TW202235571A - Two-component curing adhesive, laminated film, device for producing laminated film, and method for producing laminated film - Google Patents

Abstract

Provided is a two-component curing adhesive using a curing reaction of a polyisocyanate composition (X) and a polyol composition (Y), wherein the polyisocyanate composition (X) contains a polyisocyanate (A) and the polyol composition (Y) contains polyol (B). The extensional viscosity of the polyol composition (Y) is 0.1 Pa.s or less.

Description

Two-component hardening adhesive, laminated film, manufacturing device for laminated film, and method for manufacturing laminated film

The present invention relates to a two-component hardening adhesive, a laminated film, a laminated film manufacturing device, and a laminated film manufacturing method.

Conventionally, among laminated films formed by laminating two films with an adhesive, a two-component curable adhesive that utilizes a curing reaction between a polyisocyanate composition and a polyol composition has been used as an adhesive. As a method of producing a laminated film using a two-component curable adhesive, there is a method including a two-component mixed coating step that has been used since ancient times, and a method that includes a two-component separate coating step that has attracted attention in recent years.

In the method including the two-liquid mixed coating step, the following method may be used, the method comprising: the two-liquid mixed coating step of mixing a polyisocyanate composition and a polyol composition to prepare a mixed liquid, and applying it on the film; and an adhesive layer forming step of laminating another film on the coating film formed on the film and curing it.

As a method including a step of separately applying two liquids, there is a method including: a step of separately applying two liquids, including a first coating step and a second coating step in which polyisocyanate The composition is coated on the first film, the second coating step is to coat the polyol composition on the second film; and the adhesive layer forming step is to make the coating by laminating the first film and the second film The polyisocyanate composition on the first film is in contact with the polyol composition coated on the second film to undergo hardening reaction.

In recent years, from the viewpoint of reduction of environmental load and improvement of working environment, demand for a solvent-free two-component curing adhesive that does not use an organic solvent has increased. For example, Patent Document 1 to Patent Document 3 describe a two-liquid separately-coated adhesive: a solvent-free A agent that is liquid at room temperature when coated on one of the adherends and coated on the other. The non-solvent B agent, which is liquid at room temperature on the adherend, starts to harden when it comes into contact with it.

Patent Document 1 describes a two-component coating-type urethane-based adhesive: the agent A is composed of compounds having isocyanate groups at both ends of the molecule as the main component, and the agent B contains isocyanate groups at both ends of the molecule. A compound with an amine group at the end, a compound with a tertiary amine in the molecule, and an adhesive resin. Patent Document 2 describes a two-liquid coating-type urethane-based adhesive: the agent A is composed of compounds having isocyanate groups at both ends of the molecule as the main component, and the agent B is composed of compounds having isocyanate groups at both ends of the molecule. The main component is a compound having an amino group at the end. Patent Document 3 describes a two-component coating-type urethane-based adhesive: the agent A is composed of compounds having isocyanate groups at both ends of the molecule as the main component, and the agent B is composed of compounds having isocyanate groups in the molecule. The compound having a hydroxyl group is formed as the main component. [Prior art literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2003-171641 [Patent Document 2] Japanese Patent Laid-Open No. 2003-171642 [Patent Document 3] Japanese Patent Laid-Open No. 2003-171643

[Problem to be Solved by the Invention] However, when a laminated film is produced using a two-component curing adhesive that utilizes the curing reaction of the polyisocyanate composition and the polyol composition, the cohesive force (initial cohesive force) immediately after bonding may be insufficient. In this case, it takes time until sufficient cohesive force can be obtained, so the time of the aging step may become longer, or heating at about 40°C to 60°C may be necessary. Therefore, there is a possibility that the production efficiency of the laminated film may decrease. In particular, in most methods including separate coating steps of two liquids, the polyisocyanate composition and the polyol composition contact each other for the first time between substrates after respective coatings. Accordingly, the mixing of the composition or the reaction between the functional groups in the composition occurs slowly, and insufficient initial cohesive force often becomes a problem.

In addition, in the case of producing a laminated film using a two-component curing adhesive, in the step of coating a component containing a polyol composition on the film, misting (misting) caused by the polyol composition tends to occur ( drawing phenomenon) bad condition. If ink misting occurs, the adhesive will scatter and adhere to the manufacturing equipment or equipment, so regular operation stop and cleaning are required. On the other hand, if the rotation speed of the roller or the conveyance speed of the film is reduced in order to reduce the occurrence of ink misting, the production efficiency will decrease. Especially in the case of continuously producing a laminated film using a method including a two-liquid separate coating step, if the film conveyance speed is increased, misting of the polyol composition is likely to occur, which becomes a problem.

The present invention was made in view of the above circumstances, and an object of the present invention is to provide a two-component hardening adhesive that uses a hardening reaction between a polyisocyanate composition and a polyol composition and has an excellent initial cohesive force, and Even if the step of coating the component containing the polyol composition on the film is performed, ink misting due to the polyol composition is less likely to occur. An object of the present invention is to provide a laminated film that can be efficiently produced using a two-component hardening type adhesive excellent in initial cohesive force and has excellent characteristics using the two-component hardening type adhesive excellent in initial cohesive force The two-component curable adhesive of the curing reaction of the polyisocyanate composition and the polyol composition is less likely to cause misting due to the polyol composition even if the step of coating the film with a component containing the polyol composition is performed.

The object of the present invention is to provide a laminated film manufacturing apparatus that can be suitably used for using a two-component hardening type adhesive that utilizes a hardening reaction of a polyisocyanate composition and a polyol composition that does not easily cause flying ink and has excellent initial cohesion. A case where a laminated film is produced by a production method including a separate application step of two liquids. An object of the present invention is to provide a method for producing a laminated film that can be efficiently produced using a two-component curing adhesive that utilizes a curing reaction between a polyisocyanate composition and a polyol composition that is less likely to cause flying ink and has excellent initial cohesion. laminated film. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention suppress the application of a component containing a polyol composition on a film when using a two-component curable adhesive that utilizes a curing reaction between a polyisocyanate composition and a polyol composition. We have made repeated efforts to improve the initial cohesive force of the adhesive and the splashing ink generated in the step. As a result, it was found that the use of a polyol composition having an elongational viscosity of 1 Pa·s or less increases the initial cohesive force and suppresses the occurrence of flying ink, leading to the present invention. That is, the present invention relates to the following matters.

[1] A two-component hardening adhesive using a curing reaction between a polyisocyanate composition (X) and a polyol composition (Y), in which, The polyisocyanate composition (X) contains polyisocyanate (A), The polyol composition (Y) contains the polyol (B), and has an elongational viscosity of 1 Pa·s or less.

[2] A laminated film having an adhesive layer between a first film and a second film, The adhesive layer includes a cured product of the two-component hardening adhesive described in [1].

[3] A manufacturing device for a laminated film comprising: The first coating part applies the polyisocyanate composition (X) containing polyisocyanate (A) to the first film; In the second application part, the polyol composition (Y) containing the polyol (B) and having an elongational viscosity of 1 Pa·s or less is applied to the second film; and The bonding device bonds the polyisocyanate composition (X)-coated surface of the first film to the polyol composition (Y)-coated surface of the second film.

[4] A method of manufacturing a laminated film, comprising: The two-liquid coating step includes a first coating step and a second coating step, the first coating step is to coat the polyisocyanate composition (X) containing polyisocyanate (A) on the first film, The second coating step is coating the polyol composition (Y) containing the polyol (B) and having an elongational viscosity of 1 Pa·s or less on the second film; and Following the step of forming an agent layer, the polyisocyanate composition (X) coated on the first film and the polyisocyanate composition (X) coated on the second film are laminated by laminating the first film and the second film. The above-mentioned polyol composition (Y) on contact causes a hardening reaction. [Effect of the invention]

The two-component curable adhesive of the present invention is a two-component curable adhesive using a curing reaction between a polyisocyanate composition (X) and a polyol composition (Y) having an elongational viscosity of 1 Pa·s or less. In the two-component curable adhesive of the present invention, the polyol composition (Y) has an elongational viscosity of 1 Pa·s or less, and is excellent in initial cohesion. In addition, even if the step of coating a component containing the polyol composition (Y) on the film is performed, ink misting due to the polyol composition (Y) is less likely to occur.

Therefore, the two-component curable adhesive of the present invention can be suitably used, for example, in the case of producing a laminated film using a production method including a two-component mixing coating step, a production method including a two-component coating step, and the like. In particular, it can be suitably used in the case of continuously producing a laminated film using a method including a two-liquid coating step in which only the polyol composition (Y) is coated on one of the films.

In the laminated film of the present invention, there is an adhesive layer between the first film and the second film, and the adhesive layer contains a cured product of the two-component hardening adhesive of the present invention. Since the two-component curing adhesive of the present invention has excellent initial cohesion, it can shorten the aging time in the production steps of the laminated film, or expand the selection range of the steps, and can be produced efficiently. In addition, the laminated film of the present invention can use the two layers of the present invention that do not easily cause ink misting caused by the polyol composition (Y) even if a step of coating a component containing the polyol composition (Y) is performed on one of the films. Manufactured with liquid hardening adhesive. Therefore, the laminated film of the present invention can be efficiently produced using, for example, a production method including a two-liquid mixed coating step, a production method including a two-liquid separate coating step, and the like.

In the manufacturing apparatus of the laminated film of this invention, a 2nd application part applies the polyol composition (Y) whose elongational viscosity is 1 Pa·s or less to a 2nd film. Therefore, the production apparatus of the laminated film of the present invention can be suitably used in the case of producing a laminated film by a production method including a step of separately applying the two liquids using the two-liquid curable adhesive of the present invention.

The method for producing a laminated film of the present invention includes a separate coating step of two liquids, and in the second coating step, the polyol composition (Y) having an elongational viscosity of 1 Pa·s or less is coated on the second film. In the method for producing a laminated film of the present invention, a laminated film having excellent characteristics can be produced with high productivity by using the two-component curable adhesive having excellent initial cohesive force of the present invention. In addition, by using the two-component curable adhesive of the present invention, it is possible to continuously and efficiently produce a laminated film at a high film conveyance speed while suppressing the generation of misting caused by the polyol composition (Y).

Hereinafter, the two-component curable adhesive, laminated film, laminated film manufacturing apparatus, and laminated film manufacturing method of the present invention will be described in detail using drawings. In addition, in the drawing used in the following description, in order to understand the characteristic of this invention easily, the part which becomes a characteristic may be enlarged and shown for convenience. Therefore, the dimensional ratio and the like of each component may differ from actual ones.

[Two-component hardening adhesive] The two-component curable adhesive of the present embodiment is a two-component curable adhesive using a curing reaction of the polyisocyanate composition (X) and the polyol composition (Y). The polyisocyanate composition (X) in the two-component curable adhesive of this embodiment contains polyisocyanate (A). The polyol composition (Y) contains the polyol (B) and has an elongational viscosity of 1 Pa·s or less. The polyisocyanate composition (X) may contain a part of the polyol (B) contained in the two-component hardening-type adhesive agent as needed. The two-component curable adhesive of this embodiment is cured by the chemical reaction of the isocyanate group in the polyisocyanate composition (X) and the hydroxyl group (or hydroxyl group and amine group) in the polyol composition (Y).

(elongational viscosity of polyol composition (Y)) In the two-component curable adhesive of the present embodiment, the polyol composition (Y) has an elongational viscosity of 1 Pa·s or less, and has excellent initial cohesive force. In addition, if the elongational viscosity of the polyol composition (Y) is 1 Pa·s or less, in the case of producing a laminated film using the two-component curable adhesive of this embodiment, even if the film is coated with a polyol-containing The steps of the composition of the composition (Y) are also less likely to cause ink flying (stringing phenomenon) caused by the polyol composition (Y). Therefore, the two-component curing adhesive of this embodiment can be suitably used in the process including the step of easily causing ink flying caused by the polyol composition (Y), that is, coating only the polyol composition (Y) on the film. Y) The case where a laminated film is produced by the method of two separate coating steps.

In addition, the polyol composition (Y) having an elongational viscosity of 1 Pa·s or less has good reactivity with the polyisocyanate composition (X). Therefore, the aging temperature of the two-component curing adhesive can be lowered, or the aging time can be shortened, and a laminated film having excellent characteristics can be produced with high productivity. Among them, the elongational viscosity of the polyol composition (Y) is more preferably 0.90 Pa·s or less. In addition, in order to have a viscosity that is easy to coat on a roll coater or a gravure coater, the elongational viscosity of the polyol composition (Y) is more preferably 0.20 Pa·s or more, more preferably 0.30 Pa·s or more, and especially preferably 0.30 Pa·s or more. 0.45 Pa·s or more.

The elongational viscosity of the polyol composition (Y) can be controlled by adjusting the ratio of the low-viscosity material and the high-viscosity material contained in the materials (compounds) used in the polyol composition (Y). In addition, those skilled in the art can grasp the viscosity of the material (compound) used for the polyol composition (Y). In addition, if a person skilled in the art, by combining the materials (compounds) used in the polyol composition (Y) and adjusting the blending ratio appropriately, it is possible to obtain the desired polyol composition (Y) within the usual experimental range and based on known techniques. Polyol composition (Y) with elongational viscosity in the range of .

(Polyisocyanate (A)) It does not specifically limit as a polyisocyanate (A), A well-known thing can be used. Examples of the polyisocyanate (A) include: Cresyl diisocyanate, 2,4'-diphenylmethane diisocyanate (hereafter, diphenylmethane diisocyanate may be abbreviated as "MDI (diphenylmethane diisocyanate)"), 2,2'-MDI, 4,4 Aromatic polyisocyanate such as '-MDI, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; Xylylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), 1,3-(isocyanatomethyl)cyclohexane, 1,6-hexamethylenebis Aliphatic polyisocyanate such as isocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate; Compounds obtained by modifying some of the isocyanate groups (hereinafter sometimes referred to as "NCO groups") of these polyisocyanates with carbodiimide; Isocyanurate bodies derived from these polyisocyanates; alloformate bodies derived from these polyisocyanates; biuret bodies derived from these polyisocyanates; trimethylolpropane Modified adducts; Polyisocyanate (A1) that is a reaction product (prepolymer) of the various polyisocyanates and polyol components (hereinafter, the polyisocyanate that is the prepolymer may be referred to as "polyisocyanate (A1)") Wait.

Among polyisocyanates (A1), examples of polyol components that react with aromatic polyisocyanate and aliphatic polyisocyanate specifically include ethylene glycol, propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butyl ethyl Propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene and other chain aliphatic diols; 1,4-cyclohexanediol, 1,4 - Alicyclic diols such as cyclohexanedimethanol; trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, and pentaerythritol; bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F Bisphenols such as diols; dimer diols; addition polymerization of ethylene oxide, propylene oxide, butylene oxide in the presence of polymerization initiators such as diol diols, trifunctional or tetrafunctional aliphatic alcohols, etc. Polyether polyols made of alkylene oxides such as alkanes, phenylene oxides, epichlorohydrin, tetrahydrofuran, and cyclohexylene; by propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone , β-methyl-σ-valerolactone and other cyclic ester compounds obtained by the ring-opening polymerization reaction of polyester and the reaction product of diol or trifunctional or tetrafunctional aliphatic alcohol, that is, polyester polyol (1);

Polyester polyol (2) obtained by reacting polyhydric alcohols such as the chain aliphatic diol, alicyclic diol, dimer diol, bisphenol or polyether polyol with polycarboxylic acid; A polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; The chain aliphatic diol, alicyclic diol, dimer diol, bisphenol or polyols such as polyether polyol, the trifunctional or tetrafunctional aliphatic alcohol and polycarboxylic acid The polyester polyol (4) obtained by reaction; Polymers of hydroxy acids such as dimethylol propionic acid and castor oil fatty acid, namely polyester polyols (5); Castor oil-based polyols such as castor oil, dehydrated castor oil, hardened castor oil which is a hydrogenated product of castor oil, and an alkylene oxide 5-50 molar adduct of castor oil, and mixtures thereof.

Examples of the polyvalent carboxylic acid used in the production of the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane di Acyclic aliphatic dicarboxylic acids such as carboxylic acid, maleic anhydride and fumaric acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; Phthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, 1, Aromatic dicarboxylic acids such as 2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; anhydride or ester-forming derivatives of these aliphatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid Polyacids such as p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, and dimer acids.

Among these polyisocyanates (A), the polyisocyanate (A1) is preferred, and the polyisocyanate (A1) obtained by reacting the polyether polyol with the polyisocyanate is preferred especially in terms of wettability. Polyisocyanate. Furthermore, since it becomes polyisocyanate (A1) which has a low viscosity and is easy to handle at low temperature, it is preferable to use the polyol which has a polypropylene skeleton as a polyol component which reacts with polyisocyanate.

From the viewpoint of the flexibility of the cured coating film of the polyisocyanate (A1), as the polyol component that reacts with the polyisocyanate, it is preferable to use a number average molecular weight (Mn) of 300 to 5,000, more preferably 350 to 5,000. 3,000 polyether polyol. As an example, the proportion of the 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 amount of the polyol component may be a polyether polyol having a number average molecular weight (Mn) of 300 to 5,000.

In the present specification, weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) under the following conditions. Measuring device: HLC-8320 GPC manufactured by Tosoh Co., Ltd. String: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Co., Ltd. Detector: RI (Differential Refractometer) Data processing: Multi station GPC-8020 model II manufactured by Tosoh Co., Ltd. Measuring conditions: column temperature 40°C Solvent: Tetrahydrofuran Flow rate: 0.35 ml/min Standard: Monodisperse Polystyrene Sample: A tetrahydrofuran solution of 0.2% by mass in terms of resin solids was filtered through a microfilter (100 μl)

In the polyisocyanate (A1), it is preferable to include an aromatic polyisocyanate as the polyisocyanate reacted with the polyol component, since the reactivity with the polyamine (C) mentioned later is excellent. The blending amount of the aromatic polyisocyanate is, for example, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, out of a total of 100 parts by mass of the polyisocyanate (A1) charged at the time of synthesis. From the viewpoint of storage stability, the upper limit of the compounding amount of the aromatic polyisocyanate is preferably 60 parts by mass or less, more preferably 55 parts by mass or less.

As the polyisocyanate reacted with the polyol component, it is preferable to use an aromatic polyisocyanate in combination with at least one of aliphatic polyisocyanate and derivatives of aliphatic polyisocyanate from the viewpoint of storage stability.

The reaction ratio of the polyisocyanate and the polyol component in the polyisocyanate (A1) is preferably such that the equivalent ratio [isocyanate group/hydroxyl group] of the isocyanate group in the polyisocyanate to the hydroxyl group in the polyol component is in the range of 1.5 to 5.0. Regarding the polyisocyanate (A) using such a polyisocyanate (A1), the viscosity of the polyisocyanate composition (X) containing it is in an appropriate range, the coatability becomes good, and the two liquids containing the polyisocyanate (A) are included. Since the cohesion force of the coating film of a hardening type adhesive becomes favorable, it is preferable.

The polyisocyanate (A) preferably has a weight average molecular weight (Mw) in the range of 100 to 10,000, more preferably in the range of 200 to 5,000, from the viewpoint of shortening the aging time and securing appropriate practical packaging properties. When polyisocyanate (A) is polyisocyanate (A1), weight average molecular weight (Mw) becomes like this. Preferably it is the range of 300-10,000.

The polyisocyanate (A) preferably has an isocyanate content of 5% by mass to 20% by mass. The polyisocyanate composition (X) containing such a polyisocyanate (A) is preferable at the point which becomes an appropriate resin viscosity and is excellent in coatability. The isocyanate content rate of polyisocyanate (A) is the value calculated|required by the titration method using di-n-butylamine.

(Polyol (B)) Examples of the polyhydric alcohol (B) include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 3-methyl-1,5-pentanediol alcohol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, di Propylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol and other diols;

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; Addition polymerization of ethylene oxide, propylene oxide, butylene oxide, phenylene oxide, epichlorohydrin, tetrahydrofuran, ethylene oxide, etc. Polyether polyols made of alkylene oxides such as cyclohexyl groups; polyether urethane polyols made of polyether polyols that are further increased in molecular weight by using the aromatic polyisocyanate or aliphatic polyisocyanate; The polyester obtained by the ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone and the like Reactants of polyols such as glycol, glycerin, trimethylolpropane, pentaerythritol, namely polyester polyol (1);

Polyester polyol (2) obtained by reacting difunctional polyols such as diols, dimer diols, or bisphenols with polycarboxylic acids; A polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; A polyester polyol (4) obtained by reacting a difunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; Polymers of hydroxy acids such as dimethylol propionic acid and castor oil fatty acid, namely polyester polyols (5); The polyester polyether polyol obtained by reacting the polyester polyol (1) to polyester polyol (5) with the polyether polyol and aromatic polyisocyanate or aliphatic polyisocyanate; Polyester polyurethane polyol obtained by increasing the molecular weight of the polyester polyol (1) to polyester polyol (5) by using aromatic polyisocyanate or aliphatic polyisocyanate; Castor oil-based polyols such as castor oil, dehydrated castor oil, hardened castor oil which is a hydrogenated product of castor oil, and an alkylene oxide 5-50 molar adduct of castor oil, and mixtures thereof.

Examples of the polyvalent carboxylic acid used in the production of the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecane di Aliphatic dicarboxylic acids such as carboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, 1 ,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p' - Aromatic dicarboxylic acids such as dicarboxylic acids; and anhydride or ester-forming derivatives of these aliphatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and such Polybasic acids such as ester-forming derivatives of some dihydroxycarboxylic acids and dimer acids.

A tertiary amine compound having a plurality of hydroxyl groups can also be used as the polyol (B). The tertiary amine compound having a plurality of hydroxyl groups not only reacts with the polyisocyanate (A) to harden the hydroxyl groups, but also functions as a hardening accelerator because the amine structure promotes the hardening reaction. In the tertiary amine compound having multiple hydroxyl groups, the number of hydroxyl groups is two or more, preferably 2-6. The tertiary amine compound which has a some hydroxyl group should just have one or more tertiary amine groups, Preferably it has 1 - 2.

As the tertiary amine compound having a plurality of hydroxyl groups, specifically, polypropylene glycol ethylene diamine ether, tris(1,2-polypropylene glycol) amine, N-ethyldiethanolamine, N-methyl- N-Hydroxyethyl-N-hydroxyethoxyethylamine, pentahydroxypropyldiethylenetriamine, tetrahydroxypropylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl base) ethylenediamine, triethanolamine, propoxylated triethanolamine, etc.

A commercial item can also be used as a tertiary amine compound which has several hydroxyl groups. Examples of commercially available products include EDP-300 manufactured by ADEKA Co., Ltd., ED-500 or TE-360 manufactured by Kokudo Chemical Co., Ltd., and Volano TM800 manufactured by Dow Corporation. Alcohol (VORANOL TM800Polyol), etc.

When the polyol (B) contains a tertiary amine compound having a plurality of hydroxyl groups, the compounding ratio of the polyol other than the tertiary amine compound and the tertiary amine compound in the polyol (B) (other than the tertiary amine compound Polyol/tertiary amine compound (mass ratio)) is 100/5-100/70, more preferably 100/10-100/70.

These compounds can be used individually or in combination of multiple types as a polyol (B). The polyol (B) preferably includes a polyol having a polyether skeleton, more preferably includes a polyol having a polypropylene skeleton. Even if such a polyol (B) is a solvent-free type, it becomes the viscosity which can be applied at the temperature of 25 degreeC - 60 degreeC. In addition, the two-component curable adhesive containing such a polyol (B) is excellent in adhesive strength to metal oxides such as silica and/or alumina, metals such as aluminum, and resin films, and is preferable.

From the viewpoint of coating suitability, the content of the polyol having a polyether skeleton is preferably at least 5% by mass, more preferably at least 10% by mass, and still more preferably 15% by mass based on the total amount of the polyol (B). %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, depending on the initial cohesion of the two-component hardening adhesive. In other words, it is preferably 95% by mass or less.

From the viewpoint of the initial cohesion of the two-component hardening adhesive and the applicability, the polyol (B) preferably contains castor oil selected from the group consisting of castor oil, dehydrated castor oil, castor oil which is a hydrogenated product of castor oil, At least one castor oil-based compound in the group consisting of castor oil-based polyols such as an alkylene oxide 5-50 molar adduct of castor oil. The amount of these castor oil-based compounds is preferably at least 5% by mass, more preferably at least 10% by mass, more preferably at least 15% by mass, more preferably at least 20% by mass, based on the total amount of the polyol (B). In addition, 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 is preferably 95% by mass or less from the viewpoint of applicability.

The polyol (B) may include highly reactive low-molecular-weight polyols (liquid at room temperature, having a molecular weight of about 150 or less). By including such a low-molecular-weight polyol, the reaction with polyisocyanate (A) can be accelerated. On the other hand, when there is too much compounding quantity of the low molecular weight polyol, reaction with polyisocyanate (A) may be too quick. Therefore, the content of the low-molecular-weight polyol is preferably at most 5% by mass of the polyol (B), more preferably at most 3% by mass.

When the weight-average molecular weight (Mw) of the polyol (B) is 400 to 5000, it is in an appropriate viscosity range, so that the applicability becomes good, and the cohesive force of the two-component hardening adhesive becomes good, which is preferable.

The hydroxyl value of the polyol (B) is preferably not less than 50 mgKOH/g and not more than 300 mgKOH/g, more preferably not less than 100 mgKOH/g and not more than 250 mgKOH/g. The hydroxyl value of the polyol (B) can be measured by the hydroxyl value measuring method described in Japanese Industrial Standards (JIS)-K0070.

(Polyamine (C)) The polyol composition (Y) preferably contains polyamine (C). Polyamine (C) functions as a hardening accelerator. It does not specifically limit as a polyamine (C), A well-known thing can be used. The polyamine (C) is preferably a compound having two or more amine groups (NH ₂ group, NHR group (R represents an alkyl group)) in the molecule in order to maintain the toughness of the coating film containing the two-component curing adhesive.

Examples of polyamines (C) include methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropaneamine-2,4,8,10-tetraoxaspiro Undecane, lysine, phenylenediamine, 2,2,4-trimethylhexamethylenediamine, methylenediamine, hydrazine, piperazine, hexamethylenediamine, Propyldiamine, 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) tetramine, 1,2-diamine propane, 1,3-diaminopropane,

1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-Diaminononane, 1,10-Diaminodecane, etc., Benzylamine, Diethylenetriamine, Dipropylenetriamine, Triethylenetetramine, Tripropylenetetramine Amine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecylamine, trimethylhexamethylenediamine, etc., tetrakis (aminomethyl) methane, Tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3 -aminoethyl)amine, bis-hexamethylenetriamine, etc., 1,4-cyclohexanediamine, 4,4'-methylenebiscyclohexylamine, 4,4'-isopropylidenebicyclohexyl Amine, norbornanediamine,

Bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menthene diamine, etc., bis(aminoalkyl)benzene, bis(aminoalkane base) naphthalene, bis(cyanoethyl) diethylene triamine, o-xylylene diamine, m-xylylene diamine, p-xylylene diamine, phenylene diamine, naphthyl diamine , diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4' -Diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylphenone, 2,2'-dimethyl-4,4'-diamine Diphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, bis(aminomethyl)naphthalene, bis(aminoethyl)naphthalene, etc., N-methylpiperazine, morpholine, 1,4-bis-(8-aminopropyl )-piperazine, piperazine-1,4-diazepane, 1-(2'-aminoethylpiperazine), 1-[2'-(2''-aminoethylamino ) ethyl]piperazine, tricyclodecanediamine, polyurea amine which is a reaction product of the above-mentioned various polyamines and the above-mentioned various isocyanate components, and the like.

As the polyamine (C), it is preferable to use a polyetheramine having a polyether structure in the main chain in order to maintain the flexibility of a coating film containing a two-component curing adhesive. These polyamines (C) may be used alone or in combination of two or more.

A commercial item can also be used as a polyamine (C). Examples of commercially available products include EC-310 and EC-303 manufactured by BASF Corporation.

Functional groups in the polyisocyanate composition (X) (isocyanate groups in the polyisocyanate (A)) and functional groups in the polyol composition (Y) (hydroxyl groups in the polyol (B), polyamines (C ) molar ratio [isocyanate group/(hydroxyl+amine group)] is preferably 0.5 to 5.0, and more preferably 1.0 to 5.0 from the viewpoint of adhesive performance of the two-component hardening adhesive 3.0 range.

The ratio of the polyol (B) to the polyamine (C) in the polyol composition (Y) is ideally the molar ratio of the amine group derived from the polyamine (C) to the hydroxyl group derived from the polyol (B)[ Amino group/hydroxyl group] is 0.001 to 2.0, and is more preferably in the range of 0.1 to 1.0 from the practical point of view of both the adhesive strength of the two-component hardening adhesive, the processed appearance, and the workability. When the said molar ratio is 0.001 or more, the processability of the laminated film manufactured using a two-component hardening type adhesive becomes favorable. When the said molar ratio is 2.0 or less, the adhesive strength of a two-component curable adhesive becomes favorable.

(solvent) The two-component hardening adhesive of this embodiment can be used as a solvent-free adhesive, and the two-component hardening adhesive of this embodiment may contain a solvent as needed. In this embodiment, the term "solvent" refers to a highly soluble organic solvent capable of dissolving the polyisocyanate composition (X) and/or the polyol composition (Y). In addition, in the present embodiment, "non-solvent" means not including these highly soluble organic solvents.

Examples of highly soluble organic solvents (solvents) specifically include toluene, xylene, methylene chloride, tetrahydrofuran, methanol, ethanol, isopropanol, methyl acetate, ethyl acetate, n-butyl acetate, Acetone, methyl ethyl ketone (Methyl Ethyl Ketone, MEK), cyclohexanone, n-hexane, cyclohexane, etc. Among these, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are particularly high-soluble organic solvents.

The two-component hardening adhesive of this embodiment can be diluted with a solvent and used so that the viscosity can be desired when lowering the viscosity is required. In this case, only one of the polyisocyanate composition (X) or the polyol composition (Y) may be diluted with a solvent, or both may be diluted.

Examples of organic solvents that can be contained in the two-component curing adhesive of this embodiment include methanol, ethanol, isopropanol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, and methyl ethyl ketone. (MEK), cyclohexanone, toluene, xylene, n-hexane, cyclohexane, etc. Among these, in terms of the solubility of the polyisocyanate composition (X) and the polyol composition (Y), it is preferable to use ethyl acetate and/or methyl ethyl ketone (MEK), and it is particularly preferable to use Use ethyl acetate. The content of the organic solvent in the two-component hardening type adhesive agent of this embodiment can be suitably determined according to the required viscosity, For example, it can set it as 20 mass % - 50 mass %.

(catalyst) The two-component curing adhesive of this embodiment may also contain a catalyst. The catalyst may be included in only one of the polyisocyanate composition (X) and the polyol composition (Y), or may be included in both. In general, the catalyst is preferably Contained only in the polyol composition (Y). The catalyst may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) at the time of application of the two-component curing adhesive.

By including a catalyst in the two-component hardening adhesive, the hardening of the two-component hardening adhesive can be accelerated, and harmful low-molecular chemical substances represented by aromatic amines can be inhibited from laminating from the two-component hardening adhesive. dissolved in the film. That is, the catalyst functions as a hardening accelerator similarly to the polyamine (C) and the like.

The catalyst is not particularly limited as long as it accelerates the urethanization reaction of the polyisocyanate composition (X) and the polyol composition (Y). As the catalyst, for example, metal-based catalysts, amine-based catalysts, diazabicycloundecene (DBU), aliphatic cyclic amide compounds, titanium chelate compounds, and the like can be used.

Examples of the metal-based catalyst include metal complex-based catalysts, inorganic metal-based catalysts, and organometallic-based catalysts. As the metal complex catalyst, there may be selected from Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum) and Co ( Cobalt) metal acetylacetonates in the group consisting of, etc. Specifically, for example, iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate, etc. may be mentioned. Among these metal complex catalysts, in terms of toxicity and catalytic activity, iron acetylacetonate (Fe(acac) ₃ ) and/or manganese acetylacetonate (Mn(acac) ₂ ) are preferred. .

Examples of the organometallic catalyst include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dilauric acid Dibutyltin, dibutyltin dichloride, dioctyltin dilaurate, nickel octoate, nickel naphthenate, cobalt octoate, cobalt naphthenate, bismuth octoate, bismuth naphthenate, bismuth neodecanoate, neodecanoate Zinc acid etc. Preferred organometallic catalysts among these are stannous dioctoate, dibutyltin dilaurate, bismuth neodecanoate, zinc neodecanoate, or mixtures thereof.

啶（quinuclidine）、2-甲基

啶等。該些中，就觸媒活性優異且於工業上能夠獲取的方面而言，作為胺系觸媒，較佳為使用三伸乙基二胺及/或2-甲基三伸乙基二胺。 As the amine-based catalyst, for example, triethylenediamine, 2-methyltriethylenediamine,

quinuclidine, 2-methyl

Pyridine etc. Among these, it is preferable to use triethylenediamine and/or 2-methyltriethylenediamine as the amine-based catalyst in terms of being excellent in catalytic activity and being industrially available.

啶醇、N,N,N',N'-四甲基胍、1,3,5-三(N,N-二甲基胺基丙基)六氫-S-三嗪、1,8-二氮雜雙環[5.4.0]十一碳烯-7、N-甲基-N'-(2-二甲基胺基乙基)哌嗪、N,N'-二甲基哌嗪、二甲基環己胺、N-甲基嗎啉、N-乙基嗎啉、1-甲基咪唑、1,2-二甲基咪唑、1-異丁基-2-甲基咪唑、1-二甲基胺基丙基咪唑、N,N-二甲基己醇胺、N-甲基-N'-(2-羥基乙基)哌嗪、1-(2-羥基乙基)咪唑、1-(2-羥基丙基)咪唑、1-(2-羥基乙基)-2-甲基咪唑、1-(2-羥基丙基)-2-甲基咪唑等。 As other tertiary amine catalysts, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'',N''-pentamethyldiethylenetriamine, N,N,N',N'',N''-pentamethyl-(3-aminopropane base) ethylenediamine, N,N,N',N'',N''-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylene Diamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N' -(2-hydroxyethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propylenediamine, bis(dimethylaminopropyl)amine, bis( Dimethylaminopropyl) isopropanolamine, 3-

Pyridyl alcohol, N,N,N',N'-tetramethylguanidine, 1,3,5-tris(N,N-dimethylaminopropyl)hexahydro-S-triazine, 1,8- Diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl)piperazine, N,N'-dimethylpiperazine, di Methylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-di Methylaminopropylimidazole, N,N-Dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1- (2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole and the like.

Examples of aliphatic cyclic amide compounds that can be used as catalysts include: δ-valerolactam, ε-caprolactam, ω-enantholactam (enantholactam), η-octylactam ( capryllactam), β-propiolactam, etc. Among these aliphatic cyclic amide compounds, ε-caprolactam can more effectively accelerate the hardening of the two-component hardening adhesive.

The content of the catalyst in the two-component curing adhesive of this embodiment is not particularly limited, and may be used in a known amount. The content of the catalyst may be, for example, 0.001 mass % to 5.0 mass % with respect to the total solid content of the two-component hardening type adhesive.

(followed by Accelerator) The two-component hardening adhesive of this embodiment may also contain an adhesion accelerator. Next, the accelerator may be included in only one of the polyisocyanate composition (X) and the polyol composition (Y), or may be included in both. Then, the accelerator has high reactivity with the polyisocyanate composition (X), so it is preferable to function after the polyisocyanate composition (X) and the polyol composition (Y) are in contact. Therefore, it is preferable that the accelerator is contained only in the polyol composition (Y). Next, the accelerator may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) at the time of application of the two-component curing adhesive. Examples of the adhesion accelerator include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and epoxy resins.

As the silane coupling agent, for example, γ-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β( Aminoethyl)-γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, N-phenyl-γ-amine β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidyloxypropyltrimethoxysilane, γ-glycidyloxy Propyltriethoxysilane and other epoxysilanes; vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxysilane Propyltrimethoxysilane and other vinylsilanes; hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, etc.

As a titanate-based coupling agent, for example, tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, Tetraoctyl glycol titanate, tetrastearyl titanium, and the like. As an aluminum-type coupling agent, acetoalkoxy aluminum diisopropoxide etc. are mentioned, for example.

Examples of epoxy resins include: generally commercially available epibis type, novolak type, β-methyl epichloro type, cyclic oxirane type, and glycidyl ether type. , glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polycarboxylate type, amino glycidyl type, resorcinol type and other epoxy resins.

The content of the adhesion promoter in the two-component hardening type adhesive agent of this embodiment is not specifically limited, It can be made into a well-known usage amount. The content of the adhesion accelerator can be, for example, 0% by mass to 50% by mass with respect to the total solid content of the two-component hardening adhesive.

(pigment) The two-component hardening type adhesive agent of this embodiment may use a pigment together as needed. The pigment may be included in only one of the polyisocyanate composition (X) and the polyol composition (Y), or may be included in both. The pigment may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) at the time of application of the two-component hardening adhesive.

The pigment is not particularly limited, and various pigments are disclosed. Examples of pigments include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, metallic Powder pigments, luminous pigments, pearl pigments and other organic pigments, inorganic pigments, plastic pigments, etc.

Examples of organic pigments include various insoluble azo pigments such as benzidine yellow, sunfast yellow, and lake red 4R; soluble azo pigments such as lake red C, carmine 6B, and bordeaux 10; and phthalocyanine blue. , phthalocyanine green and other (copper) phthalocyanine pigments; rhodamine lake, methyl violet lake and other basic dyeing lakes; quinoline lake, fast blue and other mordant dye pigments; anthraquinone pigments, Various building dye pigments such as thioindigo pigments and perionone pigments; various quinacridone pigments such as Cinquasia Red B (Cinquasia RedB); various dioxazine pigments such as dioxazine violet; Various condensed azo pigments such as Cromophtal; Nigrosine, etc.

Examples of inorganic pigments include: various chromates such as yellow lead, zinc chromate, and molybdenum orange; various ferrocyanides such as Prussian blue; ), iron oxide, red iron, chromium oxide green, zirconia and other metal oxides; cadmium yellow, cadmium red, mercury sulfide and other sulfides or selenides; barium sulfate, lead sulfate and other sulfates; calcium silicate, Various silicates such as ultramarine blue; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese violet; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; the Some metal flake pigments, mica/flake pigments; metal pigments such as mica/flake pigments coated with metal oxides, mica-like iron oxide pigments or pearlescent pigments; graphite, carbon black, etc.

Examples of extender pigments include: precipitated barium sulfate, chalk, precipitated calcium carbonate, calcium bicarbonate, cold water stone, alumina white, silica, hydrous fine powder silica (white carbon), superfine powder anhydrous silica (Aerosil), silica sand (silicon dioxide sand), talc, settled magnesium carbonate, bentonite, clay, kaolin, loess, etc. Examples of plastic pigments include "Grandoll PP-1000" and "PP-2000S" manufactured by DIC Corporation.

As the pigment, it is more preferable to use inorganic oxides such as titanium oxide and zinc vitreous as white pigments, and carbon black as black pigments in terms of excellent durability, weather resistance, and designability.

The content of the pigment in the two-component curable adhesive of the present embodiment is preferably 1 to 10 parts by mass based on 100 parts by mass of the total solid content of the polyisocyanate composition (X) and the polyol composition (Y). 400 parts by mass, more preferably 10 to 300 parts by mass. When content of a pigment is 1 mass part - 400 mass parts, it becomes a two-component hardening type adhesive agent excellent in adhesiveness and blocking resistance.

(additive) The two-component hardening adhesive of the present invention may contain other additives other than the above-mentioned components as needed. The additive may be contained in only 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) at the time of application of the two-component hardening adhesive.

Examples of additives include: leveling agents; inorganic fine particles such as colloidal silica and alumina sol; organic fine particles of polymethyl methacrylate; defoamers; anti-sagging agents; property regulator; ultraviolet absorber; metal deactivator; peroxide decomposer; flame retardant; reinforcing agent; plasticizer; lubricant; rust inhibitor; fluorescent whitening agent; Flame agent; antistatic agent; dehydrating agent, etc.

The two-component curable adhesive of this embodiment is a two-component curable adhesive using a curing reaction between a polyisocyanate composition (X) and a polyol composition (Y), and the polyisocyanate composition (X) contains polyisocyanate (A ), the polyol composition (Y) contains the polyol (B) and has an elongational viscosity of 1 Pa·s or less. Therefore, even if the step of applying the component containing the polyol composition (Y) on the film is performed using the two-component curable adhesive of the present embodiment, it is difficult to generate flyaway caused by the polyol composition (Y). Ink and initial cohesion is also excellent. Therefore, the two-component curable adhesive of this embodiment can be suitably used, for example, in the case of producing a laminated film using a production method including a two-component mixing coating step, a production method including a two-component coating step, or the like.

In particular, in the case of producing a laminated film using a method including a two-liquid coating step of coating only the polyol composition (Y) on the film, splashes caused by the polyol composition (Y) tend to occur. ink. According to the two-component curable adhesive of the present embodiment, since the elongational viscosity of the polyol composition (Y) is 1 Pa·s or less, occurrence of misting can be suppressed. In addition, in the method including the step of separately applying two liquids, the initial cohesive force may be insufficient. In the present invention, the early expression of the initial cohesive force can also be realized. Therefore, the two-component curable adhesive of this embodiment can be suitably used especially when manufacturing a laminated film using the method including the two-component coating process of coating only the polyol composition (Y) on a film separately.

In the two-component curable adhesive of the present embodiment, since the elongational viscosity of the polyol composition (Y) is 1 Pa·s or less, the polyol composition (Y) has good fluidity. Therefore, in the two-component curable adhesive of the present embodiment, the reactivity between the polyol composition (Y) and the polyisocyanate composition (X) is good. Therefore, the aging temperature can be lowered, or the aging time can be shortened.

[laminated film] Next, the laminated film of this embodiment will be described in detail using drawings. FIG. 1 is a cross-sectional view showing an example of a laminated film according to this embodiment. As shown in FIG. 1, in the laminated film 11a of this embodiment, the adhesive agent layer 10 is provided between the 1st film W1 and the 2nd film W2. In the laminated film 11 a of the present embodiment, the adhesive layer 10 includes a cured product of the two-component curing adhesive of the above-mentioned embodiment.

(membrane) In the laminated film 11a of the present embodiment, it is preferable to use a plastic film used in a known laminated film as the films used as the first film W1 and the second film W2. As the first film W1, for example, a polyethylene terephthalate (hereinafter sometimes abbreviated as "PET (Polyethylene Terephthalate)") film, a nylon (Oriented Polyamide (Oriented Polyamide, OPA)) film, a biaxial Extended polypropylene (Oriented Polypropylene (OPP)) film, various vapor-deposited films and other base films, aluminum foil, etc. As the second film W2, for example, an unstretched polypropylene (cast polypropylene (Cast Polypropylene, CPP)) film, a linear low density polyethylene (Linear Low Density Polyethylene, LLDPE) film, etc. can be used. Sealant film.

Paper such as natural paper, synthetic paper, and coated paper can be used as the first film W1 and the second film W2. A printing layer may also be provided on the outer surface or the inner surface side of the 1st film W1 and/or the 2nd film W2 as needed.

The laminated film 11a of the present embodiment can be industrially used as a flexible packaging film, a flexible packaging (package whose shape is formed by putting the contents in it) materials, packaging materials filled with detergents, pharmaceuticals, food, beverages, etc. . Specifically, examples of detergents and chemicals include liquid detergents for washing, liquid detergents for kitchens, liquid detergents for baths, liquid soaps for baths, liquid shampoos, and liquid conditioners. It does not specifically limit as food and drink. The laminated film 11a of the present embodiment can be used as a package by being formed 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 contains a cured product of the two-component curing adhesive of the above-mentioned embodiment. Therefore, in the laminated film 11a of the present embodiment, the initial cohesive force is excellent, and even if the step of coating the film with a component containing the polyol composition (Y) is performed, it is difficult to generate ink flying due to the polyol composition (Y). , can be produced using the two-component hardening adhesive of the above embodiment. Therefore, the laminated film of the present embodiment can be efficiently produced using, for example, a production method including a two-liquid mixed coating step, a production method including a two-liquid separate coating step, and the like. Furthermore, since the two-component curing adhesive of the above-mentioned embodiment cures in a short time and/or at a low temperature, the laminated film 11a of the present embodiment can be produced with less energy.

[Laminated film production equipment] Next, the manufacturing apparatus of the laminated film 11a of this embodiment is demonstrated in detail with reference to drawing. Fig. 2 is a front view of a manufacturing apparatus of a laminated film according to the present embodiment. Fig. 3 is a front view showing a main part of a polyisocyanate coating unit in the production apparatus of the laminated film shown in Fig. 2 . Fig. 4 is a front view showing a main part of a polyol application unit in the multilayer film manufacturing apparatus shown in Fig. 2 .

The laminated film manufacturing apparatus 1 shown in FIG. 2 is an apparatus for manufacturing the laminated film 11a of the present embodiment described above. The laminated film 11a of the present embodiment uses the two-component curing adhesive of the present embodiment, and The 1st film W1 unwound from the roll and the 2nd film W2 unwound from the roll are bonded together, the adhesive agent layer 10 is formed between the 1st film W1 and the 2nd film W2, and it winds up in roll form.

As shown in FIG. 2 , the laminated film manufacturing apparatus 1 of this embodiment includes a first unwinding unit 11, a polyisocyanate coating unit 12 (first coating unit), a second unwinding unit 13, a polyol coating unit 14 (second coating unit), and a bonding device 15 . The first unwinding unit 11 sends out the first film W1 to the polyisocyanate coating unit 12 . The first film W1 is rotatably attached to the film attachment portion 111 of the first unwinding portion 11 .

The polyisocyanate coating part 12 applies the polyisocyanate composition (X) of the two-component hardening type adhesive agent of this embodiment to the 1st film W1 sent out from the 1st unwinding part 11. As shown in FIG. 3 , the polyisocyanate coating unit 12 is a four-squeeze roll type roll coater. The polyisocyanate coating unit 12 includes an application roll 121 , a doctor roll 122 , a metering roll 123 , a coating roll 124 , and a backing roll 125 . The liquid storage part 120 is included in the facing part of the application roller 121 and the doctor roller 122.

The application roller 121 is a roller including an outer peripheral surface of an elastic material such as rubber. The doctor roller 122 is a roller including a metal (non-elastic material) outer peripheral surface. As shown in FIG. 3 , the application roller 121 and the doctor roller 122 are rotatably supported by the polyisocyanate coating part 12 so that their rotation axes are parallel to each other. The outer peripheral surface of the application roller 121 and the outer peripheral surface of the doctor roller 122 oppose with a slight gap.

A pair of weir plates 126 are provided at predetermined intervals in the direction of the rotation axis of the application roller 121 and the doctor roller 122 on the upper portion of the facing portion of the application roller 121 and the doctor roller 122 . The liquid storage portion 120 is formed by a pair of weir plates 126 , the outer peripheral surface of the application roller 121 , and the outer peripheral surface of the doctor roller 122 . The liquid storage unit 120 temporarily stores the polyisocyanate composition (X). The polyisocyanate composition (X) is supplied to the liquid storage unit 120 from a polyisocyanate supply unit (not shown). Thereby, the polyisocyanate composition (X) stored in the liquid storage part 120 is kept at a constant amount.

The doctor roll 122 preferably includes an unillustrated temperature adjustment unit. The temperature adjustment unit maintains the polyisocyanate composition (X) stored in the liquid storage unit 120 at a constant temperature to stabilize the viscosity of the polyisocyanate composition (X). Thereby, the outer peripheral surface of the doctor roll 122 is maintained in constant temperature. As shown in FIG. 3 , the application roller 121 and the scraper roller 122 rotate downward at the liquid storage part 120 . Thus, the polyisocyanate composition (X) passing through the minute gap is applied to the outer peripheral surface of the doctor roll 122 .

As shown in FIG. 3 , the polyisocyanate coating unit 12 supports a metering roll 123 , a coating roll 124 , and a backup roll 125 so that rotation is possible. The polyisocyanate composition (X) coated on the outer peripheral surface of the doctor roll 122 is transferred to the metering roll 123 . The rotation axis of the metering roller 123 is arranged parallel to the rotation axis of the doctor roller 122 . The outer peripheral surface of the metering roller 123 is formed of an elastic material such as rubber. The outer peripheral surface of the metering roller 123 is in pressure contact with the outer peripheral surface of the doctor roller 122 .

The polyisocyanate composition (X) applied on the outer peripheral surface of the metering roller 123 is transferred to the application roller 124 . The rotation axis of the coating roller 124 is arranged parallel to the rotation axis of the metering roller 123 . In addition, the outer peripheral surface of the coating roller 124 is formed of a metal material. The outer peripheral surface of the coating roller 124 is in pressure contact with the outer peripheral surface of the metering roller 123 .

The backup roll 125 is arranged such that the coating roll 124 and the rotation shaft are parallel to each other. The backup roll 125 and the coating roll 124 hold|interpose the 1st film W1, and convey the 1st film W1. The backup roll 125 assists the transfer of the polyisocyanate composition (X) applied on the outer peripheral surface of the coating roll 124 to the first film W1 . The outer peripheral surface of the backup roller 125 is formed of an elastic material such as rubber. Like the doctor roll 122, the coating roller 124 preferably maintains a constant temperature of the outer peripheral surface by a temperature adjustment unit (not shown). Thereby, the viscosity of the polyisocyanate composition (X) coated on the first film W1 is stabilized.

The second unwinding unit 13 sends out the second film W2 to the polyol coating unit 14 . The second film W2 is rotatably attached to the film attachment portion 131 of the second unwinding portion 13 . The polyol coating unit 14 coats the polyol composition (Y) of the two-component curable adhesive of the present embodiment on the second film W2 sent out from the second unwinding unit 13 . As shown in FIG. 4 , the polyol coating unit 14 is a gravure coater (gravure coater) that coats the polyol composition (Y) by gravure printing. The polyol coating unit 14 includes a gravure roll 141 , a chamber 142 , an impression cylinder 143 , a coating liquid tank 144 , a pump 145 , and a temperature regulator 146 .

The gravure roll 141 is a metal roll that is rotatably supported by the polyol coating unit 14 . A plurality of concave portions (gravure patterns) 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.

As shown in FIG. 4 , the chamber 142 is a container for storing the polyol composition (Y). The chamber 142 is disposed on one radial side of the gravure roll 141 . The chamber 142 includes a storage portion 142a that stores the polyol composition (Y). The storage portion 142a opens toward 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 142 a. The storage part 142a is sealed by the scraper 142b, the sealing plate 142c, and a pair of side plates 142d.

The chamber 142 includes a plate-like scraper 142b. The scraper 142b protrudes toward the gravure roll 141 from the opening upper end of the reservoir 142a. The material of the scraper 142b is not particularly limited, and may be metal or resin, for example, may include stainless steel. The front end portion of the scraper 142b is in pressure contact with the outer peripheral surface of the gravure roll 141 . The front end portion of the scraper 142b seals the downstream side of the storage portion 142a in the roller rotation direction. The scraper 142 b scrapes and measures excess polyol composition (Y) adhering to the outer peripheral surface of the gravure roll 141 by the rotation of the gravure roll 141 .

The chamber 142 includes a plate-shaped sealing plate 142c. The sealing plate 142c is made of resin. The sealing plate 142c protrudes toward the gravure roll 141 from the opening lower end portion of the storage portion 142a. The front end portion of the sealing plate 142c is in pressure contact with the outer peripheral surface of the gravure roll 141 . The front end portion of the seal plate 142c seals the upstream side of the storage portion 142a in the roller rotation direction.

The chamber 142 includes 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 in the direction of the rotation axis of the gravure roll 141 . As shown in FIG. 4 , the side surface of the side plate 142 d on the gravure roll 141 side has an arcuate shape along the shape of the gravure roll 141 and is brought into pressure contact with the gravure roll 141 .

As shown in FIG. 4 , the impression roll 143 holds the second film W2 between the gravure roll 141 and conveys the second film W2 . The impression cylinder 143 press-contacts the second film W2 to the gravure roll 141 , and transfers the polyol composition (Y) coated on the outer peripheral surface of the gravure roll 141 to the second film W2 . In general, ink mist occurs when the polyol composition (Y) moves between rollers by transfer. According to this embodiment, the misting of the polyol composition (Y) occurs in the vicinity where the gravure roll 141 and the impression cylinder 143 are brought into pressure contact. When splashing occurs, in order to suppress generation of splashing, it is necessary to reduce the rotation speed of each roller and the conveyance speed of the 2nd film W2. However, if the conveyance speed of the 2nd film W2 is made low, the production efficiency of the laminated film 11a will fall. In the present embodiment, by using a composition having a specific elongational viscosity as the polyol composition (Y), generation of misting can be suppressed. As a result, the laminated film 11a having excellent characteristics can be efficiently produced.

The coating liquid tank 144 is a container for storing the polyol composition (Y). As shown in FIG. 4 , the coating liquid tank 144 is connected to a pump 145 that flows the polyol composition (Y) into the chamber 142 via piping. In addition, the coating liquid tank 144 is connected to the chamber 142 via piping. Thereby, the polyol composition (Y) overflowing from the storage portion 142 a of the chamber 142 is recovered into the coating liquid tank 144 .

The pump 145 is connected to the coating liquid tank 144 and the chamber 142 through piping. The pump 145 supplies the polyol composition (Y) stored in the coating liquid tank 144 to the storage portion 142 a of the chamber 142 . As the pump 145 , for example, a sine pump can be used.

The temperature adjuster 146 adjusts the temperature of the polyol composition (Y) stored in the coating liquid tank 144 . Thereby, the temperature of the polyol composition (Y) is kept constant, and the viscosity of the polyol composition (Y) is stabilized. The temperature regulator 146 is, for example, a water temperature regulator that heats water as a heat medium with a heater and circulates it around the polyol composition (Y) stored in the coating liquid tank 144 .

As shown in FIG. 2 , the bonding device 15 includes a bonding part 151 and a winding part 152 . The bonding unit 151 combines the polyisocyanate composition (X) coated surface of the first film W1 sent out from the polyisocyanate coating unit 12 with the polyol composition of the second film W2 sent out from the polyol coating unit 14 . The coated surface of the object (Y) is bonded. The winding part 152 winds up the laminated film 11 a bonded by the bonding part 151 .

As shown in FIG. 2, the bonding part 151 has a pair of lamination roll R1, R2. The lamination roll R1 and the lamination roll R2 sandwich the 1st film W1 and the 2nd film W2, join, and convey. The temperature of the outer peripheral surface of two lamination rolls R1 and R2 is kept constant by the temperature control part which is not shown in figure. This stabilizes the curing of the two-component curing adhesive.

As shown in FIG. 2 , the bonding unit 151 passes the first film W1 and the second film W2 between the two lamination rolls R1 and R2 facing each other, and the first film W1 sent out from the polyisocyanate coating unit 12 The application surface of the 2nd film W2 sent out from the polyol application part 14 is in contact with the application surface of the 2nd film W2, and is bonded together. In the laminating part 151, by mixing the polyisocyanate composition (X) coated on the first film W1 and the polyol composition (Y) coated on the second film W2, a two-component hardening adhesive is started. hardening, the first film W1 and the second film W2 are bonded together and fixed.

The winding part 152 winds up the laminated film 11 a formed by bonding the first film W1 and the second film W2 in the bonding part 151 .

[Manufacturing method of laminated film] Next, as the method of manufacturing the laminated film of the present embodiment, the production of the laminated film shown in FIG. 1 using the manufacturing apparatus 1 of the laminated film shown in FIGS. The case of the laminated film 11a will be described as an example. The manufacturing method of the laminated film 11a of the present embodiment includes a step of applying two liquids separately and a step of forming an adhesive layer. In this embodiment, the two-liquid separate coating step and the adhesive agent layer forming step are continuously performed.

(Two liquid coating steps separately) The separate coating steps of the two liquids include: a first coating step of coating the polyisocyanate composition (X) containing polyisocyanate (A) on the first film W1; and a second coating step of coating the polyisocyanate composition (X) containing polyisocyanate (B ) and a polyol composition (Y) having an elongational viscosity of 1 Pa·s or less is applied to the second film W2. In this embodiment, the first coating step and the second coating step are performed simultaneously.

"First Coating Step" A method of performing the first coating step using the laminated film manufacturing apparatus 1 shown in FIGS. 2 to 4 will be described. First, the first film W1 is fed out from the first unwinding unit 11 to the polyisocyanate coating unit 12 . In the polyisocyanate coating section 12, each roll is rotated in the direction indicated by the arrow in FIG. 3 . Thereby, the polyisocyanate composition (X) stored in the liquid storage part 120 is coated on the surface of the doctor roll 122 .

In this embodiment, it is preferable to set the temperature of the polyisocyanate composition (X) stored in the liquid storage part 120 at 25° C. to 80° C., more preferably at 25° C. ℃～40℃. In this embodiment, the shear viscosity of the polyisocyanate composition (X) at 40° C. is preferably 3000 mPa·s or less, more preferably 2000 mPa·s or less.

The polyisocyanate composition (X) applied on the doctor roll 122 is transferred to the metering roll 123 and the coating roll 124 in this order. Each roll of the polyisocyanate coating part 12 is set so that rotation speed may become larger sequentially. Thereby, the thickness of the coating film of the polyisocyanate composition (X) is gradually reduced, and is adjusted so as to become a predetermined coating film thickness (coating amount) by the coating roller 124 .

The polyisocyanate composition (X) transferred to the application roll 124 is transferred to the first film W1 conveyed between the application roll 124 and the backup roll 125 . Thereby, the polyisocyanate composition (X) is coated on the first film W1. In this embodiment, the coating amount of the polyisocyanate composition (X) coated on the first film W1 is preferably 0.5 g/m ² to 3.0 g/m ² , more preferably 0.5 g/m ² to 2.0 g /m ² . In the polyisocyanate coating unit 12 , the first film W1 coated with the polyisocyanate composition (X) is sent out to the bonding device 15 .

"Second Coating Step" Next, a method of performing the second coating step using the laminated film manufacturing apparatus 1 shown in FIGS. 2 to 4 will be described. First, the second film W2 is fed out from the second unwinding unit 13 to the polyol coating unit 14 . In the polyol coating section 14, the gravure roll 141 and the impression roll 143 are rotated in the direction indicated by the arrow in FIG. 4 . By the rotation of the gravure roll 141 , the polyol composition (Y) in the chamber 142 is applied to the second film W2 via the surface of the gravure roll 141 .

In this embodiment, the coating amount of the polyol composition (Y) coated on the second film W2 is preferably 0.5 g/m ² to 3.0 g/m ² , more preferably 0.5 g/m ² to 2.0 g /m ² .

In this embodiment, the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is preferably set at 25° C. to 80° C., more preferably at 25° C. to 25° C. 40°C. In the present embodiment, the viscosity of the polyol composition (Y) is set to a viscosity suitable for a gravure coater.

The rotation direction of the gravure roll 141 may be the same direction as the conveyance direction of the 2nd film W2, ie, normal rotation, or may be the opposite direction to the conveyance direction of the 2nd film W2, ie, reverse rotation. In this embodiment, as shown in FIG. 4 , the gravure roll 141 transfers the polyol composition (Y) to the second film W2 while rotating in a direction opposite to the conveyance direction of the second film W2 . Thereby, the appearance of the polyol composition (Y) coated on the second film W2 can be made to have a favorable appearance without vertical stripes, texture of a roll, or the like. In the polyol coating unit 14 , the second film W2 coated with the polyol composition (Y) is sent out to the bonding device 15 .

(Adhesive layer formation step) In the adhesive layer forming step, by laminating the first film W1 and the second film W2, the polyisocyanate composition (X) coated on the first film W1 and the polyol coated on the second film W2 The composition (Y) undergoes a hardening reaction upon contact.

In the bonding part 151 of the bonding device 15, as shown in FIG. 2, in the state where the first film W1 and the second film W2 are in contact, they are sandwiched by two laminating rollers R1 and R2 arranged oppositely, and passed through Between two lamination rollers R1, R2. Then, the first film W1 and the second film W2 are bonded together by pressure from the two lamination rolls R1 and R2.

In the present embodiment, it is preferable to set the temperature of the outer peripheral surfaces of the two lamination rolls R1 and R2 to 40°C to 80°C, more preferably to 40°C to 60°C. The pressure from the two lamination rolls R1 and R2 to the first film W1 and the second film W2 can be, for example, 3 kg/cm ² to 300 kg/cm ² . In the present embodiment, the coated surface of the first film W1 sent out from the polyisocyanate coating unit 12 and the second film W2 sent out from the polyol coating unit 14 are separated by being sandwiched between the two lamination rolls R1 and R2. contact with the coated surface. As a result, the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2 are mixed to start curing of the two-component curable adhesive.

The laminated film 11a having the adhesive layer 10 between the first film W1 and the second film W2 can be obtained by curing the two-component curing adhesive. The laminated film 11 a produced by bonding the first film W1 and the second film W2 by the bonding part 151 is conveyed to the winding part 152 . The laminated film 11 a conveyed to the winding part 152 is wound up by the winding part 152 .

In the method for producing the laminated film 11a according to this embodiment, the film conveyance speed (winding speed of the laminated film 11a in the winding unit 152 ) at the time of producing the laminated film 11a can be set to, for example, 30 m/min to 300 m/min. , preferably set at 100 m/min to 250 m/min. In the method for producing the laminated film 11a of the present embodiment, the laminated film 11a is produced using the two-component curable adhesive of the present embodiment, so the occurrence of misting caused by the polyol composition (Y) can be suppressed. Therefore, even if the film conveyance speed is set to 30 m/min or more, workability does not decrease due to ink flying of the polyol composition (Y). Therefore, a laminated film can be efficiently produced continuously at a high film conveyance speed of 30 m/min or more. If the film conveyance speed exceeds 300 m/min, it may cause coating failures other than ink flying, failures in the conveyance itself, and failures at the time of sticking. Therefore, the film conveyance speed is preferably set at 300 m/min or less.

Regarding the laminated film 11a obtained by the production method of this embodiment, the first film W1 and the second film W2 are bonded together in the bonding part 151, and after being wound up by the winding part 152, the film is heated at room temperature or heated as necessary. It was stored under low temperature for 3 hours to 48 hours to perform aging. By aging, the two-component curing adhesive is sufficiently cured, and may exhibit practical properties as the adhesive layer 10 . In the present embodiment, the polyol composition (Y) uses a two-component hardening adhesive having a specific elongational viscosity and excellent initial cohesion, so that aging time can be shortened. In addition, since the initial cohesion of the two-component curable adhesive is high, the laminated film 11a wound up on the winding portion 152 can be easily processed before aging. Therefore, in the manufacturing method of the present embodiment, the selection range of manufacturing steps is wide, and work efficiency can be improved.

The manufacturing apparatus 1 of the laminated film 11a of this embodiment has: the polyisocyanate coating part 12 which applies the polyisocyanate composition (X) to the 1st film W1; The polyol composition (Y) of s or less is applied to the second film W2; The coated surface of the object (Y) is bonded. Therefore, the manufacturing apparatus 1 of the laminated film 11a of the present embodiment can be suitably used to manufacture the laminated film 11a by the manufacturing method of the present embodiment including the step of separately applying the two liquids using the two-liquid curable adhesive of the present embodiment. Case.

In the manufacturing apparatus 1 of the laminated film 11 a of the present embodiment, the polyol coating unit 14 applies the polyol composition (Y) having an elongational viscosity of 1 Pa·s or less to the second film W2 . Therefore, the occurrence of misting in the polyol composition (Y) is suppressed, and the multilayer film 11 a can be efficiently produced continuously at a high film conveyance speed.

In the manufacturing apparatus 1 of the laminated film 11a of this embodiment, the occurrence of misting caused by the polyol composition (Y) at the time of manufacturing the laminated film 11a can be suppressed. Therefore, the polyol coating unit 14 may include a gravure coater that can expand the range of options such as the viscosity of the polyol composition (Y), or may include a roll coating that is likely to cause misting of the polyol composition (Y). machine, the option of the coating device for the polyol composition (Y) in the polyol coating section 14 can be increased. In the case where a gravure coater is selected as the coating device for the polyol composition (Y) in the polyol coating section 14, even if the viscosity of the polyol composition (Y) is low, dripping occurs in the roll coater. In the case of adverse conditions such as liquid, it is also possible to manufacture a high-quality laminated film 11a that does not cause dripping and improves coating quality. Moreover, by using a gravure coater, the structure of the polyol coating part 14 can be simplified, and the manufacturing apparatus of the laminated film 11a can be downsized.

In the manufacturing apparatus 1 of the laminated film 11 a of the present embodiment, a roll coater is used in the polyisocyanate coating part 12 where the polyisocyanate composition (X) with a high viscosity is coated on the first film W1 . By using a roll coater, coating can be performed even when the viscosity of a polyisocyanate composition (X) is high, and the range of selection of the material of a polyisocyanate composition (X) expands.

The manufacturing method of the laminated film 11a of this embodiment includes: a two-liquid coating step, including a first coating step and a second coating step. The first coating step applies the polyisocyanate composition (X) to The first film W1, the second coating step of coating the polyol composition (Y) with an elongational viscosity of 1 Pa·s or less on the second film W2; and the adhesive layer forming step of laminating the first film W1 and the second film W2 bring the polyisocyanate composition (X) coated on the first film W1 into contact with the polyol composition (Y) coated on the second film W2 to cause a hardening reaction. Since the method of manufacturing the laminated film 11 a of the present embodiment includes a step of applying two liquids separately, the step of mixing the polyisocyanate composition (X) and the polyol composition (Y) is unnecessary. Therefore, compared with the case including the step of mixing the polyisocyanate composition (X) and the polyol composition (Y), workability is excellent. In addition, since the polyisocyanate composition (X) and the polyol composition (Y) are not mixed, there is no limit to the pot life of the two-component curing adhesive, and the two-component curing adhesive of this embodiment that hardens quickly can be used. agent.

In the method for producing the laminated film 11 a of the present embodiment, in the second coating step, the polyol composition (Y) having an elongational viscosity of 1 Pa·s or less is coated on the second film W2 . Therefore, in the method for producing the laminated film 11a of the present embodiment, the use of the two-component curable adhesive of the present embodiment can suppress the occurrence of ink misting caused by the polyol composition (Y) in the second coating step. At the same time, laminated films are efficiently manufactured continuously at a high film conveyance speed.

In the above embodiment, a roll coater is used as the polyisocyanate coating part 12 , but a gravure coater may be used as the polyisocyanate coating part 12 when the viscosity of the polyisocyanate composition (X) is low. In addition, in the above-described embodiment, a gravure coater is used as the polyol coating unit 14, but a roll coater may be used as the polyol coating unit 14 when the polyol composition (Y) can be coated. .

In addition, in the polyol coating unit 14 in the manufacturing apparatus 1 of the laminated film 11a of the above-mentioned embodiment, the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is adjusted by the temperature regulator 146 , Furthermore, the temperature of the polyol composition (Y) stored in the storage part 142a of the chamber 142 and/or the temperature of the gravure roll 141 can also be adjusted. Thereby, the viscosity of the polyol composition (Y) at the time of coating can be made more stable, and the coating quality and the quality of the laminated film 11a can be further improved.

In the present embodiment, the case where the laminated film 11a is manufactured by a manufacturing method including a step of separately applying two liquids by using the manufacturing apparatus 1 of the laminated film 11a is taken as an example for description. The manufacturing apparatus 1 of the laminated film 11a has: The polyisocyanate coating part 12 applies the polyisocyanate composition (X) to the first film W1; the polyol coating part 14 applies the polyol composition (Y) to the second film W2; and a bonding device 15. The first film W1 and the second film W2 are bonded together, and the laminated film 11a can also be produced by a production method including a two-liquid mixing and coating step using the production equipment shown below, for example.

FIG. 5 is a front view illustrating another example of the manufacturing apparatus used for manufacturing the laminated film according to the present embodiment. The laminated film manufacturing apparatus 1A shown in FIG. 5 is an apparatus for manufacturing the laminated film 11a of the present embodiment described above. The laminated film 11a of the present embodiment uses the two-component curing adhesive of the present embodiment, The 1st film W1 unwound from the roll and the 2nd film W2 unwound from the roll are bonded together, the adhesive agent layer 10 is formed between the 1st film W1 and the 2nd film W2, and it winds up in roll form.

The manufacturing apparatus 1A of the laminated|multilayer film shown in FIG. The difference between the manufacturing apparatus 1A of laminated film shown in FIG. 5 and the manufacturing apparatus 1 of laminated film shown in FIG. The polyol coating part 14 in the manufacturing apparatus 1 of the laminated film shown. 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. 2 are denoted by the same reference numerals, and description thereof will be omitted.

The difference between the mixed solution application section 12A in the laminated film manufacturing apparatus 1A shown in FIG. 5 and the polyisocyanate coating section 12 in the laminated film manufacturing apparatus 1 shown in FIG. The mixed solution of the polyisocyanate composition (X) and the polyol composition (Y) of the two-component curable adhesive of this embodiment is coated with the 1st film W1 sent out from the part 11. An unillustrated mixing device for mixing the polyisocyanate composition (X) and the polyol composition (Y) of the two-component curable adhesive is installed in the laminated film manufacturing apparatus 1A shown in FIG. 5 . In addition, instead of the polyisocyanate supply part of the laminated film manufacturing apparatus 1 shown in FIG. 2, the laminated film manufacturing apparatus 1A shown in FIG.

As a method of manufacturing the laminated film 11 a of the present embodiment using the laminated film manufacturing apparatus 1A shown in FIG. 5 , for example, a manufacturing method shown below can be used. First, the first film W1 is fed out from the first unwinding unit 11 to the mixed liquid application unit 12A. In the mixed solution application section 12A, each roller is rotated in the direction indicated by the arrow in FIG. 3 . Thereby, the liquid mixture of the polyisocyanate composition (X) and the polyol composition (Y) stored in the liquid storage part 120 is applied to the surface of the doctor roll 122 .

In this embodiment, the temperature of the mixed liquid stored in the liquid storage unit 120 is preferably set at 25° C. to 80° C., more preferably at 25° C. to 40° C. by a temperature adjustment unit not shown. In this embodiment, the shear viscosity of the mixed liquid is preferably below 2000 mPa·s at 40° C., more preferably below 1800 mPa·s. In the present embodiment, the curing of the two-component curing adhesive starts by mixing the polyol composition (Y) and the polyisocyanate composition (X) in the mixing device.

The mixed solution applied to the doctor roll 122 is transferred to the metering roll 123 and the coating roll 124 in this order. The mixed solution transferred to the coating roll 124 is transferred to the first film W1 conveyed between the coating roll 124 and the backup roll 125 . Thereby, the liquid mixture is applied on the first film W1. In this embodiment, the coating amount of the mixed solution coated on the first film W1 is preferably 0.5 g/m ² -3.0 g/m ² , more preferably 0.5 g/m ² -2.0 g/m ² . In the mixed liquid application part 12A, as shown in FIG. 5, the 1st film W1 to which the mixed liquid was applied is sent out to the bonding apparatus 15. As shown in FIG.

Moreover, as shown in FIG. 5, the 2nd film W2 is sent out from the 2nd unwinding part 13, and is sent out to the bonding apparatus 15. In the bonding unit 151 of the bonding device 15, as shown in FIG. R1, R2 clamp, and pass between two lamination rollers R1, R2. Then, the first film W1 and the second film W2 are bonded together by pressure from the two lamination rolls R1 and R2.

In the present embodiment, it is preferable to set the temperature of the outer peripheral surfaces of the two lamination rolls R1 and R2 to 40°C to 80°C, more preferably to 40°C to 60°C. The pressure from the two lamination rolls R1 and R2 to the first film W1 and the second film W2 can be, for example, 3 kg/cm ² to 300 kg/cm ² .

The laminated film 11a having the adhesive layer 10 between the first film W1 and the second film W2 can be obtained by curing the two-component curing adhesive. The laminated film 11 a produced by bonding the first film W1 and the second film W2 by the bonding part 151 is conveyed to the winding part 152 . The laminated film 11 a conveyed to the winding part 152 is wound up by the winding part 152 .

In the method for producing the laminated film 11a according to this embodiment, the film conveyance speed (winding speed of the laminated film 11a in the winding unit 152 ) at the time of producing the laminated film 11a can be set to, for example, 30 m/min to 300 m/min. , preferably set at 100 m/min to 250 m/min. In the method for producing the laminated film 11a of the present embodiment, the laminated film 11a is produced using the two-component curing adhesive of the present embodiment, so that splashing caused by the mixed liquid as a component containing the polyol composition (Y) can be suppressed. ink. Therefore, even if the film conveyance speed is set to 30 m/min or more, workability will not be lowered due to ink flying of the mixed liquid. Therefore, a laminated film can be efficiently produced continuously at a high film conveyance speed of 30 m/min or more. If the film conveyance speed exceeds 300 m/min, it may cause coating failures other than ink flying, failures in the conveyance itself, and failures at the time of sticking. Therefore, the film conveyance speed is preferably set at 300 m/min or less.

The laminated film 11a of the present embodiment is manufactured using the two-component curing adhesive of the present embodiment, so even if a mixed liquid containing a component of the polyol composition (Y) is applied on the second film W2, it is less likely to cause Fog caused by polyol composition (Y). Therefore, the laminated film 11 a of the present embodiment can be efficiently produced using a production method including a two-liquid mixture coating step.

In the above-described embodiment, a production method including a step of coating only the polyol composition (Y) on a film using a two-liquid separate coating step is cited as a production method including a two-liquid separate coating step to manufacture a laminated film. The case of 11a will be described as an example, but as a production method including a step of applying two liquids separately, for example, the method (1) or the method (2) shown below can also be used.

(1) In the first coating step, a mixture of the polyisocyanate composition and the polyol composition is coated on the first film, and in the second coating step, a solution containing a hardening accelerator is coated on the second film. (2) In the first coating step, a mixture of a part of the polyol composition and the polyisocyanate composition is coated on the first film, and in the second coating step, the remaining polyol composition is coated. A solution of the portion and the hardening accelerator is applied to the second film. [Example]

Hereinafter, the present invention will be described more specifically by means of examples. In addition, this invention is not limited only to the following Example. In the following examples, "parts" and "%" are based on mass unless otherwise specified.

(polyisocyanate composition (X)) [Manufacture of polyisocyanate (A-1)] 4,4'-MDI: 41.9 parts, 2,4'-MDI: 13.0 parts, and xylylene diisocyanate: 0.1 parts were charged into a reaction vessel in a flask including a stirrer, a thermometer, and a nitrogen gas introduction tube. Stir under nitrogen and heat to 60°C. In the flask, 20.0 parts of difunctional polypropylene glycol (hereinafter referred to as "PPG (Polypropylene glycol)") with a number average molecular weight of 400 (hereinafter referred to as "PPG"): 20.0 parts, and 25.0 parts of difunctional PPG with a number average molecular weight of 2000 were added dropwise several times. The polyisocyanate (A-1) was obtained by stirring at 80 degreeC for 5 hours - 6 hours, and making it perform a urethanization reaction.

About polyisocyanate (A-1), the isocyanate content rate was measured by the titration method using di-n-butylamine. As a result, it was 14% by mass. Moreover, about the polyisocyanate (A-1), the melt shear viscosity in 40 degreeC was measured. The result was 1500 mPa·s.

(Polyol composition (Y-1) to polyol composition (Y-6)) The polyol (B), polyamine (C) and additives described in Table 1 were mixed in the ratio shown in Table 1 to obtain polyol composition (Y-1) to polyol composition (Y-6).

[Table 1] Hydroxyl value or amine value (mgKOH/g) Y-1 Y-2 Y-3 Y-4 Y-5 Y-6 Polyol (B) (parts by mass) castor oil 160 73.3 70.0 70.0 70.0 70.0 D-1000 112 18.3 76.8 15.8 20.7 16.75 15.5 TE-360 520 18.2 Aikenuo (EXCENOL) 430 400 6.6 6.6 7.5 EDP300 750 6.6 4.4 Polyamine (C) (parts by mass) EC310 350 6.6 4.4 6.6 6.8 Additives (parts by mass) ε-Caprolactam 0 0.9 1.0 0.5 δ-Verolactamide 0 5.0 DBTDL 0 0.05 Bi-Zn 0 0.2 OFS-6040 0 0.6 KBM-903 0 0.3 total 100.0 100.0 100.0 100.0 100.0 100.0 Total hydroxyl value + amine value (mgKOH/g) 187.3 180.7 179.2 183.6 180.3 183.2

The abbreviations in Table 1 are as follows. "Polyol (B)" Castor oil: Refined castor oil (manufactured by Ito Oil Co., Ltd., hydroxyl value 160 mgKOH/g, melt shear viscosity 250 mPa·s at 40°C) D-1000: Polypropylene glycol (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., number average molecular weight about 1,000, hydroxyl value 112 mgKOH/g, melt shear viscosity 150 mPa·s at 40°C) Actcall D-1000 TE-360: Propoxylated Triethanolamine EXCENOL 430: polypropylene glycol (manufactured by AGC Co., Ltd.; functional group 3, number average molecular weight about 430, hydroxyl value 400 mgKOH/g, melt viscosity at 25°C 350 mPa s) EDP-300: N,N,N',N'-Tetrakis(2-hydroxypropyl)ethylenediamine (manufactured by ADEKA Co., Ltd.)

"Polyamine (C)" EC310: polyoxypropylene polyamine (manufactured by BASF) Baxxdur EC310 "catalyst" ε-caprolactam: 2-oxohexamethyleneimine (manufactured by Kanto Chemical Co., Ltd.) δ-Verolactamide: Tetrahydro-2H-pyran-2-one (manufactured by Kanto Chemical Co., Ltd.) DBTDL: Dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.) Neostann U-100 Bi-Zn: Mixed catalyst of bismuth neodecanoate and zinc neodecanoate (manufactured by The Shepherd Chemical Company) Bicat8108/Z mixed "Following Accelerator" OFS-6040: 3-glycidyloxypropyltrimethoxysilane (manufactured by Toray Dow Corning Co., Ltd.) KBM903: 3-Aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

(Polyol composition (Y-7) to polyol composition (Y-8)) As polyol component Y-7 and polyol component Y-8, those shown below were prepared. Y-7: HA-234B (manufactured by DIC Co., Ltd.), hydroxyl value: 90 mgKOH/g Y-8: HA-700B (manufactured by DIC Co., Ltd.), hydroxyl value: 120 mgKOH/g

Regarding the materials used in the polyol composition (Y-1) to the polyol composition (Y-8), the hydroxyl value or the amine value was determined by the method shown below. The hydroxyl value was calculated|required based on the hydroxyl value measuring method of JIS-K0070. The amine value is calculated according to the amine value standard test method of American Society for Testing Materials (ASTM) D2073. Then, the total of the hydroxyl values and amine values contained in the polyol composition (Y-1) to the polyol composition (Y-8) was calculated. The results are shown in Table 1 and Table 2.

Regarding the polyol composition (Y-1) to the polyol composition (Y-8), the elongational viscosity at an elongation speed of 4000 s ⁻¹ was measured by the method shown below. The results are shown in Table 2. The elongational viscosity was measured in accordance with the capillary rheometer evaluation method described in JIS-7199 (International Organization for Standardization (ISO) 11443, ASTM D 3835). Specifically, using a double capillary type device (manufactured by Gottfert; rheometer (RHEOGRAPH) 20), a capillary mold with a length of 10 mm and a diameter of 0.5 mm and a mold with a length of 0.25 mm and a diameter of 0.5 mm were used. The capillary mold uses Bagley Correction to remove the pressure loss from the apparent shear viscosity (pressure) measured at a temperature of 40°C and a shear rate of 1000 s ^-1 to 300000 s ^-1 to obtain a true shear viscosity. Furthermore, from the true shear viscosity and pressure loss, the elongational viscosity corresponding to the elongation speed is obtained using the Cogswell equation.

"Example 1 to Example 6, Comparative Example 1 to Comparative Example 2" Use polyisocyanate (A-1) and polyol composition (Y-1) to polyol composition (Y-8) in the ratio shown in Table 2, and use Fig. 2 to Fig. 4 by the method shown below In the production apparatus shown, the laminated films of Examples 1 to 6 and Comparative Examples 1 to 2 were produced at film transport speeds of 100 m/min, 150 m/min, 200 m/min, and 250 m/min. .

[Table 2] Functional group amount Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Polyisocyanate composition (parts by mass) A-1 14.0 100 100 100 100 100 100 100 100 Polyol composition (parts by mass) Y-1 187.3 70 Y-2 180.7 70 Y-3 179.2 70 Y-4 183.6 70 Y-5 180.3 70 Y-6 183.2 70 Y-7 90.0 140 Y-8 120.0 100 NCO excess rate 1.43 1.48 1.49 1.45 1.48 1.46 1.48 1.56 Y-1～Y-8 elongational viscosity (Pa·s) 0.67 0.52 0.47 0.74 0.88 0.52 3.55 14.0 Evaluation of ink splashing (film transfer speed: m/min) 100 4 4 4 4 4 4 3 2 150 4 4 4 4 4 4 2 2 200 4 4 4 4 4 4 1 1 250 4 4 4 4 4 4 1 1 Initial Cohesion Evaluation 3 hours 4 4 4 4 4 4 1 1 6 hours 4 4 4 4 4 4 1 1 12 hours 4 4 4 4 4 4 1 1 24 hours 4 4 4 4 4 4 2 2

In Table 2, the ratio of the polyisocyanate (A-1) to the polyol composition (Y-1) to the polyol composition (Y-8) is the isocyanate group contained in the polyisocyanate (A-1), and the polyol composition The molar ratio [isocyanate group / (hydroxyl value + amine value)] of the sum of the hydroxyl value and the amine value of the alcohol composition (Y-1) to the polyol composition (Y-8) is in the range of 1.4 to 1.6 . In Table 2, the molar ratio is described as an NCO excess ratio. In addition, the functional group amount of the polyisocyanate composition described in Table 2 is the isocyanate content rate (%) which polyisocyanate (A-1) has. The functional group amount of the polyol composition described in Table 2 is the sum of the hydroxyl value and the amine value of the polyol composition (mgKOH/g).

Polyisocyanate (A-1) was coated on the corona-treated surface of a single-side corona-treated PET film (first film) with a thickness of 12 μm by a roll coater (first coating step). The first coating step was performed by setting the temperature of the polyisocyanate composition (X) stored in the coating liquid tank to 40°C. Simultaneously with the first coating step, the polyol composition (Y-1) was coated on the aluminum vapor-deposited surface of the aluminum vapor-deposited polypropylene (VMCPP) film (second film) with a thickness of 25 μm using a gravure coater (Y-1)～ Either of the polyol compositions (Y-8) (second coating step). In the 2nd coating process, the 2nd coating part in the coating process was visually confirmed, and ink-spattering property was evaluated based on the reference|standard mentioned later. In the first coating step and the second coating step, the total coating amount of polyisocyanate (A-1) and polyol composition (Y-1) to polyol composition (Y-8) is 2.0 g/m ² way.

Then, the adhesive agent layer formation process is performed continuously from a 1st coating process and a 2nd coating process. The adhesive layer forming step is carried out by laminating the first film and the second film so that the polyisocyanate (A-1) coated on the first film and the polyol coated on the second film are composed Any one of the substance (Y-1) to the polyol composition (Y-8) is contacted to cause a hardening reaction.

Regarding the laminated films of Examples 1 to 6 and Comparative Examples 1 to 2 manufactured at film transport speeds of 100 m/min, 150 m/min, 200 m/min, and 250 m/min, the following Based on the above criteria, the ink flying property in the second coating step was evaluated, and 3 or more was regarded as acceptable. The results are shown in Table 2. (Evaluation of ink splashing) 4: No flying ink 3: Generate some flying ink 2: Generate ink mist 1: Ink misting occurs violently

Regarding the laminated films of Examples 1 to 6 and Comparative Examples 1 to 2 manufactured at a film conveying speed of 200 m/min, the shear strength was measured and evaluated by the method shown below as the initial Cohesion evaluation. After the adhesive layer forming step was completed, the shear strength was measured respectively after 3 hours, 6 hours, 12 hours or 24 hours had passed at an ambient temperature of 25°C. The results are shown in Table 2.

(Measurement method of shear strength) The laminated film was cut into a strip with a width of 10 mm and a length of 200 mm, and only the first film was cut from the surface on the first film side in the width direction. Next, only the second film was cut from the surface on the second film side of the laminated film in the width direction at positions spaced apart by 10 mm in the longitudinal direction in a plan view from the cutting position of the first film. Accordingly, a test piece having an adhesive layer with a planar area of 100 mm ² between the cutting position of the first film and the cutting position of the second film was obtained. One end of the obtained test piece in the longitudinal direction was held by a clamp, and the other end was stretched in the longitudinal direction at a tensile speed of 5 mm/min using a tensile testing machine (Autograph AGS-J, manufactured by Shimadzu Corporation), and the shear was measured. cutting strength.

(initial cohesion evaluation) The evaluation of the shear strength was performed according to the following criteria, and the aging time was shortened to 5 N/10 mm or more (3 or more) as a pass. 1: Less than 1 N/10mm 2: More than 1 N/10 mm and less than 5 N/10 mm 3: More than 5 N/10 mm and less than 10 N/10 mm 4: 10 N/10 mm or more

As shown in Table 2, in Examples 1 to 6 in which the elongational viscosity of the polyol composition is 1 Pa·s or less, even at a high-speed film conveyance speed of 250 m/min, no misting occurs and good maintenance is maintained. workability. On the other hand, in Comparative Example 1 in which the elongational viscosity of the polyol composition exceeded 1 Pa·s, even if the film transport speed was 100 m/min, some flying ink was generated. In addition, in Comparative Example 2 in which the elongational viscosity of the polyol composition exceeded 10 Pa·s, even if the film conveyance speed was 100 m/min, misting occurred. From these results, it was confirmed that when the elongational viscosity of the polyol composition (Y) is 1 Pa·s or less, generation of flying ink can be suppressed, and good workability can be obtained. From this, it can be seen that the production efficiency can be improved when the elongational viscosity of the polyol composition (Y) is 1 Pa·s or less.

In addition, as is clear from Table 2, in Examples 1 to 6, high shear strengths of 10 N/10 mm or more were obtained even after 3 hours had elapsed after the adhesive layer formation step was completed. Accordingly, in Examples 1 to 6, after the adhesive layer formation step was completed, the early shear strength increased, and a high initial cohesive force was confirmed. On the other hand, in Comparative Examples 1 to 2, it was confirmed that the shear strength was less than 5 N/10 mm even after 24 hours after the completion of the adhesive layer formation step, and the shear strength did not increase at the early stage, and the initial Poor cohesion. As described above, the laminated film obtained by using the two-component curable adhesive of the present invention has excellent initial cohesive force and does not easily generate ink flying during its production, has excellent characteristics, and can be efficiently produced.

1. 1A: Manufacturing device/manufacturing device of laminated film 10: Adhesive layer 11: Volume 1 Exit 11a:Laminated film 12:Polyisocyanate Coating Section (First Coating Section) 12A: Mixed liquid coating part 13: Volume 2 Exit 14: Polyol coating section (second coating section) 15: Fitting device 111: Membrane installation department 120: Liquid reservoir 121: Applicator roller 122: scraper roller 123: metering roller 124: coating roller 125: backup roller 126: weir plate 131: Membrane installation department 141: gravure roll 142: chamber 142a: storage department 142b: Scraper 142c: sealing plate 142d: side panel 143: Embossing roller 144: Coating liquid tank 145: pump 146: Temperature regulator 151:Fitting part 152: Winding department R1, R2: lamination roller W1: first film W2: Second film X: Polyisocyanate composition Y: polyol composition

FIG. 1 is a cross-sectional view showing an example of a laminated film according to this embodiment. Fig. 2 is a front view of a manufacturing apparatus of a laminated film according to the present embodiment. Fig. 3 is a front view showing a main part of a polyisocyanate coating unit in the production apparatus of the laminated film shown in Fig. 2 . Fig. 4 is a front view showing a main part of a polyol application unit in the multilayer film manufacturing apparatus shown in Fig. 2 . FIG. 5 is a front view illustrating another example of the manufacturing apparatus used for manufacturing the laminated film according to the present embodiment.

Claims (4)

A two-component hardening adhesive that uses a hardening reaction of a polyisocyanate composition (X) and a polyol composition (Y). In the two-component hardening adhesive, The polyisocyanate composition (X) contains polyisocyanate (A), The polyol composition (Y) contains a polyol (B), and the elongational viscosity of the polyol composition (Y) is 1 Pa·s or less. A laminated film having an adhesive layer between a first film and a second film, The adhesive layer includes a cured product of the two-component hardening adhesive described in Claim 1. A manufacturing device for a laminated film, comprising: The first coating part applies the polyisocyanate composition (X) containing polyisocyanate (A) to the first film; In the second application part, the polyol composition (Y) containing the polyol (B) and having an elongational viscosity of 1 Pa·s or less is applied to the second film; and The bonding device bonds the polyisocyanate composition (X)-coated surface of the first film to the polyol composition (Y)-coated surface of the second film. A method of manufacturing a laminated film, comprising: The two-liquid coating step includes a first coating step and a second coating step, the first coating step is to coat the polyisocyanate composition (X) containing polyisocyanate (A) on the first film, The second coating step is coating the polyol composition (Y) containing the polyol (B) and having an elongational viscosity of 1 Pa·s or less on the second film; and Following the step of forming an agent layer, the polyisocyanate composition (X) coated on the first film and the polyisocyanate composition (X) coated on the second film are laminated by laminating the first film and the second film. The above-mentioned polyol composition (Y) on contact causes a hardening reaction.

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