141 transfers the polyol composition (Y) to the second film W2 while rotating in the direction opposite to the conveying direction of the second film W2.
  • the appearance of the polyol composition (Y) applied to the second film W2 can be made good without vertical streaks, roll marks, and the like.
  • the second film W ⁇ b>2 coated with the polyol composition (Y) is delivered to the bonding device 15 .
  • Adhesive layer forming step In the adhesive layer forming step, by laminating the first film W1 and the second film W2, the polyisocyanate composition (X) applied on the first film W1 and the polyol applied on the second film It is brought into contact with the composition (Y) to cause a curing reaction.
  • the first film W1 and the second film W2 are sandwiched between two lamination rolls R1 and R2 facing each other while being in contact with each other. pass between two laminate rolls R1, R2. Then, the first film W1 and the second film W2 are laminated together by the pressure from the two lamination rolls R1 and R2.
  • the temperature of the outer peripheral surfaces of the two laminate rolls R1 and R2 is preferably 40°C to 80°C, more preferably 40°C to 60°C.
  • the pressure from the two laminating rolls R1, R2 to the first film W1 and the second film W2 can be, for example, 3-300 kg/cm 2 .
  • the coated surface of the first film W1 delivered from the polyisocyanate coating unit 12 and the second film delivered from the polyol coating unit 14 are sandwiched between the two lamination rolls R1 and R2.
  • the coated surface of W2 contacts.
  • the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2 are mixed, and curing of the two-component curable adhesive is started. be.
  • the laminated film 11a having the adhesive layer 10 between the first film W1 and the second film W2 is obtained.
  • the laminated film 11a produced by bonding the first film W1 and the second film W2 together in the bonding section 151 is conveyed to the winding section 152 .
  • the laminated film 11 a conveyed to the winding section 152 is wound by the winding section 152 .
  • the film transport speed (the winding speed of the laminated film 11a in the winding unit 152) when manufacturing the laminated film 11a can be set to, for example, 30 to 300 m/min. preferably 100 to 250 m/min.
  • a laminated film can be produced efficiently when the film transport speed is 30 m/min or more. If the film transport speed exceeds 300 m/min, problems such as problems in coating, problems in transport itself, and problems in bonding may occur. Therefore, it is preferable to set the film transport speed to 300 m/min or less.
  • the laminated film 11a obtained by the manufacturing method of the present embodiment is obtained by bonding the first film W1 and the second film W2 together in the bonding section 151, and after being wound up by the winding section 152, Alternatively, aging is performed by storing for 3 to 48 hours under heating. Since the two-component curing adhesive of this embodiment cures quickly at a low temperature, it can be aged for 3 to 24 hours at room temperature of about 25°C. In this embodiment, aging may be performed at 40° C. for 48 to 72 hours for more reliable curing. By appropriately selecting and setting the aging as described above, the two-component curing adhesive is sufficiently cured, and practical physical properties as the adhesive layer 10 are exhibited.
  • the manufacturing apparatus 1 of the laminated film 11a of the present embodiment includes a polyisocyanate coating unit 12 that applies the polyisocyanate composition (X) to the first film W1, and a polyol composition (Y) to the second film W2. It has a polyol coating part 14 and a bonding device 15 for bonding the polyisocyanate composition (X)-coated surface of the first film W1 and the polyol composition (Y)-coated surface of the second film W2. Therefore, the manufacturing apparatus 1 of the laminated film 11a of the present embodiment uses the two-component curing adhesive of the present embodiment, and the manufacturing method of the present embodiment having the two-component separate application step achieves excellent heat sealability. It can be suitably used when manufacturing a multi-layered film 11a.
  • the polyol coating unit 14 may be equipped with a gravure coater that expands the range of selection such as the viscosity of the polyol composition (Y), or may be equipped with a roll coater.
  • a gravure coater is selected as the device for applying the polyol composition (Y) in the polyol coating section 14, the viscosity of the polyol composition (Y) is low and problems such as dripping may occur with a roll coater. However, dripping does not occur, and coating quality can be improved to manufacture a high-quality laminated film 11a.
  • the configuration of the polyol coating section 14 can be simplified, and the manufacturing apparatus for the laminated film 11a can be miniaturized.
  • a roll coater is used in the polyisocyanate coating section 12 that applies the relatively high viscosity polyisocyanate composition (X) to the first film W1.
  • a roll coater it is possible to apply even when the viscosity of the polyisocyanate composition (X) is relatively high, and the range of selection of the material of the polyisocyanate composition (X) is widened.
  • the method for producing the laminated film 11a of the present embodiment includes a first coating step of coating the polyisocyanate composition (X) on the first film W1, and a second coating step of coating the polyol composition (Y) on the second film W2.
  • the workability is excellent as compared with the case of having a step of mixing the polyisocyanate composition (X) and the polyol composition (Y).
  • the polyisocyanate composition (X) and the polyol composition (Y) are not mixed, there is no limitation due to the pot life of the two-component curing adhesive, and the two-component curing adhesive of the present embodiment, which cures quickly. drug can be used.
  • the two-component curing adhesive of the present embodiment having good reactivity between the polyisocyanate composition (X) and the polyol composition (Y) is used to prepare the first film.
  • the laminated film 11a is manufactured by laminating W1 and the second film W2. Therefore, it is not necessary to heat the two-component curable adhesive in order to cure the two-component curable adhesive, the aging temperature can be set to room temperature (25° C.), and the aging time can be shortened. Therefore, a laminated film having good heat-sealing properties can be produced efficiently with a small amount of energy.
  • a roll coater is used as the polyisocyanate-coated portion 12, but when the viscosity of the polyisocyanate composition (X) is low, etc., a gravure coater may be used as the polyisocyanate-coated portion 12. . Further, in the above-described embodiment, a gravure coater is used as the polyol-coated portion 14, but a roll coater may be used as the polyol-coated portion 14 when the polyol composition (Y) can be applied. .
  • the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is adjusted by the temperature controller 146. Furthermore, the temperature of the polyol composition (Y) stored in the storage section 142a of the chamber 142 and/or the temperature of the gravure roll 141 may be adjusted. Thereby, the viscosity of the polyol composition (Y) during coating can be further stabilized, and the coating quality and the quality of the laminated film 11a can be further improved.
  • the polyol coating section 14 that applies the polyol composition (Y) to the second film W2 and the An example of manufacturing the laminated film 11a by a production method having a two-liquid separate application process using the laminated film 11a production apparatus 1 having the laminating device 15 for laminating the first film W1 and the second film W2.
  • the laminated film 11a may be manufactured by a manufacturing method having a two-liquid mixing coating process using the manufacturing apparatus shown below, for example.
  • FIG. 5 is a front view for explaining another example of the manufacturing apparatus used for manufacturing the laminated film of this embodiment.
  • a laminated film manufacturing apparatus 1A shown in FIG. the apparatus forms the adhesive layer 10 between the first film W1 and the second film W2, and manufactures the laminated film 11a of the present embodiment, which is wound into a roll.
  • the laminated film manufacturing apparatus 1A shown in FIG. 5 includes, as shown in FIG. . 5 differs from the laminated film manufacturing apparatus 1 shown in FIG. 2 in that a mixture coating section 12A is provided instead of the polyisocyanate coating section 12; It is only the portion without the polyol coating section 14 in the laminated film manufacturing apparatus 1 shown in FIG. In the laminated film manufacturing apparatus 1A shown in FIG. 5, the same members as those in the laminated film manufacturing apparatus 1 shown in FIG.
  • the laminated film manufacturing apparatus 1A shown in FIG. 5 is provided with a mixing device (not shown) for mixing the polyisocyanate composition (X) and the polyol composition (Y) of the two-component curing adhesive. Further, in the laminated film manufacturing apparatus 1A shown in FIG. 5, instead of the polyisocyanate supplying section of the laminated film manufacturing apparatus 1 shown in FIG. is provided.
  • the following manufacturing method can be used.
  • the first film W1 is delivered from the first unwinding section 11 to the mixed liquid coating section 12A.
  • each roll is rotated in the direction indicated by the arrow in FIG.
  • the mixed liquid of the polyisocyanate composition (X) and the polyol composition (Y) stored in the liquid reservoir 120 is applied to the surface of the doctor roll 122 .
  • the temperature of the mixed liquid stored in the liquid reservoir 120 is preferably adjusted to 25° C. to 80° C., more preferably 25° C. to 40° C., by a temperature control unit (not shown). .
  • the shear viscosity of the mixture at 40° C. is preferably 2000 mPa ⁇ s or less, more preferably 1800 mPa ⁇ s or less.
  • the polyol composition (Y) and the polyisocyanate composition (X) are mixed in the mixing device to initiate curing of the two-component curing adhesive.
  • the mixed liquid applied to the doctor roll 122 is sequentially transferred to the metering roll 123 and the coating roll 124 .
  • the mixed liquid transferred to the coating roll 124 is transferred to the first film W ⁇ b>1 conveyed between the coating roll 124 and the backing roll 125 .
  • the mixed liquid is applied to the first film W1.
  • the coating amount of the mixture applied to the first film W1 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2.0 g/m 2 . is.
  • the first film W1 coated with the mixed liquid in the mixed liquid coating section 12A is delivered to the bonding device 15 as shown in FIG.
  • the laminating unit 151 of the laminating device 15 As shown in FIG. 5, two laminates are arranged facing each other in a state where the surface of the first film W1 coated with the liquid mixture is in contact with the second film W2. It is sandwiched between rolls R1 and R2 and passes between the two laminating rolls R1 and R2. Then, the first film W1 and the second film W2 are laminated together by the pressure from the two lamination rolls R1 and R2.
  • the temperature of the outer peripheral surfaces of the two laminate rolls R1 and R2 is preferably 40°C to 80°C, more preferably 40°C to 60°C.
  • the pressure from the two laminating rolls R1, R2 to the first film W1 and the second film W2 can be, for example, 3-300 kg/cm 2 .
  • the laminated film 11a having the adhesive layer 10 between the first film W1 and the second film W2 is obtained.
  • the laminated film 11a produced by bonding the first film W1 and the second film W2 together in the bonding section 151 is conveyed to the winding section 152 .
  • the laminated film 11 a conveyed to the winding section 152 is wound by the winding section 152 .
  • the film transport speed (the winding speed of the laminated film 11a in the winding unit 152) when manufacturing the laminated film 11a can be set to, for example, 30 to 300 m/min. preferably 100 to 250 m/min.
  • a laminated film can be produced efficiently when the film transport speed is 30 m/min or more. If the film transport speed exceeds 300 m/min, problems such as problems in coating, problems in transport itself, and problems in bonding may occur. Therefore, it is preferable to set the film transport speed to 300 m/min or less.
  • a curable adhesive is used to bond the first film W1 and the second film W2 together. Therefore, it is not necessary to heat the two-component curable adhesive in order to cure the two-component curable adhesive, the aging temperature can be set to room temperature (25° C.), and the aging time can be shortened. Therefore, the laminated film 11a having good heat-sealing properties can be efficiently manufactured with a small amount of energy.
  • the laminated film 11a is formed by using a manufacturing method having a two-component separate coating process including a step of coating only the polyol composition (Y) on the film as the manufacturing method having the two-component separate coating process.
  • a manufacturing method having a two-component separate coating process including a step of coating only the polyol composition (Y) on the film as the manufacturing method having the two-component separate coating process.
  • a mixed solution of the polyisocyanate composition and the polyol composition is applied onto the first film
  • a solution containing a curing accelerator is applied onto the second film.
  • a mixture of a part of the polyol composition and the polyisocyanate composition is applied on the first film
  • the remainder of the polyol composition and the curing accelerator are applied.
  • the solution containing is applied to the second film.
  • Polyisocyanate composition (X-1) [Production of polyisocyanate (A-1)]
  • HDI nurate hexamethylene diisocyanate nurate
  • polyisocyanate composition (X-1) comprising polyisocyanate (A-1).
  • the isocyanate content of the polyisocyanate composition (X-1) was measured by a titration method using di-n-butylamine. As a result, it was 14%. Further, the melt shear viscosity at 40° C. was measured for the polyisocyanate composition (X-1). As a result, 1500mPa. was s.
  • Polyisocyanate composition (X-2) [Production of polyisocyanate (A-2)]
  • a stirrer, a thermometer, a flask equipped with a nitrogen gas inlet tube, 4,4-MDI; 41.7 parts, 2,4'-MDI; 11.3 parts, xylylene diisocyanate; 3.0 parts was charged into a reaction vessel, stirred under nitrogen gas, and heated to 60°C.
  • 19.2 parts of a bifunctional PPG with a number average molecular weight of 400 and 24.9 parts of a bifunctional PPG with a number average molecular weight of 2000 were added dropwise in several portions, and 5 to 5 at 80 ° C.
  • a polyisocyanate composition (X-2) composed of the polyisocyanate (A-2) was obtained by stirring for 6 hours to cause a urethanization reaction.
  • the isocyanate content of the polyisocyanate composition (X-2) was measured by a titration method using di-n-butylamine. As a result, it was 14% by mass. Further, the melt shear viscosity at 40° C. was measured for the polyisocyanate composition (X-2). As a result, 1500mPa. was s.
  • Polyisocyanate composition (X-3)) 2K-SF-220A (manufactured by DIC Corporation) was prepared as the polyisocyanate composition (X-3).
  • the isocyanate content of the polyisocyanate composition (X-3) was measured by a titration method using di-n-butylamine. As a result, it was 14% by mass. Further, the melt shear viscosity at 40° C. was measured for the polyisocyanate composition (X-3). As a result, 1500mPa. was s.
  • Polyol Compositions (Y-1) to (Y-7) The polyol (B), polyamine (C) and additives shown in Table 1 were mixed in the proportions shown in Table 1 to obtain polyol compositions (Y-1) to (Y-7).
  • EXCENOL430 polypropylene glycol (manufactured by AGC; functional group 3, number average molecular weight of about 430, hydroxyl value of 400 mgKOH/g, 25°C melt shear viscosity of 350 mPa s)
  • EDP-300 N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (manufactured by ADEKA Co., Ltd.)
  • Polyamine (C) Polyoxypropylene polyamine (manufactured by BASF)
  • ⁇ -caprolactam 2-oxohexamethyleneimine (manufactured by Kanto Chemical Co., Ltd.)
  • Polyol composition (Y-8) HA-234B (manufactured by DIC Corporation) with a hydroxyl value of 90 mgKOH/g was used as the polyol component Y-8.
  • the hydroxyl value was measured for the materials used in the polyol compositions (Y-1) to (Y-8).
  • a hydroxyl value means the number of milligrams of potassium hydroxide corresponding to 1 g of the hydroxyl group of the sample.
  • a method for measuring the hydroxyl value is not particularly limited, and it can be calculated using a known method. In this example, the hydroxyl value was measured according to the hydroxyl value measurement method of JIS-K0070.
  • the amine value was measured for the materials used in the polyol compositions (Y-1) to (Y-8). Amine number refers to milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample.
  • the method for measuring the amine value is not particularly limited, and it can be calculated using a known method. In this example, it was measured according to the amine value standard test method of ASTM D2073. Then, the sum of the hydroxyl value and the amine value contained in the polyol compositions (Y-1) to (Y-8) was determined.
  • Two-component curing adhesive of Examples 1 to 16 and Comparative Example 1 Polyisocyanates (X-1) to (X-3) and polyol compositions (Y-1) to (Y-8) were mixed at 25° C. in the proportions shown in Table 2 or Table 3, and mixed. The shear viscosity or complex viscosity after 1 minute at 25° C. (from the start of the curing reaction) was measured using a rotational rheometer (trade name: MCR-102, manufactured by Anton Paar).
  • the shear viscosity of the mixture was started at a shear rate of 10 s ⁇ 1 in accordance with JIS-Z8803 (2011). The shear viscosity of the mixture was then continuously measured. If the shear viscosity exceeds 8 Pa s before 1 minute from the start of the curing reaction, the vibration measurement conforms to JIS-K7244-10 (2005) when the shear viscosity exceeds 8 Pa s. . Then, at an angular frequency of 10/s, the complex viscosity of the mixture (two-liquid curing adhesive) was measured one minute after the initiation of the curing reaction.
  • Table 2 or Table 3 shows the shear viscosity of the mixture after 1 minute when the shear viscosity is 8 Pa s or less after 1 minute from the start of the curing reaction, or the shear viscosity of 8 Pa before 1 minute from the start of the curing reaction. • Describe the complex viscosity of the mixture after 1 minute from the start of the curing reaction when exceeding s.
  • a corona-treated polyamide film (first film) having a thickness of 15 ⁇ m was coated with one of polyisocyanates (X-1) to (X-3) (first coating step).
  • first coating step the temperature of the polyisocyanate compositions (X-1) to (X-3) stored in the coating liquid tank was set to 40°C.
  • one of the polyol compositions (Y-1) to (Y-8) was applied to a 60 ⁇ m-thick linear low-density polyethylene (LLDPE) film (second film) (second coating process).
  • LLDPE linear low-density polyethylene
  • the total coating amount of the polyisocyanates (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-8) is 1.5. ⁇ 2.0 g/m 2 .
  • the adhesive layer forming process was performed continuously from the first coating process and the second coating process.
  • the adhesive layer forming step by laminating the first film and the second film, any of the polyisocyanates (X-1) to (X-3) applied on the first film and on the second film It was carried out by contacting any of the polyol compositions (Y-1) to (Y-8) applied to the surface to cause a curing reaction.
  • the ratio of the polyisocyanates (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-8) is the isocyanate possessed by the polyisocyanates (X-1) to (X-3).
  • the molar ratio [isocyanate group/(hydroxyl value + amine value)] of the group to the sum of the hydroxyl value and amine value of the polyol compositions (Y-1) to (Y-8) is 1.4 to 1. .6 range.
  • the functional group content of the polyisocyanate compositions shown in Tables 2 and 3 is the isocyanate content (%) of the polyisocyanates (X-1) to (X-3).
  • the functional group content of the polyol composition described in Table 2 or Table 3 is the sum of the hydroxyl value and amine value of the polyol composition (mgKOH/g).
  • the laminated films obtained after the adhesive layer forming step were aged by storing at 25° C. for 1 hour, 3 hours, 6 hours and 24 hours. After that, two test pieces each having a length of 200 mm and a width of 15 mm were cut out from the laminated film, and laminated with the linear low-density polyethylene (LLDPE) film sides facing each other.
  • LLDPE linear low-density polyethylene
  • For the two laminated test pieces using a heat seal bar with a width of 1 cm from the outside (polyamide film), heat and pressurize for 1 second under the conditions of a temperature of 180 ° C. and a pressure of 0.1 bar to heat seal (melt adhesion )did. The heat-sealed test piece was cut so that the length of the heat-sealed portion was 15 mm, peeled at a speed of 300 mm/min, and the heat-seal strength was measured.
  • the shear viscosity or complex viscosity after 1 minute at 25°C after mixing the polyisocyanate (X) and the polyol composition (Y) (from the start of the curing reaction) is 10 Pa ⁇ .
  • the two-component curing adhesive having a shear viscosity or complex viscosity of less than 10 Pa s after 1 minute was used.
  • good heat sealability was obtained.
  • the evaluation of heat seal strength was "4" or "5" even when low-temperature and short-time aging was performed by storing at 25 ° C. for 6 hours. ”, and good heat-sealability was obtained.
  • the laminated film of Comparative Example 1 was evaluated as "3" in terms of heat seal strength even after aging for 24 hours, indicating insufficient heat sealability.
  • 1 laminated film manufacturing apparatus, 10: adhesive layer, 11: first unwinding section, 11a: laminated film, 12: polyisocyanate coating section (first coating section), 13: second unwinding section, 14: Polyol coating part (second coating part), 15: Bonding device, 111: Film mounting part, 120: Liquid reservoir part, 121: Application roll, 122: Doctor roll, 123: Metering roll, 124: Coating roll, 125: backing roll, 126: barrier plate, 131: film mounting part, 141: gravure roll, 142: chamber, 142a: storage part, 142b: doctor blade, 142c: seal plate, 142d: side plate, 143: Impression cylinder, 144: Coating liquid tank, 145: Pump, 146: Temperature controller, 151: Bonding unit, 152: Winding unit, R1, R2: Lamination roll, W1: First film, W2: Second film .

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Citations (6)

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Publication number Priority date Publication date Assignee Title
JP2018030905A (ja) * 2016-08-22 2018-03-01 東洋インキＳｃホールディングス株式会社 接着剤組成物
WO2019167638A1 (ja) * 2018-02-27 2019-09-06 Dic株式会社 軟包装用フィルムの製造方法
WO2019181921A1 (ja) * 2018-03-23 2019-09-26 Dic株式会社 接着剤、積層フィルム、及び積層フィルムの製造方法
JP2019533034A (ja) * 2016-09-29 2019-11-14 Dic株式会社 接着剤、それを使用した積層フィルム、及び接着剤用ポリオール組成物
JP2020041104A (ja) * 2018-09-13 2020-03-19 Dic株式会社 ２液型接着剤、積層フィルム及び包装体
WO2020130073A1 (ja) * 2018-12-21 2020-06-25 Dic株式会社 接着剤、積層フィルム、及び積層フィルムの製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018030905A (ja) * 2016-08-22 2018-03-01 東洋インキＳｃホールディングス株式会社 接着剤組成物
JP2019533034A (ja) * 2016-09-29 2019-11-14 Dic株式会社 接着剤、それを使用した積層フィルム、及び接着剤用ポリオール組成物
WO2019167638A1 (ja) * 2018-02-27 2019-09-06 Dic株式会社 軟包装用フィルムの製造方法
WO2019181921A1 (ja) * 2018-03-23 2019-09-26 Dic株式会社 接着剤、積層フィルム、及び積層フィルムの製造方法
JP2020041104A (ja) * 2018-09-13 2020-03-19 Dic株式会社 ２液型接着剤、積層フィルム及び包装体
WO2020130073A1 (ja) * 2018-12-21 2020-06-25 Dic株式会社 接着剤、積層フィルム、及び積層フィルムの製造方法

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