WO2022172840A1 - 積層フィルム製造装置、積層フィルムの製造方法、二液硬化型接着剤、積層フィルム - Google Patents

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

Info

Publication number
WO2022172840A1
WO2022172840A1 PCT/JP2022/004165 JP2022004165W WO2022172840A1 WO 2022172840 A1 WO2022172840 A1 WO 2022172840A1 JP 2022004165 W JP2022004165 W JP 2022004165W WO 2022172840 A1 WO2022172840 A1 WO 2022172840A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
polyol
polyisocyanate
composition
laminated film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/004165
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
健二 中村
厚美 佐野
智雄 大久保
雅裕 丹羽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to JP2022580586A priority Critical patent/JP7343063B2/ja
Publication of WO2022172840A1 publication Critical patent/WO2022172840A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
    • B29C65/48—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding
    • B29C65/52—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor using adhesives, i.e. using supplementary joining material; solvent bonding characterised by the way of applying the adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/04—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving separate application of adhesive ingredients to the different surfaces to be joined

Definitions

  • the present invention relates to a laminated film manufacturing apparatus, a laminated film manufacturing method, a two-component curing adhesive, and a laminated film.
  • some laminated films which are made by bonding two films together with an adhesive, are manufactured using a two-component curing adhesive that uses a curing reaction between a main agent and a curing agent.
  • Two-part curing adhesives that use a polyisocyanate composition as a main agent and a polyol composition as a curing agent are widely used.
  • Laminated films are generally manufactured using laminating equipment.
  • Various devices have been proposed as laminating devices used for producing laminated films.
  • Patent Document 1 after applying a two-component curable adhesive to one film using a roll coater, it is laminated with the other film to produce a laminated film.
  • An agent coating apparatus is disclosed.
  • the laminated films described above are often used by heat-sealing (melt-bonding) the laminated films together or the laminated film and another film.
  • heat-sealing melting-bonding
  • the ends of the laminated film to form a bag it is widely used as a packaging material for foods and daily necessities (detergents, medicines, etc.).
  • a method for producing a laminated film there is a method in which only one of two films is coated with a two-component curing adhesive using a roll coater, and then the other film is pasted together.
  • the main component of the two-component curing adhesive and the curing agent are mixed before applying the two-component curing adhesive to the film. Therefore, the curing reaction of the two-component curable adhesive is initiated prior to applying the two-component curable adhesive to the film. Therefore, when a laminated film is produced by the above method, the gelled product of the two-part curing adhesive tends to adhere to each roll provided in the production apparatus.
  • a gelled product or the like of the two-component curable adhesive adhering to each roll may enter between the two films as a foreign matter and deteriorate the quality of the laminated film.
  • the present invention has been made in view of the above circumstances, and an apparatus for manufacturing a laminated film capable of manufacturing a laminated film having good heat-sealing properties with high production efficiency while suppressing the occurrence of loss due to pot life. and to provide a manufacturing method.
  • the present invention also provides a two-component curable adhesive that can be suitably used in the above laminated film manufacturing apparatus and manufacturing method, and a heat-sealable adhesive layer comprising a cured product of the above two-component curable adhesive.
  • An object of the present invention is to provide a laminated film having good properties.
  • the present inventor uses a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition and a polyol composition to provide an adhesive between the first film and the second film.
  • Intensive studies have been made in order to solve problems in production and to improve the properties of the resulting film in a method for producing a laminated film having layers formed thereon.
  • the present invention relates to the following matters.
  • a first coating section that applies a polyisocyanate composition (X) containing a polyisocyanate (A) and exhibiting elongation-curing behavior to the first film; a second coating section that applies a polyol composition (Y) that contains a polyol (B) and exhibits elongation-curing behavior to the second film;
  • An apparatus for producing a laminated film comprising a lamination device for laminating the surface of the first film coated with the polyisocyanate composition (X) and the surface of the second film coated with the polyol composition (Y).
  • a two-component separate coating step comprising a second coating step of applying a polyol composition (Y) containing a polyol (B) and exhibiting elongation curing behavior to a second film;
  • the polyisocyanate composition (X) applied on the first film and the polyol composition (Y) applied on the second film By laminating the first film and the second film, the polyisocyanate composition (X) applied on the first film and the polyol composition (Y) applied on the second film ) and an adhesive layer forming step of contacting and curing reaction.
  • a two-component curing adhesive that uses a curing reaction between a polyisocyanate composition (X) applied to a first film and a polyol composition (Y) applied to a second film, wherein the poly The isocyanate composition (X) contains a polyisocyanate (A), The polyol composition (Y) contains a polyol (B), A two-component curing adhesive in which the polyisocyanate composition (X) and the polyol composition (Y) exhibit extensional curing behavior.
  • [4] having an adhesive layer between the first film and the second film; A laminated film, wherein the adhesive layer is a cured product of the two-component curing adhesive according to [1].
  • the first coating section applies the polyisocyanate composition (X) exhibiting elongation-curing behavior to the first film
  • the second coating section exhibits elongation-curing behavior. is applied to the second film. Therefore, according to the laminated film manufacturing apparatus of the present invention, in the laminating device, the polyisocyanate composition (X)-coated surface of the first film and the polyol composition (Y)-coated surface of the second film By laminating together, it is possible to produce a laminated film having good heat sealability with high production efficiency while suppressing the occurrence of loss due to pot life.
  • the method for producing a laminated film of the present invention has a two-part separate coating step, in the first coating step, the polyisocyanate composition (X) exhibiting elongation curing behavior is applied to the first film, and in the second coating step , a polyol composition (Y) exhibiting elongational cure behavior is applied to the second film.
  • the method for producing a laminated film of the present invention by laminating the first film and the second film, the polyisocyanate composition (X) applied on the first film and the polyisocyanate composition (X) applied on the second film
  • the adhesive layer forming step of contacting the polyol composition (Y) obtained above and causing a curing reaction the loss due to pot life is suppressed, and high production efficiency and good heat sealability are obtained. Laminated films can be produced.
  • the polyisocyanate composition (X) applied to the first film and the polyol composition (Y) applied to the second film exhibit elongation curing behavior. Therefore, the two-component curing adhesive of the present invention can be suitably used in the laminated film manufacturing apparatus and manufacturing method of the present invention.
  • a laminated film in which an adhesive layer is formed between the first film and the second film using the two-component curing adhesive of the present invention provides excellent bonding strength by heat sealing. Therefore, the two-part curable adhesive of the present invention can be suitably used when manufacturing a laminated film.
  • the laminated film of the present invention has an adhesive layer between the first film and the second film, and the adhesive layer is made of the cured two-component curable adhesive of the present invention. Therefore, the laminated film of the present invention has good heat-sealing properties that provide excellent bonding strength by heat-sealing.
  • FIG. 1 is a cross-sectional view showing an example of a laminated film according to the present embodiment manufactured using the laminated film manufacturing apparatus of the present embodiment.
  • FIG. 2 is a front view of the laminated film manufacturing apparatus according to the present embodiment.
  • 3 is a front view showing a main part of a polyisocyanate coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • FIG. 4 is a front view showing a main part of a polyol coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • FIG. 1 is a cross-sectional view showing an example of a laminated film according to the present embodiment manufactured using the laminated film manufacturing apparatus of the present embodiment.
  • the laminated film 11a of this embodiment has an adhesive layer 10 between the first film W1 and the second film W2.
  • the adhesive layer 10 is made of the cured two-component curing adhesive of the present embodiment.
  • the two-component curing adhesive of the present embodiment comprises a polyisocyanate composition (X) that exhibits elongation-curing behavior applied to the first film W1, and a polyol composition that exhibits elongation-curing behavior applied to the second film W2. It is a two-component curable adhesive that uses a curing reaction with (Y).
  • FIG. 2 is a front view of a laminated film manufacturing apparatus according to this embodiment.
  • 3 is a front view showing a main part of a polyisocyanate coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • FIG. 4 is a front view showing a main part of a polyol coating section in the laminated film manufacturing apparatus shown in FIG. 2.
  • the laminated film manufacturing apparatus 1 shown in FIG. 2 uses the two-component curing adhesive of the present embodiment to bond the first film W1 unwound from the roll and the second film W2 unwound from the roll. , the adhesive layer 10 is formed between the first film W1 and the second film W2, and the laminated film 11a of the present embodiment wound into a roll is manufactured.
  • the laminated film manufacturing apparatus 1 of the present embodiment includes a first unwinding section 11, a polyisocyanate coating section 12 (first coating section), a second unwinding section 13, A polyol coating unit 14 (second coating unit) and a bonding device 15 are provided.
  • the first unwinding section 11 delivers the first film W1 to the polyisocyanate coating section 12 .
  • the first film W1 is rotatably mounted on the film mounting portion 111 of the first unwinding portion 11 .
  • the polyisocyanate coating section 12 applies the polyisocyanate composition (X) of the two-component curing adhesive of the present embodiment to the first film W1 delivered from the first unwinding section 11 .
  • the polyisocyanate coating section 12 is a four-roll squeeze roll coater.
  • the polyisocyanate coating section 12 includes an application roll 121 , a doctor roll 122 , a metering roll 123 , a coating roll 124 and a backing roll 125 .
  • a liquid reservoir 120 is provided at a portion where the application roll 121 and the doctor roll 122 face each other.
  • the application roll 121 is a roll having an outer peripheral surface made of an elastic material such as rubber.
  • the doctor roll 122 is a roll having an outer peripheral surface made of metal (inelastic material). As shown in FIG. 3, the application roll 121 and the doctor roll 122 are rotatably supported by the polyisocyanate coating section 12 so that their rotation axes are parallel to each other. The outer peripheral surface of the application roll 121 and the outer peripheral surface of the doctor roll 122 face each other with a minute gap therebetween.
  • a pair of barrier plates 126 is installed at a predetermined interval in the direction of the rotation axis of the application roll 121 and the doctor roll 122 above the portion where the application roll 121 and the doctor roll 122 face each other.
  • a liquid reservoir 120 is formed by the pair of barrier plates 126 , the outer peripheral surface of the application roll 121 , and the outer peripheral surface of the doctor roll 122 .
  • the liquid reservoir 120 temporarily stores the polyisocyanate composition (X).
  • the polyisocyanate composition (X) is supplied to the liquid reservoir 120 from a polyisocyanate supply section (not shown). Thereby, the polyisocyanate composition (X) stored in the liquid reservoir 120 is held at a constant amount.
  • the doctor roll 122 preferably has a temperature control section (not shown).
  • the temperature control section keeps the polyisocyanate composition (X) stored in the liquid reservoir section 120 at a constant temperature and stabilizes the viscosity of the polyisocyanate composition (X). Thereby, the outer peripheral surface of the doctor roll 122 is kept at a constant temperature.
  • the application roll 121 and doctor roll 122 rotate downward in the liquid reservoir 120 .
  • the outer peripheral surface of the doctor roll 122 is coated with the polyisocyanate composition (X) that has passed through the minute gaps.
  • the polyisocyanate coating section 12 rotatably supports a metering roll 123, a coating roll 124, and a backing roll 125.
  • the polyisocyanate composition (X) applied to the outer peripheral surface of the doctor roll 122 is transferred to the metering roll 123 .
  • the rotating shaft of the metering roll 123 is arranged parallel to the rotating shaft of the doctor roll 122 .
  • the outer peripheral surface of the metering roll 123 is made of an elastic material such as rubber. The outer peripheral surface of the metering roll 123 is pressed against the outer peripheral surface of the doctor roll 122 .
  • the polyisocyanate composition (X) applied to the outer peripheral surface of the metering roll 123 is transferred to the coating roll 124 .
  • the rotation axis of the coating roll 124 is arranged parallel to the rotation axis of the metering roll 123 .
  • the outer peripheral surface of the coating roll 124 is formed of a metal material. The outer peripheral surface of the coating roll 124 is pressed against the outer peripheral surface of the metering roll 123 .
  • the backing roll 125 is arranged so that the rotating shafts of the coating roll 124 are parallel to each other.
  • the backing roll 125 sandwiches the first film W1 between itself and the coating roll 124, and conveys the first film W1.
  • the backing roll 125 assists the transfer of the polyisocyanate composition (X) applied to the outer peripheral surface of the coating roll 124 to the first film W1.
  • the outer peripheral surface of the backing roll 125 is made of an elastic material such as rubber.
  • the coating roll 124 preferably has a constant temperature of the outer peripheral surface by a temperature control unit (not shown). This stabilizes the viscosity of the polyisocyanate composition (X) applied to the first film W1.
  • the second unwinding section 13 delivers the second film W2 to the polyol coating section 14 .
  • the second film W2 is rotatably mounted on the film mounting portion 131 of the second unwinding portion 13 .
  • the polyol coating section 14 applies the polyol composition (Y) of the two-component curing adhesive of the present embodiment to the second film W2 delivered from the second unwinding section 13 .
  • the polyol coating unit 14, as shown in FIG. 4, is a gravure coating machine (gravure coater) that applies the polyol composition (Y) by gravure printing.
  • the polyol coating section 14 includes a gravure roll 141 , a chamber 142 , an impression cylinder 143 , a coating liquid tank 144 , a pump 145 and a temperature controller 146 .
  • the gravure roll 141 is a metal roll rotatably supported by the polyol coating section 14 .
  • a plurality of recesses are formed on the surface of the gravure roll 141 by, for example, laser engraving. By changing the volume, opening ratio, depth, etc. of the recesses, the amount of the coating liquid applied to the surface of the gravure roll 141 can be adjusted.
  • the gravure pattern applied to the surface of the gravure roll 141 is not particularly limited, and may be, for example, a honeycomb pattern.
  • the chamber 142 is a container that stores the polyol composition (Y).
  • the chamber 142 is arranged on one radial side of the gravure roll 141 .
  • the chamber 142 has a storage part 142a that stores the polyol composition (Y).
  • the storage part 142a is open to the gravure roll 141 side. A part of the outer peripheral surface of the gravure roll 141 is immersed in the polyol composition (Y) stored in the storage part 142a.
  • the reservoir 142a is sealed by a doctor blade 142b, a seal plate 142c, and a pair of side plates 142d.
  • the chamber 142 has a plate-like doctor blade 142b.
  • the doctor blade 142b protrudes toward the gravure roll 141 from the upper end of the opening of the reservoir 142a.
  • the material of the doctor blade 142b is not particularly limited, and may be metal or resin, for example, stainless steel.
  • the tip of the doctor blade 142 b is pressed against the outer peripheral surface of the gravure roll 141 .
  • the tip of the doctor blade 142b seals the downstream side of the reservoir 142a in the roll rotation direction.
  • the doctor blade 142b scrapes off excess polyol composition (Y) adhering to the outer peripheral surface of the gravure roll 141 by rotating the gravure roll 141 and weighs it.
  • the chamber 142 has a plate-like seal plate 142c.
  • the seal plate 142c is made of resin.
  • the seal plate 142c protrudes toward the gravure roll 141 from the lower end of the opening of the reservoir 142a.
  • the tip of the seal plate 142 c is pressed against the outer peripheral surface of the gravure roll 141 .
  • the tip of the seal plate 142c seals the upstream side of the reservoir 142a in the roll rotation direction.
  • the chamber 142 has a side plate 142d made of resin.
  • the side plates 142d are attached to both side surfaces of the chamber 142, that is, both ends of the gravure roll 141 in the rotation axis direction.
  • the side surface of the side plate 142 d on the side of the gravure roll 141 has an arc shape along the shape of the gravure roll 141 and is pressed against the gravure roll 141 .
  • the impression cylinder 143 holds the second film W2 between itself and the gravure roll 141, and conveys the second film W2.
  • the impression cylinder 143 presses the second film W2 against the gravure roll 141 to transfer the polyol composition (Y) applied to the outer peripheral surface of the gravure roll 141 to the second film W2.
  • the coating liquid tank 144 is a container that stores the polyol composition (Y). As shown in FIG. 4, the coating liquid tank 144 is connected via a pipe to a pump 145 for flowing the polyol composition (Y) into the chamber 142 . Also, the coating liquid tank 144 is connected to the chamber 142 via a pipe. As a result, the polyol composition (Y) overflowing from the reservoir 142 a of the chamber 142 is recovered in the coating liquid tank 144 .
  • the pump 145 is connected to the coating liquid tank 144 and the chamber 142 via piping.
  • the pump 145 supplies the polyol composition (Y) stored in the coating liquid tank 144 to the reservoir 142 a of the chamber 142 .
  • a sine pump for example, can be used as the pump 145 .
  • the temperature controller 146 adjusts the temperature of the polyol composition (Y) stored in the coating liquid tank 144. This keeps the temperature of the polyol composition (Y) constant and stabilizes the viscosity of the polyol composition (Y).
  • the temperature controller 146 is, for example, a water temperature controller that heats water, which is a heat medium, with a heater and circulates around the polyol composition (Y) stored in the coating liquid tank 144 .
  • the bonding device 15 includes a bonding section 151 and a winding section 152, as shown in FIG.
  • the bonding portion 151 is a surface coated with the polyisocyanate composition (X) in the first film W1 delivered from the polyisocyanate coating portion 12 and a polyol composition in the second film W2 delivered from the polyol coating portion 14.
  • the coated surface of (Y) is pasted together.
  • the winding section 152 winds up the laminated film 11 a bonded by the bonding section 151 .
  • the lamination section 151 has a pair of lamination rolls R1 and R2, as shown in FIG.
  • the lamination rolls R1 and R2 sandwich and bond the first film W1 and the second film W2, and convey them.
  • the two laminate rolls R1 and R2 are kept at a constant temperature on the outer peripheral surface by a temperature control unit (not shown). This stabilizes the curing of the two-component curing adhesive.
  • the lamination unit 151 passes the first film W1 and the second film W2 between two laminate rolls R1 and R2 arranged opposite to each other, and sends them out from the polyisocyanate coating unit 12.
  • the coated surface of the first film W1 fed from the first film W1 and the coated surface of the second film W2 delivered from the polyol coating unit 14 are brought into contact with each other and bonded together.
  • the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2 are mixed to form a two-component curing adhesive. Curing of the agent is started, and the first film W1 and the second film W2 are attached and fixed.
  • the winding section 152 winds up the laminated film 11a formed by bonding the first film W1 and the second film W2 together in the bonding section 151 .
  • the method for manufacturing the laminated film 11a of the present embodiment includes a two-liquid separate coating process and an adhesive layer forming process. In this embodiment, the two-liquid separate application step and the adhesive layer forming step are performed continuously.
  • the two-liquid separate coating step includes a first coating step of applying a polyisocyanate composition (X) that contains a polyisocyanate (A) and exhibits elongation curing behavior to the first film W1, and a polyol (B) that includes elongation curing. and a second coating step of coating the second film W2 with the polyol composition (Y) exhibiting behavior.
  • a polyisocyanate composition X
  • A polyisocyanate
  • B that includes elongation curing
  • Y polyol composition
  • first coating process A method of performing the first coating step using the laminated film manufacturing apparatus 1 shown in FIGS. 2 to 4 will be described.
  • the first film W1 is delivered from the first unwinding section 11 to the polyisocyanate coating section 12 .
  • each roll is rotated in the direction indicated by the arrow in FIG.
  • the polyisocyanate composition (X) stored in the liquid reservoir 120 is applied to the surface of the doctor roll 122 .
  • the temperature of the polyisocyanate composition (X) stored in the liquid reservoir 120 is preferably adjusted to 25° C. to 80° C., preferably 25° C. to 40° C., by a temperature control unit (not shown). is more preferable.
  • the 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 to the doctor roll 122 is sequentially transferred to the metering roll 123 and the coating roll 124 .
  • Each roll of the polyisocyanate coating section 12 is set so that the rotational speed increases sequentially.
  • the coating thickness of the polyisocyanate composition (X) gradually decreases, and the coating roll 124 adjusts the coating thickness (coating amount) to a predetermined level.
  • the polyisocyanate composition (X) transferred to the coating roll 124 is transferred to the first film W ⁇ b>1 conveyed between the coating roll 124 and the backing roll 125 . Thereby, the polyisocyanate composition (X) is applied to the first film W1.
  • the coating amount of the polyisocyanate composition (X) applied to the first film W1 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2 .0 g/ m2 .
  • the first film W ⁇ b>1 coated with the polyisocyanate composition (X) is delivered to the bonding device 15 .
  • the second film W2 is delivered from the second unwinding section 13 to the polyol coating section .
  • the gravure roll 141 and impression cylinder 143 are rotated in the directions indicated by the arrows in FIG.
  • the rotation of the gravure roll 141 causes the polyol composition (Y) in the chamber 142 to be applied to the second film W2 through the surface of the gravure roll 141 .
  • the coating amount of the polyol composition (Y) applied to the second film W2 is preferably 0.5 to 3.0 g/m 2 , more preferably 0.5 to 2.0 g / m2 .
  • the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is preferably adjusted to 25° C. to 80° C., preferably 25° C. to 40° C., by the temperature controller 146. is more preferable.
  • the viscosity of the polyol composition (Y) is set to a viscosity suitable for a gravure coating machine.
  • the rotation direction of the gravure roll 141 may be forward rotation, which is the same direction as the transport direction of the second film W2, or reverse rotation, which is the opposite direction to the transport direction of the second film W2.
  • the gravure roll 141 transfers the polyol composition (Y) to the second film W2 while rotating in the direction opposite to the conveying direction of the second film W2.
  • the appearance of the polyol composition (Y) applied to the second film W2 can be made good without vertical streaks, roll marks, and the like.
  • the second film W ⁇ b>2 coated with the polyol composition (Y) is delivered to the bonding device 15 .
  • Adhesive layer forming step In the adhesive layer forming step, by laminating the first film W1 and the second film W2, the polyisocyanate composition (X) applied on the first film W1 and the polyol applied on the second film It is brought into contact with the composition (Y) to cause a curing reaction.
  • the first film W1 and the second film W2 are sandwiched between two lamination rolls R1 and R2 facing each other while being in contact with each other. pass between two laminate rolls R1, R2. Then, the first film W1 and the second film W2 are laminated together by the pressure from the two lamination rolls R1 and R2.
  • the temperature of the outer peripheral surfaces of the two laminate rolls R1 and R2 is preferably 40°C to 80°C, more preferably 40°C to 60°C.
  • the pressure from the two laminating rolls R1, R2 to the first film W1 and the second film W2 can be, for example, 3-300 kg/cm 2 .
  • the coated surface of the first film W1 delivered from the polyisocyanate coating unit 12 and the second film delivered from the polyol coating unit 14 are sandwiched between the two lamination rolls R1 and R2.
  • the coated surface of W2 contacts.
  • the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2 are mixed, and curing of the two-component curable adhesive is started. be.
  • the laminated film 11a having the adhesive layer 10 between the first film W1 and the second film W2 is obtained.
  • the laminated film 11a produced by bonding the first film W1 and the second film W2 together in the bonding section 151 is conveyed to the winding section 152 .
  • the laminated film 11 a conveyed to the winding section 152 is wound by the winding section 152 .
  • the film transport speed (the winding speed of the laminated film 11a in the winding unit 152) when manufacturing the laminated film 11a can be set to, for example, 30 to 300 m/min. preferably 100 to 250 m/min.
  • a laminated film can be produced efficiently when the film transport speed is 30 m/min or more. If the film transport speed exceeds 300 m/min, problems such as problems in coating, problems in transport itself, and problems in bonding may occur. Therefore, it is preferable to set the film transport speed to 300 m/min or less.
  • the laminated film 11a obtained by the manufacturing method of the present embodiment is obtained by bonding the first film W1 and the second film W2 together in the bonding section 151, and after being wound up by the winding section 152, is allowed to stand at room temperature as necessary.
  • aging is performed by storing for 3 to 48 hours under heating. By performing aging, the two-component curing adhesive is sufficiently cured, and practical physical properties as the adhesive layer 10 may be exhibited.
  • the manufacturing apparatus 1 of the laminated film 11a of the present embodiment includes a polyisocyanate coating unit 12 that applies a polyisocyanate composition (X) exhibiting elongation-curing behavior to the first film W1, and a polyol composition exhibiting elongation-curing behavior ( Y) on the second film W2, the polyisocyanate composition (X)-coated surface of the first film W1, and the polyol composition (Y)-coated surface of the second film W2. and a bonding device 15 for bonding. Therefore, the manufacturing apparatus 1 of the laminated film 11a of the present embodiment uses the two-component curing adhesive of the present embodiment, and the manufacturing method of the present embodiment having the two-component separate application process causes a pot life.
  • the laminated film 11a with good heat-sealability can be manufactured with high production efficiency while suppressing the occurrence of loss.
  • the polyol coating unit 14 may be equipped with a gravure coater that expands the range of selection such as the viscosity of the polyol composition (Y), or may be equipped with a roll coater.
  • a gravure coater is selected as the device for applying the polyol composition (Y) in the polyol coating section 14, the viscosity of the polyol composition (Y) is low and problems such as dripping may occur with a roll coater. However, dripping does not occur, and coating quality can be improved to manufacture a high-quality laminated film 11a.
  • the configuration of the polyol coating section 14 can be simplified, and the manufacturing apparatus for the laminated film 11a can be miniaturized.
  • a roll coater is used in the polyisocyanate coating section 12 that applies the relatively high viscosity polyisocyanate composition (X) to the first film W1.
  • a roll coater it is possible to apply even when the viscosity of the polyisocyanate composition (X) is relatively high, and the range of selection of the material of the polyisocyanate composition (X) is widened.
  • the method for producing the laminated film 11a of the present embodiment includes a first coating step of applying a polyisocyanate composition (X) exhibiting elongation-curing behavior to the first film W1, and a polyol composition (Y) exhibiting elongation-curing behavior.
  • the method for manufacturing the laminated film 11a of the present embodiment has a two-component separate application step, so the step of mixing the polyisocyanate composition (X) and the polyol composition (Y) is unnecessary. Therefore, the workability is excellent as compared with the case of having a step of mixing the polyisocyanate composition (X) and the polyol composition (Y).
  • the polyisocyanate composition (X) and the polyol composition (Y) are not mixed, there is no limitation due to the pot life of the two-component curing adhesive, and the two-component curing adhesive of the present embodiment, which cures quickly. drug can be used.
  • the polyisocyanate composition (X) exhibiting elongation-curing behavior is applied to the first film
  • the polyol exhibiting elongation-curing behavior The composition (Y) is applied to the second film W2. Therefore, according to the method for manufacturing the laminated film 11a of the present embodiment, the laminated film 11a of the present embodiment, in which the two-component curing adhesive of the present embodiment is used to obtain excellent bonding strength by heat sealing, is produced. can be manufactured.
  • a roll coater is used as the polyisocyanate-coated portion 12, but when the viscosity of the polyisocyanate composition (X) is low, etc., a gravure coater may be used as the polyisocyanate-coated portion 12. . Further, in the above-described embodiment, a gravure coater is used as the polyol-coated portion 14, but a roll coater may be used as the polyol-coated portion 14 when the polyol composition (Y) can be applied. .
  • the temperature of the polyol composition (Y) stored in the coating liquid tank 144 is adjusted by the temperature controller 146. Furthermore, the temperature of the polyol composition (Y) stored in the storage section 142a of the chamber 142 and/or the temperature of the gravure roll 141 may be adjusted. Thereby, the viscosity of the polyol composition (Y) during coating can be further stabilized, and the coating quality and the quality of the laminated film 11a can be further improved.
  • the two-component curing adhesive of this embodiment uses a curing reaction between the polyisocyanate composition (X) applied to the first film W1 and the polyol composition (Y) applied to the second film W2. It is a liquid curing adhesive.
  • the polyisocyanate composition (X) in the two-component curing adhesive of the present embodiment contains the polyisocyanate (A) and exhibits extensional curing behavior.
  • Polyol composition (Y) contains polyol (B) and exhibits extensional cure behavior.
  • the polyisocyanate composition (X) may contain part of the polyol (B) contained in the two-component curing adhesive, if necessary.
  • the two-component curable adhesive of this embodiment is cured by a chemical reaction between the isocyanate groups in the polyisocyanate composition (X) and the hydroxyl groups (or hydroxyl groups and amino groups) in the polyol composition (Y).
  • elongational hardening means that the elongational viscosity doubles when the elongation speed is doubled. That is, “exhibiting elongational hardening behavior” means that the elongational viscosity doubles or more when the elongation speed is doubled. “Does not exhibit elongational hardening behavior” means that the elongational viscosity is less than doubled when the elongation rate is doubled. Further, in the present embodiment, the "elongation speed at which elongation hardening starts” is the lowest elongation speed at which elongation hardening behavior occurs.
  • both the polyisocyanate composition (X) and the polyol composition (Y) exhibit extensional curing behavior. Therefore, the laminated film in which the adhesive layer is formed between the first film and the second film using the two-component curing adhesive of the present embodiment can obtain excellent bonding strength by heat sealing. .
  • the elongation speed at which the elongation curing of the polyisocyanate composition (X) and the polyol composition (Y) starts is substantially 100 s -1 or more in view of the measurable range.
  • the lower limit of the elongation speed at which elongation hardening starts is not particularly limited, it is preferably 4000 s ⁇ 1 or more.
  • the upper limit of the elongation speed at which elongation hardening starts is not particularly limited, but it is preferably 50000 s -1 or less, more preferably 40000 s -1 or less, and 38000 s -1 or less. More preferred.
  • the extensional curing behavior of the polyisocyanate composition (X) can be controlled by adjusting the ratio of the low-viscosity material and the high-viscosity material contained in the material (compound) used in the polyisocyanate composition (X).
  • the extensional hardening behavior 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 material (compound) used in the polyol composition (Y).
  • a person skilled in the art can grasp the viscosity of the materials (compounds) used for the polyisocyanate composition (X) and the polyol composition (Y). Further, a person skilled in the art can combine the materials (compounds) used for the polyisocyanate composition (X) and the polyol composition (Y) and appropriately adjust the compounding ratio, within the scope of ordinary experiments, A polyisocyanate composition (X) and a polyol composition (Y) exhibiting elongational curing behavior can be obtained on the basis of known techniques.
  • Polyisocyanate (A) As the polyisocyanate (A), known ones can be used without particular limitation.
  • Examples of the polyisocyanate (A) include tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate may be simply referred to as "MDI"), 2,2'-MDI, 4,4'-MDI, 1,5-naphthalene diisocyanate , aromatic polyisocyanates such as triphenylmethane triisocyanate; Aliphatic polyisocyanates such as xylylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate ; Compounds in which
  • polystyrene resin examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1 ,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol , dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, and other chain aliphatic glycols; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and other alicyclic glycols; g
  • a polyester polyol (2) obtained by reacting a polyol such as the linear aliphatic glycol, alicyclic glycol, dimer diol, bisphenol, or polyether polyol with a polyvalent carboxylic acid; polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid; A polyester obtained by reacting a polyol such as the chain aliphatic glycol, alicyclic glycol, dimer diol, bisphenol, or polyether polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polycarboxylic acid.
  • Polyester polyol (5) which is a polymer of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acid; Castor oil, dehydrated castor oil, hydrogenated castor oil, castor oil-based polyols such as adducts of 5 to 50 moles of alkylene oxide of castor oil, and mixtures thereof.
  • Examples of the polyvalent carboxylic acid used for producing the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid.
  • non-cyclic aliphatic dicarboxylic acids such as; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; Anhydrides or ester-forming derivatives of aromatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, polybasic acids such as dimer acid is mentioned.
  • the polyisocyanate (A1) is preferred, and the polyisocyanate obtained by reacting the polyether polyol and the polyisocyanate is particularly preferred from the viewpoint of wettability. Furthermore, it is preferable to use a polyol having a polypropylene skeleton as the polyol component to be reacted with the polyisocyanate, since the polyisocyanate (A1) has a low viscosity and is easy to handle at low temperatures.
  • the polyol component to be reacted with the polyisocyanate has a number average molecular weight (Mn) of 300 to 5,000, more preferably 350 to 3,000.
  • Ether polyols are preferably used.
  • the proportion of polyether polyol having a number average molecular weight (Mn) of 300 to 5,000 in the polyol component is preferably 50% by mass or more.
  • the total polyol component may be a polyether polyol having a number average molecular weight (Mn) of 300-5,000.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device HLC-8320GPC manufactured by Tosoh Corporation Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation Detector; RI (differential refractometer) Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation Measurement conditions; column temperature 40°C Solvent; tetrahydrofuran flow rate; 0.35 ml/min standard; monodisperse polystyrene sample; 0.2% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 ⁇ l)
  • the polyisocyanate to be reacted with the polyol component preferably contains an aromatic polyisocyanate because of its excellent reactivity with the polyamine (C) described later.
  • the amount of the aromatic polyisocyanate to be blended is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, for 100 parts by mass of the total charged amount for synthesizing the polyisocyanate (A1).
  • the upper limit of the amount of the aromatic polyisocyanate compounded is preferably 60 parts by mass or less, more preferably 55 parts by mass or less.
  • polyisocyanate to be reacted with the polyol component, it is preferable to use at least one of aliphatic polyisocyanate and aliphatic polyisocyanate derivative together with aromatic polyisocyanate from the viewpoint of storage stability.
  • the reaction ratio of the polyisocyanate and the polyol component in the polyisocyanate (A1) is such that the equivalent ratio [isocyanate group/hydroxyl group] between the isocyanate group in the polyisocyanate and the hydroxyl group in the polyol component is 1.5 to 5.0. A range is preferred.
  • the polyisocyanate (A) employing such a polyisocyanate (A1) has an appropriate viscosity of the polyisocyanate composition (X) containing it, and the coating property is improved, and the polyisocyanate (A ) is preferable because the cohesive force of the coating film made of the two-component curing adhesive containing is improved.
  • the polyisocyanate (A) preferably has a weight average molecular weight (Mw) in the range of 100 to 10,000 from the viewpoint of shortening the aging time and ensuring proper packaging properties. A range is more preferred.
  • Mw weight average molecular weight
  • the polyisocyanate (A) is the polyisocyanate (A1), it preferably has a weight average molecular weight (Mw) in the range of 300 to 10,000.
  • the polyisocyanate (A) preferably has an isocyanate content of 5 to 25% by mass.
  • the polyisocyanate composition (X) containing such a polyisocyanate (A) is preferable because it has an appropriate resin viscosity and is excellent in coatability.
  • the isocyanate content of polyisocyanate (A) is a value determined by a titration method using di-n-butylamine.
  • polyol (B) examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6 - hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol , 1,4-cyclohexanedimethanol, glycols such as triethylene glycol;
  • trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, and pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, and hydrogenated bisphenol F; dimer diols;
  • polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or bisphenol with a polyvalent carboxylic acid
  • polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid
  • a polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid
  • Polyester polyol (5) which is a polymer of hydroxy acids such as dimethylolpropionic acid and castor oil fatty acid
  • Polyester polyether polyols obtained by reacting the polyester polyols (1) to (5), the polyether polyols, and an aromatic or aliphatic polyisocyanate
  • polyester polyurethane polyols obtained by polymerizing the polyester polyols (1) to (5) with aromatic or aliphatic polyisocyanates
  • Castor oil dehydrated castor oil, hydrogenated castor oil,
  • Examples of the polyvalent carboxylic acid used for producing the polyester polyol (2), (3) or (4) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, and fumaric acid.
  • a tertiary amine compound having a plurality of hydroxyl groups may be used as the polyol (B).
  • a tertiary amine compound having a plurality of hydroxyl groups not only cures when the hydroxyl groups react with the polyisocyanate (A), but also functions as a curing accelerator because the amine structure accelerates the curing reaction.
  • the number of hydroxyl groups is 2 or more, preferably 2 to 6.
  • a tertiary amine compound having a plurality of hydroxyl groups may have one or more tertiary amino groups, preferably one or two.
  • tertiary amine compounds having a plurality of hydroxyl groups include polypropylene glycol ethylene diamine ether, tri(1,2-polypropylene glycol) amine, N-ethyldiethanolamine, N-methyl-N-hydroxyethyl-N-hydroxy ethoxyethylamine, pentakishydroxypropyldiethylenetriamine, tetrakishydroxypropylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, triethanolamine, triethanolamine propoxylated and the like.
  • a commercially available product may be used as the tertiary amine compound having multiple hydroxyl groups.
  • Examples of commercially available products include EDP-300 manufactured by ADEKA Corporation, ED-500 and TE-360 manufactured by Kokuto Kako, and VORANOL TM800 Polyol manufactured by DOW.
  • the mixing ratio of the polyol other than the tertiary amine compound in the polyol (B) and the tertiary amine compound (polyol other than the tertiary amine compound/ The tertiary amine compound (mass ratio)) is preferably from 100/5 to 100/70, more preferably from 100/10 to 100/70.
  • Polyol (B) preferably contains a polyol having a polyether skeleton, and more preferably contains a polyol having a polypropylene skeleton.
  • a polyol (B) has a viscosity that enables coating at a temperature of 25° C. to 60° C. even if it is a non-solvent type.
  • the two-component curing adhesive containing such a polyol (B) is preferable because it exhibits excellent adhesion strength to metal oxides such as silica and/or alumina, metals such as aluminum, and resin films.
  • the content of the polyol having a polyether skeleton is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass, based on the total amount of the polyol (B) from the viewpoint of coatability. It is more preferable to be above.
  • the upper limit of the content of the polyol having a polyether skeleton is not particularly limited, and the total amount of the polyol (B) may be a polyol having a polyether skeleton. From the viewpoint, it is preferably 95% by mass or less.
  • Polyol (B) is castor oil, dehydrated castor oil, hydrogenated castor oil that is a hydrogenated product of castor oil, and 5 to 50 moles of alkylene oxide added to castor oil, from the viewpoint of the initial cohesive strength and coatability of the two-component curing adhesive. It preferably contains at least one castor oil-based compound selected from the group consisting of castor oil-based polyols such as castor oil-based polyols. These castor oil-based compounds are preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more, and 20% by mass of the total amount of polyol (B). It is more preferable to be above. Also, the upper limit of the castor oil-based compound is not particularly limited, and the total amount of the polyol (B) may be a castor oil-based compound, but from the viewpoint of coatability, it is preferably 95% by mass or less.
  • the polyol (B) may contain a highly reactive low-molecular-weight polyol (liquid at room temperature and having a molecular weight of about 150 or less). By containing such a low-molecular-weight polyol, the reaction with the polyisocyanate (A) can be accelerated. On the other hand, if the amount of the low-molecular-weight polyol is too large, the reaction with the polyisocyanate (A) may be too fast. Therefore, the content of the low-molecular-weight polyol is preferably 5% by mass or less, more preferably 3% by mass or less, of the polyol (B).
  • the viscosity of the polyol (B) is 400 to 5000, so the coatability is improved, and the cohesive force of the two-component curing adhesive is improved, which is preferable. .
  • the hydroxyl value of the polyol (B) is preferably 50 mgKOH/g or more and 300 mgKOH/g or less, more preferably 100 mgKOH/g or more and 250 mgKOH/g or less.
  • the hydroxyl value of the polyol (B) can be measured by the hydroxyl value measuring method described in JIS-K0070.
  • the polyol composition (Y) preferably contains a polyamine (C).
  • Polyamine (C) functions as a curing accelerator.
  • the polyamine (C) known ones can be used without particular limitation.
  • Polyamine (C) has two amino groups ( NH2 group, NHR group (R represents an alkyl group)) in the molecule in order to maintain the toughness of the coating film made of a two-component curing adhesive. It is desirable that the compound has the above.
  • Polyamines (C) include, for example, methylenediamine, ethylenediamine, isophoronediamine, 3,9-dipropanamine-2,4,8,10-tetraoxaspironedecane, lysine, phenylenediamine, 2,2,4-trimethyl Hexamethylenediamine, tolylenediamine, hydrazine, piperazine, hexamethylenediamine, propylenediamine, dicyclohexylmethane-4,4-diamine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine , 2-hydroxypropylethylenediamine, or di-2-hydroxypropylethylenediamine, poly(propylene glycol) diamine, poly(propylene glycol) triamine, poly(propylene glycol) tetraamine, 1,2-diaminopropane, 1,3-diaminoprop
  • 1,4-diaminobutane 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, etc.
  • benzyl amine diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, trimethylhexamethylenediamine, etc., tetra(aminomethyl)methane, tetrakis ( 2-aminoethylaminomethyl)methane, 1,3-bis(2′-aminoethylamino)propane, triethylene-bis(trimethylene)hexamine, bis(3-aminoethy
  • polyamine (C) it is preferable to use a polyetheramine having a polyether structure in the main chain in order to maintain the flexibility of the coating film composed of the two-component curing adhesive.
  • These polyamines (C) may be used alone or in combination of two or more.
  • a commercially available product may be used as the polyamine (C).
  • Commercially available products include EC-310 and EC-303 manufactured by BASF.
  • the functional group in the polyisocyanate composition (X) (the isocyanate group of the polyisocyanate (A)) and the functional group in the polyol composition (Y) (the hydroxyl group of the polyol (B), the amino group of the polyamine (C), group) molar ratio [isocyanate group / (hydroxyl group + amino group)] is preferably 0.5 to 5.0, and from the viewpoint of the adhesive performance of the two-component curing adhesive, 1.0 to 3.0 is more desirable.
  • the ratio of the polyol (B) and the polyamine (C) in the polyol composition (Y) is such that the molar ratio [amino group/hydroxyl group] of the amino group derived from the polyamine (C) and the hydroxyl group derived from the polyol (B) is 0. .001 to 2.0 is desirable, and from the viewpoint of achieving both the adhesive strength of the two-part curing adhesive, the processed appearance, and the practicality of workability, the range of 0.1 to 1.0 is more preferable. preferable.
  • the above molar ratio is 0.001 or more, the workability of the laminated film produced using the two-component curing adhesive becomes favorable.
  • the molar ratio is 2.0 or less, the adhesion strength of the two-component curing adhesive becomes good.
  • the two-component curable adhesive of the present embodiment can be used as a solventless adhesive, but the two-component curable adhesive of the present embodiment may contain a solvent if necessary.
  • the "solvent” refers to a highly soluble organic solvent capable of dissolving the polyisocyanate composition (X) and/or the polyol composition (Y).
  • solvent-free refers to not containing these highly soluble organic solvents.
  • solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, and methyl ethyl ketone (MEK). , cyclohexanone, n-hexane, cyclohexane, and the like.
  • solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are particularly highly soluble organic solvents.
  • the two-component curable adhesive of this embodiment can be used by diluting it with a solvent so as to obtain the desired viscosity when it is required to lower the viscosity.
  • a solvent may be used to dilute either one of the polyisocyanate composition (X) or the polyol composition (Y), or both.
  • organic solvents examples include methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, Examples include toluene, xylene, n-hexane, cyclohexane and the like.
  • ethyl acetate and/or methyl ethyl ketone (MEK) it is preferable to use ethyl acetate, from the viewpoint of the solubility of the polyisocyanate composition (X) and the polyol composition (Y).
  • MEK methyl ethyl ketone
  • the content of the organic solvent in the two-component curing adhesive of the present embodiment can be appropriately determined according to the required viscosity, and can be, for example, 20 to 50% by mass.
  • the two-component curing adhesive of this embodiment may contain a catalyst.
  • the catalyst may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both.
  • the catalyst generally has a high reactivity with the polyisocyanate composition, and after the polyisocyanate composition (X) and the polyol composition (Y) are brought into contact with each other, the catalyst is effectively activated. It is preferably contained only in (Y).
  • the catalyst may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • the two-component curing adhesive contains a catalyst
  • the curing of the two-component curing adhesive is accelerated, and the laminate film produced using the two-component curing adhesive is exposed to harmful low-grade compounds such as aromatic amines. Elution of molecular chemicals can be suppressed. That is, the catalyst also works as a curing accelerator like polyamine (C) and the like.
  • the catalyst is not particularly limited as long as it promotes the urethanization reaction between the polyisocyanate composition (X) and the polyol composition (Y).
  • catalysts that can be used include metal-based catalysts, amine-based catalysts, diazabicycloundecene (DBU), aliphatic cyclic amide compounds, and titanium chelate complexes.
  • Metal-based catalysts include metal complex-based catalysts, inorganic metal-based catalysts, and organic metal-based catalysts.
  • the metal complex catalyst from the group consisting of Fe (iron), Mn (manganese), Cu (copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum) and Co (cobalt) Acetylacetonate salts of selected metals and the like are included. Specific examples include iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, and zirconia acetylacetonate.
  • iron acetylacetonate Fe(acac) 3
  • manganese acetylacetonate Mn(acac) 2
  • Organometallic catalysts include stannus diacetate, stannus dioctoate, stannus dioleate, stannus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, bismuth neodecanoate, zinc neodecanoate and the like.
  • preferred organometallic catalysts are stannous dioctoate, dibutyltin dilaurate, bismuth neodecanoate, zinc neodecanoate, or mixtures thereof.
  • amine-based catalysts examples include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine.
  • triethylenediamine and/or 2-methyltriethylenediamine are preferably used as the amine-based catalyst because of their excellent catalytic activity and industrial availability.
  • tertiary amine catalysts include N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'',N ′′-pentamethyldiethylenetriamine, N,N,N′,N′′,N′′-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N′,N′′,N′′-pentamethyldipropylenetriamine, N, N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxy ethyl)ethylenediamine, N,N-dimethyl-N'-(2-hydroxyethyl)propanediamine, bis(dimethylaminoprop
  • aliphatic cyclic amide compounds used as catalysts include ⁇ -valerolactam, ⁇ -caprolactam, ⁇ -enanthrolactam, ⁇ -capryllactam and ⁇ -propiolactam.
  • ⁇ -caprolactam can more effectively accelerate the curing of two-component curing adhesives.
  • the content of the catalyst in the two-component curing adhesive of this embodiment is not particularly limited, and can be a known amount.
  • the content of the catalyst can be, for example, 0.001 to 5.0% by mass with respect to the total solid content of the two-component curing adhesive.
  • the two-component curing adhesive of this embodiment may contain an adhesion promoter.
  • the adhesion promoter may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both. Since the adhesion promoter has high reactivity with the polyisocyanate composition (X), it is preferred to act after the polyisocyanate composition (X) and the polyol composition (Y) are brought into contact with each other. Therefore, the adhesion promoter is preferably contained only in the polyol composition (Y).
  • the adhesion promoter may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • Adhesion promoters include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, epoxy resins, and the like.
  • Silane coupling agents include, for example, ⁇ -aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethoxysilane, Aminosilanes such as N- ⁇ (aminoethyl)- ⁇ -aminopropyltrimethyldimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane; ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycides epoxysilanes such as xypropyltrimethoxysilane and ⁇ -glycidoxypropyltriethoxysilane; vinylsilanes such as vinyltris( ⁇ -methoxyethoxy)silane, vinyltrie
  • titanate-based coupling agents examples include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, tetrastearoxytitanium, and the like. can be mentioned.
  • aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.
  • epoxy resin generally commercially available epi-bis type, novolac type, ⁇ -methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polyvalent carboxylic acid ester type, aminoglycidyl type, resorcinol type, and other epoxy resins.
  • the content of the adhesion promoter in the two-component curing adhesive of this embodiment is not particularly limited, and can be a known amount.
  • the content of the adhesion promoter can be, for example, 0 to 50% by mass with respect to the total solid content of the two-component curing adhesive.
  • the two-component curing adhesive of the present embodiment may be used in combination with a pigment, if necessary.
  • the pigment may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both.
  • the pigment may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • the pigment is not particularly limited, and includes various pigments.
  • pigments include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, green pigments, blue pigments, and metal powders described in the 1970 edition of Handbook of Paint Materials (edited by the Japan Paint Manufacturers Association).
  • organic pigments such as pigments, luminescent pigments and pearlescent pigments, inorganic pigments, and plastic pigments.
  • organic pigments examples include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R; soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.
  • insoluble azo pigments such as Benzidine Yellow, Hansa Yellow and Laked 4R
  • soluble azo pigments such as Laked C, Carmine 6B and Bordeaux 10
  • various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.
  • Pigments various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant pigments such as quinoline lake and fast sky blue; various vat dyes such as anthraquinone pigments, thioindigo pigments and perinone pigments dye-based pigments; various quinacridone-based pigments such as Cincasia Red B; various dioxazine-based pigments such as dioxazine violet; various condensed azo pigments such as chromophtal;
  • inorganic pigments include various chromates such as yellow lead, zinc chromate, and molybdate orange; various ferrocyanic compounds such as Prussian blue; titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, and chromium oxide.
  • various metal oxides such as green and zirconium oxide; various sulfides and selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder. pigments; flake pigments of these metals, mica flake pigments; metallic pigments and pearl pigments such as mica flake pigments coated with metal oxides and mica-like iron oxide pigments; graphite, carbon black and the like.
  • Extender pigments include, for example, precipitated barium sulfate, rice flour, precipitated calcium carbonate, calcium bicarbonate, Kansui stone, alumina white, silica, hydrous fine silica (white carbon), ultrafine anhydrous silica (Aerosil), silica sand (silica sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess, and the like.
  • plastic pigments include "Glandole PP-1000" and "PP-2000S” manufactured by DIC Corporation.
  • inorganic oxides such as titanium oxide and zinc oxide as white pigments, and carbon black as black pigments, since they are excellent in durability, weather resistance, and design.
  • the content of the pigment in the two-component curing adhesive of the present embodiment is 1 to 400 parts by mass with respect to 100 parts by mass of the total solid content of the polyisocyanate composition (X) and the polyol composition (Y). is preferred, and 10 to 300 parts by mass is more preferred.
  • the content of the pigment is 1 to 400 parts by mass, a two-part curing adhesive having excellent adhesion and anti-blocking properties can be obtained.
  • the two-component curing adhesive of the present invention may contain other additives in addition to the components described above, if necessary.
  • the additive may be contained in either one of the polyisocyanate composition (X) and the polyol composition (Y), or may be contained in both.
  • the additive may be contained in the polyisocyanate composition (X) and/or the polyol composition (Y) during coating of the two-component curing adhesive.
  • Additives include, for example, leveling agents; inorganic fine particles such as colloidal silica and alumina sol; polymethylmethacrylate-based organic fine particles; antifoaming agents; Deactivator; peroxide decomposer; flame retardant; reinforcing agent; plasticizer; lubricant; rust inhibitor; fluorescent whitening agent; is mentioned.
  • the two-component curable adhesive of the present embodiment is a two-component curable adhesive using a curing reaction between the polyisocyanate composition (X) and the polyol composition (Y), wherein the polyisocyanate composition (X) is The polyisocyanate (A) is included, the polyol composition (Y) includes the polyol (B), and the polyisocyanate composition (X) and the polyol composition (Y) exhibit extensional curing behavior.
  • a laminated film in which an adhesive layer is formed between the first film and the second film using the two-component curing adhesive of this embodiment can obtain excellent bonding strength by heat sealing. Therefore, the two-part curable adhesive of the present invention can be suitably used when manufacturing a laminated film.
  • the laminated film 11a of this embodiment has an adhesive layer 10 between the first film W1 and the second film W2.
  • the adhesive layer 10 is made of a cured product of the two-component curing adhesive of this embodiment.
  • the film In the laminated film 11a of the present embodiment, it is preferable to use plastic films used for known laminated films for the films used as the first film W1 and the second film W2.
  • the first film W1 include base films such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") film, nylon (OPA) film, biaxially oriented polypropylene (OPP) film, various vapor deposition films, Aluminum foil or the like can be used.
  • PET polyethylene terephthalate
  • OPA nylon
  • OPP biaxially oriented polypropylene
  • various vapor deposition films Aluminum foil or the like
  • Aluminum foil or the like can be used.
  • a sealant film such as an unstretched polypropylene (CPP) film or a linear low density polyethylene (LLDPE) film can be used.
  • CPP unstretched polypropylene
  • LLDPE linear low density polyethylene
  • Paper such as natural paper, synthetic paper, and coated paper may be used as the first film W1 and the second film W2.
  • a printed layer may be provided on the outer surface or inner surface side of the first film W1 and/or the second film W2, if necessary.
  • the laminated film 11a of the present embodiment is industrially used as a flexible packaging film, a flexible packaging (package whose shape is formed by putting contents in it) material, a packaging material for filling detergents, medicines, foods, beverages, etc. can be used as intended.
  • Specific examples of detergents and chemicals include liquid laundry detergents, liquid kitchen detergents, liquid bath detergents, liquid bath soaps, liquid shampoos, and liquid conditioners. Foods and beverages are not particularly limited.
  • the laminated film 11a of this embodiment can be used as a package by forming it into a bag shape.
  • the laminated film 11a of the present embodiment has an adhesive layer 10 between the first film W1 and the second film W2, and the adhesive layer 10 is formed from the cured two-component curable adhesive of the above embodiment. Become. Therefore, the laminated film 11a of the present embodiment has good heat-sealing properties such that excellent bonding strength can be obtained by heat-sealing.
  • Polyisocyanate composition (X-1) [Production of polyisocyanate (A)] A stirrer, a thermometer, a flask equipped with a nitrogen gas inlet tube, 4,4'-MDI; 41.9 parts, 2,4'-MDI; 13.0 parts, and xylylene diisocyanate; 0.1 parts was charged into a reaction vessel, stirred under nitrogen gas, and heated to 60°C.
  • a polyisocyanate composition (X-1) composed of the polyisocyanate (A) was obtained by adding dropwise in batches and stirring at 80° C. for 5 to 6 hours to cause a urethanization reaction.
  • the isocyanate content of polyisocyanate (A) was measured by a titration method using di-n-butylamine. As a result, it was 14% by mass. Moreover, the melt viscosity at 40° C. was measured for the polyisocyanate (A). As a result, it was 1500 mPa ⁇ s.
  • Polyisocyanate compositions (X-2) to (X-4) The following polyisocyanate compositions (X-2) to (X-4) were prepared.
  • X-2 2K-SF-220A (manufactured by DIC Corporation)
  • X-3 2K-SF-700A (manufactured by DIC Corporation)
  • X-4 Takenate 500, isocyanate content 44.7% by mass (manufactured by Mitsui Chemicals, Inc.)
  • polyisocyanate compositions (X-2) to (X-4) the isocyanate content was measured by a titration method using di-n-butylamine. The results are shown in Tables 3 and 4 as functional group amounts together with the results of polyisocyanate composition (X-1) (isocyanate content of polyisocyanate (A)).
  • Polyol composition (Y-1) A stirrer, a thermometer, a flask equipped with a nitrogen gas inlet tube, polyol castor oil: 70 parts, polyol D-1000: 15.8 parts, polyol EXCENOL 430: 6.6 parts, polyamine 6.6 parts of EC310 and 1.0 part of ⁇ -caprolactam as a catalyst were charged, heated to 80° C. under nitrogen gas, and stirred. After confirming that the solution became uniform, a polyol composition (Y-1) containing a polyol was obtained.
  • the hydroxyl value was measured for the materials used in the polyol composition (Y-1).
  • a hydroxyl value means the number of milligrams of potassium hydroxide corresponding to 1 g of the hydroxyl group of the sample.
  • a method for measuring the hydroxyl value is not particularly limited, and it can be calculated using a known method. In this example, the hydroxyl value was measured according to the hydroxyl value measurement method of JIS-K0070.
  • the amine value was measured for the materials used in the polyol composition (Y-1). Amine number refers to milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample.
  • the method for measuring the amine value is not particularly limited, and it can be calculated using a known method.
  • Polyol Compositions (Y-2) to (Y-4) Polyol composition (Y -2) to (Y-4) were obtained.
  • the hydroxyl value and amine value of the polyol compositions (Y-2) to (Y-4) were measured in the same manner as for the polyol composition (Y-1), and the total was obtained. The results are also shown in Table 1.
  • EXCENOL430 polypropylene glycol (manufactured by AGC; functional group 3, number average molecular weight of about 430, hydroxyl value of 400 mgKOH/g, 25°C melt shear viscosity of 350 mPa s)
  • EDP-300 N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (manufactured by ADEKA Co., Ltd.)
  • EC310 Polyoxypropylene polyamine (manufactured by BASF)
  • ⁇ -caprolactam 2-oxohexamethyleneimine (manufactured by Kanto Chemical Co., Ltd.)
  • DBTDL Dibutyltin dilaurate (manufactured by Nitto Kasei Co., Ltd.)
  • Bi-Zn Mixed catalyst of bismuth neodecanoate and zinc neodecanoate (manufactured by The Shepherd Chemical Company) Bicat 8108/Z mixture
  • Polyol Compositions (Y-5) to (Y-7) The following polyol compositions (Y-5) to (Y-7) were prepared.
  • Y-5 HA-234B, hydroxyl value 90 mgKOH/g (manufactured by DIC Corporation)
  • Y-6 HA-700B, hydroxyl value 120 mgKOH/g (manufactured by DIC Corporation)
  • Y-7 D-1000 (bifunctional polypropylene glycol, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., number average molecular weight of about 1,000), hydroxyl value: 112 mg KOH / g, 40 ° C. melt shear viscosity 150 mPa s)
  • the elongation viscosity at 40° C. and the elongation speed were determined by the methods described below.
  • the ⁇ elongation speed at which elongation hardening starts'' which is the lowest elongation speed at which the ⁇ elongation hardening behavior'' at which the elongation viscosity doubles or more occurs when the viscosity is doubled, was determined.
  • the elongational viscosity was measured according to the capillary rheometer evaluation method described in JIS-7199 (ISO 11443, ASTM D 3835). Specifically, a twin capillary device (RHEOGRAPH20 manufactured by Gottfert) was used. A capillary die with a length of 10 mm and a diameter of 0.5 mm and a capillary die with a length of 0.25 mm and a diameter of 0.5 mm were used.
  • Examples 1 to 6, Comparative Examples 1 to 3 Using the polyisocyanate compositions (X-1) to (X-4) and the polyol compositions (Y-1) to (Y-7) at the ratios (mass ratios) shown in Tables 3 and 4, Laminated films of Examples 1 to 6 and Comparative Examples 1 to 3 were prepared by the method shown below using the manufacturing apparatus shown in FIGS. 2 to 4, and heat-sealed by the method shown below. evaluated the sex.
  • any one of polyisocyanates (X-1) to (X-4) was applied to a corona-treated polyamide film (first film) having a thickness of 15 ⁇ m (first application step).
  • first coating step the temperature of the polyisocyanate compositions (X-1) to (X-4) stored in the coating liquid tank was set to 40°C.
  • one of the polyol compositions (Y-1) to (Y-7) was applied to a 60 ⁇ m thick linear low density polyethylene (LLDPE) film (second film) (second coating process).
  • LLDPE linear low density polyethylene
  • the total coating amount of the polyisocyanates (X-1) to (X-4) and the polyol compositions (Y-1) to (Y-7) is 2.0 g. / m2 .
  • the adhesive layer forming process was performed continuously from the first coating process and the second coating process.
  • the adhesive layer forming step by laminating the first film and the second film, any of the polyisocyanates (X-1) to (X-4) applied on the first film and on the second film It was carried out by contacting any of the polyol compositions (Y-1) to (Y-7) applied to the surface to cause a curing reaction.
  • the ratios of the polyisocyanate compositions (X-1) to (X-4) and the polyol compositions (Y-1) to (Y-7) are the polyisocyanate compositions (X-1) to (X-4). ) in the polyisocyanate (A) and the molar ratio of the sum of the hydroxyl groups and amino groups in the polyol compositions (Y-1) to (Y-7) [isocyanate group/(hydroxyl group + amino group) ] is in the range of 1.4 to 1.6. In Tables 3 and 4, the above molar ratios are listed as NCO excess.
  • the functional group content of the polyisocyanate composition shown in Tables 3 and 4 is the isocyanate content (%) of the polyisocyanate composition.
  • the functional group content of the polyol composition shown in Tables 3 and 4 is the sum of the hydroxyl value and amine value of the polyol composition (mgKOH/g).
  • the laminated films of Examples 1 to 6 and Comparative Examples 1 to 3 thus obtained were each aged at a temperature of 40° C. for 48 hours. After that, two test pieces each having a length of 200 mm and a width of 15 mm were cut out from the laminated film, and laminated with the linear low-density polyethylene (LLDPE) film sides facing each other.
  • LLDPE linear low-density polyethylene
  • For the two laminated test pieces using a heat seal bar with a width of 1 cm from the outside (polyamide film), heat and pressurize for 1 second under the conditions of a temperature of 180 ° C. and a pressure of 0.1 bar to heat seal (melt adhesion )did. The heat-sealed test piece was cut so that the length of the heat-sealed portion was 15 mm, peeled at a speed of 300 mm/min, and the heat-seal strength was measured.
  • the laminated film in which the adhesive layer is formed using the two-component curing adhesive in which the polyisocyanate composition (X) and the polyol composition (Y) exhibit elongation curing behavior has good heat sealability. I was able to confirm something.
  • 1 laminated film manufacturing apparatus, 10: adhesive layer, 11: first unwinding section, 11a: laminated film, 12: polyisocyanate coating section (first coating section), 13: second unwinding section, 14: Polyol coating part (second coating part), 15: Bonding device, 111: Film mounting part, 120: Liquid reservoir part, 121: Application roll, 122: Doctor roll, 123: Metering roll, 124: Coating roll, 125: backing roll, 126: barrier plate, 131: film mounting part, 141: gravure roll, 142: chamber, 142a: storage part, 142b: doctor blade, 142c: seal plate, 142d: side plate, 143: Impression cylinder, 144: Coating liquid tank, 145: Pump, 146: Temperature controller, 151: Bonding unit, 152: Winding unit, R1, R2: Lamination roll, W1: First film, W2: Second film .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
PCT/JP2022/004165 2021-02-15 2022-02-03 積層フィルム製造装置、積層フィルムの製造方法、二液硬化型接着剤、積層フィルム Ceased WO2022172840A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2022580586A JP7343063B2 (ja) 2021-02-15 2022-02-03 積層フィルム製造装置、積層フィルムの製造方法、二液硬化型接着剤、積層フィルム

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-021930 2021-02-15
JP2021021930 2021-02-15

Publications (1)

Publication Number Publication Date
WO2022172840A1 true WO2022172840A1 (ja) 2022-08-18

Family

ID=82837791

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/004165 Ceased WO2022172840A1 (ja) 2021-02-15 2022-02-03 積層フィルム製造装置、積層フィルムの製造方法、二液硬化型接着剤、積層フィルム

Country Status (3)

Country Link
JP (1) JP7343063B2 (https=)
TW (1) TW202242049A (https=)
WO (1) WO2022172840A1 (https=)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020071134A1 (ja) * 2018-10-01 2020-04-09 Dic株式会社 接着剤、積層体および積層体の製造方法
JP2020062786A (ja) * 2018-10-16 2020-04-23 藤森工業株式会社 袋用ラミネートフィルム及びその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020071134A1 (ja) * 2018-10-01 2020-04-09 Dic株式会社 接着剤、積層体および積層体の製造方法
JP2020062786A (ja) * 2018-10-16 2020-04-23 藤森工業株式会社 袋用ラミネートフィルム及びその製造方法

Also Published As

Publication number Publication date
JPWO2022172840A1 (https=) 2022-08-18
JP7343063B2 (ja) 2023-09-12
TW202242049A (zh) 2022-11-01

Similar Documents

Publication Publication Date Title
JP7004090B2 (ja) 接着剤、積層フィルム、及び積層フィルムの製造方法
CN111886313B (zh) 粘接剂、层叠膜和层叠膜的制造方法
JP6451021B2 (ja) 反応型接着剤、積層フィルム及び包装体
CN108138022A (zh) 粘接剂、使用其的层叠膜、以及粘接剂用多元醇组合物
JP6452018B1 (ja) ２液型接着剤用の硬化剤、２液型接着剤、積層フィルム及び包装体
JP7003572B2 (ja) 無溶剤型ラミネート接着剤、その硬化物、積層体及び包装体
JP7332066B2 (ja) 積層フィルム製造装置、積層フィルムの製造方法、二液硬化型接着剤、積層フィルム
JP7136363B1 (ja) 二液硬化型接着剤、積層フィルム、積層フィルム製造装置、積層フィルムの製造方法
JP7343063B2 (ja) 積層フィルム製造装置、積層フィルムの製造方法、二液硬化型接着剤、積層フィルム
JP7136364B1 (ja) 二液硬化型接着剤、積層フィルム、積層フィルム製造装置、積層フィルムの製造方法
WO2022172839A1 (ja) 二液硬化型接着剤、積層フィルム、積層フィルム製造装置、積層フィルムの製造方法
WO2022172841A1 (ja) 二液硬化型接着剤、積層フィルム、積層フィルム製造装置、積層フィルムの製造方法
TW202202549A (zh) 多元醇化合物及用其製備之黏著劑組合物
CN115836098A (zh) 多元醇化合物和用其制备的粘合剂组合物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22752667

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022580586

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22752667

Country of ref document: EP

Kind code of ref document: A1