JP7332066B2 - LAMINATED FILM MANUFACTURING APPARATUS, LAMINATED FILM MANUFACTURING METHOD, TWO-PART CURING ADHESIVE, LAMINATED FILM - Google Patents

Description

TECHNICAL FIELD The present invention relates to a laminated film manufacturing apparatus, a laminated film manufacturing method, a two-component curing adhesive, and a laminated film.

Conventionally, there is a laminated film produced by laminating two films with an adhesive, which is produced using a two-component curing adhesive that uses a curing reaction between a main agent and a curing agent. As the two-component curing adhesive, those using 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.
For example, in 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-adhering) the laminated films together or the laminated film and another film. For example, by heat-sealing 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.).

JP-A-58-122074

As 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. When using this method, 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.

Therefore, when the gelled product of the two-component curing adhesive adheres to each roll, it is necessary to clean each roll, which sometimes hinders the production efficiency of the laminated film. In particular, when manufacturing a laminated film used as a food packaging material, it is often the case that a large variety of small-lot products are sequentially produced by switching the type of film. If the curing reaction of the two-component curable adhesive progresses when the type of film is switched, gelled products of the two-component curable adhesive and the like tend to adhere to each roll. For this reason, the frequency of cleaning each roll has increased, which has been time-consuming.

In addition, in the above laminated film manufacturing method, if the manufacturing is unexpectedly stopped for a certain period of time due to manufacturing troubles, etc., the mixed main agent and curing agent that have undergone the curing reaction must be discarded. Ta.
The loss and trouble due to the pot life of these two-component curing adhesives have been a problem because they cause an increase in the manufacturing cost of laminated films.

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.

In order to solve the above problems, 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.

As a result, as a two-component curing type adhesive, one having a storage elastic modulus of 10 Pa or more within 1 hour from the start of the curing reaction by causing a curing reaction of the main agent and the curing agent at 25° C. was used. After coating the film and applying the curing agent onto the second film, the main agent-coated surface of the first film and the curing agent-coated surface of the second film are bonded together to mix the main agent and the curing agent, and the film The present inventors have found that the above-mentioned problems can be solved by simultaneously performing the lamination and lamination, and have conceived the present invention.
That is, the present invention relates to the following matters.

[1] A polyisocyanate composition (X) containing a polyisocyanate (A) and a polyol composition (Y) containing a polyol (B) are subjected to a curing reaction at 25°C within 1 hour from the start of the curing reaction. A laminated film manufacturing apparatus for bonding a first film and a second film using a two-component curing adhesive having a storage elastic modulus of 10 Pa or more,
A first coating unit that applies the polyisocyanate composition (X) to the first film;
a second coating unit that applies the polyol composition (Y) 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).

[2] A polyisocyanate composition (X) containing a polyisocyanate (A) and a polyol composition (Y) containing a polyol (B) are subjected to a curing reaction at 25° C. within 1 hour from the start of the curing reaction. A method of manufacturing a laminated film by bonding a first film and a second film together using a two-component curing adhesive having a storage elastic modulus of 10 Pa or more,
A first application step of applying the polyisocyanate composition (X) to the first film;
A two-liquid separate coating step consisting of a second coating step of coating the polyol composition (Y) on a 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.

[3] Curing of the polyisocyanate composition (X) containing the polyisocyanate (A) and applied to the first film and the polyol composition (Y) containing the polyol (B) and applied to the second film A two-component curing adhesive that uses a reaction,
A two-component curing adhesive having a storage elastic modulus of 10 Pa or more within 1 hour from the start of the curing reaction by curing the polyisocyanate composition (X) and the polyol composition (Y) at 25°C. .

[4] The two-component curable adhesive according to [3], wherein tan δ is 8 or less one hour after the initiation of the curing reaction.

[5] having an adhesive layer between the first film and the second film;
A laminated film, wherein the adhesive layer comprises a cured product of the two-component curing adhesive according to [3] or [4].

The apparatus for producing a laminated film of the present invention causes the polyisocyanate composition (X) and the polyol composition (Y) to undergo a curing reaction at 25° C., so that the storage elastic modulus is 10 Pa or more within 1 hour from the start of the curing reaction. A laminated film manufacturing apparatus that laminates a first film and a second film using a two-component curing adhesive, and the first coating unit applies the polyisocyanate composition (X) to the first film The second coating section applies the polyol composition (Y) 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.

In the method for producing a laminated film of the present invention, the polyisocyanate composition (X) and the polyol composition (Y) are cured at 25° C., and the storage elastic modulus is 10 Pa or more within 1 hour from the start of the curing reaction. A method for producing a laminated film by bonding the first film and the second film using a two-component curing adhesive, which has a two-component separate coating step, and in the first coating step, the polyisocyanate composition (X) is applied to the first film, and in a second application step the polyol composition (Y) is applied to the second film. Therefore, in 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 By performing 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 two-component curable adhesive of the present invention is obtained by subjecting the polyisocyanate composition (X) applied to the first film and the polyol composition (Y) applied to the second film to a curing reaction at 25 ° C. , the storage elastic modulus becomes 10 Pa or more within 1 hour from the start of the curing reaction. Therefore, the two-component curing adhesive of the present invention has good reactivity and can be efficiently cured with a small amount of energy. In addition, the laminated film in which the adhesive layer is formed between the first film and the second film using the two-component curing adhesive of the present invention can obtain excellent bonding strength by heat sealing.

The laminated film of the present invention has an adhesive layer between the first film and the second film, and the adhesive layer is composed of a cured product of the two-component curable adhesive of the present invention. Therefore, the laminated film of the present invention can be produced efficiently with a small amount of energy by using the two-component curing adhesive of the present invention having good reactivity between the polyisocyanate composition (X) and the polyol composition (Y). can be manufactured. In addition, the laminate film has good heat-sealing properties, and excellent bonding strength can be obtained by heat-sealing.

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.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The laminated film manufacturing apparatus, laminated film manufacturing method, two-component curing adhesive, and laminated film of the present invention will be described in detail below with reference to the drawings. In the drawings used in the following description, in order to make it easier to understand the features of the present invention, there are cases where the feature portions are enlarged for the sake of convenience. Therefore, the dimensional ratio of each component may differ from the actual one.

[Laminated film manufacturing equipment]
Next, the laminated film manufacturing apparatus of the present embodiment will be described in detail with reference to the drawings.
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. As shown in FIG. 1, the laminated film 11a of this embodiment has an adhesive layer 10 between the first film W1 and the second film W2. In the laminated film 11a of the present embodiment, the adhesive layer 10 is made of the cured two-component curing adhesive of the present embodiment. 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.

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.

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.

As shown in FIG. 2, 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 .
As shown in FIG. 3, 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.
As shown in FIG. 3, the application roll 121 and doctor roll 122 rotate downward in the liquid reservoir 120 . As a result, the outer peripheral surface of the doctor roll 122 is coated with the polyisocyanate composition (X) that has passed through the minute gaps.

As shown in FIG. 3, the polyisocyanate coating section 12 rotatably supports a metering roll 123, a coating roll 124, and a backing roll 125. As shown in FIG.
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 . Moreover, 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.
Like the doctor roll 122, 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 (gravure pattern) 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 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.
As shown in FIG. 4 , 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 .

As shown in FIG. 4, 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 .

A temperature adjuster 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 bonding section 151 has a pair of laminate 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.

As shown in FIG. 2, 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. In the bonding portion 151, 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 unit 152 winds up the laminated film 11 a formed by bonding the first film W<b>1 and the second film W<b>2 in the bonding unit 151 .

[Method for producing laminated film]
Next, as a method for manufacturing a laminated film of the present embodiment, using the laminated film manufacturing apparatus 1 shown in FIGS. A case of manufacturing the laminated film 11a shown in FIG. 1 by laminating the second film W2 will be described as an example.
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.

(Two-liquid separate application process)
The two-liquid separate application step includes a first application step of applying the polyisocyanate composition (X) containing the polyisocyanate (A) to the first film W1, and a second application of the polyol composition (Y) containing the polyol (B). and a second coating step of coating the film W2. In this embodiment, the first coating process and the second coating process are performed simultaneously.

"First coating process"
A method of performing the first coating step using the laminated film manufacturing apparatus 1 shown in FIGS. 2 to 4 will be described.
First, the first film W1 is delivered from the first unwinding section 11 to the polyisocyanate coating section 12 . In the polyisocyanate coating section 12, each roll is rotated in the direction indicated by the arrow in FIG. As a result, the polyisocyanate composition (X) stored in the liquid reservoir 120 is applied to the surface of the doctor roll 122 .

In the present embodiment, the temperature of the polyisocyanate composition (X) stored in the liquid reservoir 120 is preferably set to 25° C. to 80° C., preferably 25° C. to 40° C., by a temperature control unit (not shown). is more preferable.
In the present embodiment, the 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. As a result, 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.
In this embodiment, 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 .
In the polyisocyanate coating section 12 , the first film W<b>1 coated with the polyisocyanate composition (X) is delivered to the bonding device 15 .

"Second coating process"
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 delivered from the second unwinding section 13 to the polyol coating section . In the polyol coating section 14, 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 .

In this embodiment, 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 .

In the present embodiment, 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.
In this embodiment, 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. In the present embodiment, as shown in FIG. 4, 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. As a result, 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.
In the polyol coating section 14 , 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.

In the lamination unit 151 of the lamination device 15, as shown in FIG. 2, 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.

In this embodiment, 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 .
In this embodiment, 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. 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, and curing of the two-component curable adhesive is started. be.

By curing the two-component curing adhesive, 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 .

In the method for manufacturing the laminated film 11a of the present embodiment, the film transport speed (the winding speed of the laminated film 11a in the winding unit 152) when manufacturing the laminated film 11a can be set to, for example, 30 to 300 m/min. preferably 100 to 250 m/min. A laminated film can be produced efficiently when the film transport speed is 30 m/min or more. If the film transport speed exceeds 300 m/min, problems such as problems in coating, problems in transport itself, and problems in bonding may occur. Therefore, it is preferable to set the film transport speed to 300 m/min or less.

The laminated film 11a obtained by the manufacturing method of the present embodiment is obtained by bonding the first film W1 and the second film W2 together in the bonding section 151, and after being wound up by the winding section 152, Alternatively, aging is performed by storing for 3 to 48 hours under heating. Since the two-component curing adhesive of this embodiment cures quickly at a low temperature, it can be aged at room temperature of about 25° C. for 3 to 24 hours. In this embodiment, aging may be performed at 40° C. for 48 to 72 hours for more reliable curing. By appropriately selecting and setting the aging as described above, the two-component curing adhesive is sufficiently cured, and practical physical properties as the adhesive layer 10 are exhibited.

The manufacturing apparatus 1 of the laminated film 11a of the present embodiment includes a polyisocyanate coating unit 12 that applies the polyisocyanate composition (X) to the first film W1, and a polyol composition (Y) to the second film W2. It has a polyol coating part 14 and a bonding device 15 for bonding the polyisocyanate composition (X)-coated surface of the first film W1 and the polyol composition (Y)-coated surface of the second film W2. Therefore, the manufacturing apparatus 1 of the laminated film 11a of the present embodiment uses the two-component curing adhesive of the present embodiment, and the manufacturing method of the present embodiment having the two-component separate application 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.

In the manufacturing apparatus 1 of the laminated film 11a of the present embodiment, 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. may be When 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. Moreover, by using a gravure coater, the configuration of the polyol coating section 14 can be simplified, and the manufacturing apparatus for the laminated film 11a can be miniaturized.

In the production apparatus 1 for the laminated film 11a of the present embodiment, a roll coater is used in the polyisocyanate coating section 12 that coats the first film W1 with the polyisocyanate composition (X) having a relatively high viscosity. By using a roll coater, it is possible to apply even when the viscosity of the polyisocyanate composition (X) is relatively high, and the range of selection of the material of the polyisocyanate composition (X) is widened.

The method for producing the laminated film 11a of the present embodiment includes a first coating step of coating the polyisocyanate composition (X) on the first film W1, and a second coating step of coating the polyol composition (Y) on the second film W2. By laminating the first film W1 and the second film W2, the polyisocyanate composition (X) applied on the first film W1 and the second film W2 on and an adhesive layer forming step of bringing into contact with the polyol composition (Y) applied to the surface to cause a curing reaction.

Since the method for manufacturing the laminated film 11a of the present embodiment has a two-component separate application step, the step of mixing the polyisocyanate composition (X) and the polyol composition (Y) is not required. 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). In addition, since 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.

In the method for producing the laminated film 11a of the present embodiment, the two-component curing adhesive of the present embodiment having good reactivity between the polyisocyanate composition (X) and the polyol composition (Y) is used to prepare the first film. The laminated film 11a is manufactured by laminating W1 and the second film W2. Therefore, it is not necessary to heat the two-component curable adhesive in order to cure the two-component curable adhesive, the aging temperature can be set to room temperature (25° C.), and the aging time can be shortened. Therefore, a laminated film having good heat-sealing properties can be produced efficiently with a small amount of energy.

In the above-described embodiment, 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. .

Further, in the polyol coating section 14 in the manufacturing apparatus 1 for the laminated film 11a of the above embodiment, 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.

[Two-component curing adhesive]
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 polyisocyanate (A). Polyol composition (Y) contains polyol (B). The polyisocyanate composition (X) may contain part of the polyol (B) contained in the two-component curing adhesive, if necessary.
The two-component curable adhesive of this embodiment cures through a chemical reaction between the isocyanate groups in the polyisocyanate composition (X) and the hydroxyl groups (or hydroxyl groups and amino groups) in the polyol composition (Y).

(Storage modulus when cured at 25°C)
The two-component curable adhesive of the present embodiment has a storage modulus of 10 Pa within 1 hour from the start of the curing reaction by curing the polyisocyanate composition (X) and the polyol composition (Y) at 25 ° C. That's it. Therefore, the two-component curing adhesive of the present embodiment has good reactivity and can be efficiently cured with a small amount of energy. Specifically, there is no need to heat the two-component curable adhesive in order to cure the two-component curable adhesive, and the aging temperature can be set to room temperature (25° C.), and the aging time can be shortened. . As a result, energy consumption can be reduced, processes can be shortened, and work efficiency can be improved. In addition, the two-component curable adhesive of the present embodiment is used to form an adhesive layer between the first film and the second film, so that excellent bonding strength can be obtained by heat sealing. Can form films.

Since the two-component curable adhesive of the present embodiment is a two-component curable adhesive with even better reactivity, the curing reaction is performed at 25 ° C., and the storage elasticity reaches within 1 hour from the start of the curing reaction. is preferably 15 Pa or more, more preferably 100 Pa or more, even more preferably 300 Pa or more, particularly preferably 1000 Pa or more, particularly preferably 2500 Pa or more, particularly preferably 8000 Pa or more. It is most preferable to be When the polyisocyanate composition (X) and the polyol composition (Y) are subjected to a curing reaction at 25° C., the storage elastic modulus within 1 hour from the initiation of the curing reaction is preferably 50 MPa or less. This is because, when the adhesive layer 10 of the laminated film 11a is a cured product of the two-component curing type adhesion of the present embodiment, the adhesive layer 10 can be bent, stretched, etc., of the first film W1 and the second film W2. This is because the strength of the laminated film 11a is not affected by the inability to follow the deformation.

The storage elastic modulus within 1 hour from the start of the curing reaction when the polyisocyanate composition (X) and the polyol composition (Y) are cured at 25° C. can be adjusted by adjusting the content of the curing accelerator. You can control it.
It should be noted that those skilled in the art can obtain the polyisocyanate composition (X) and the polyol composition (Y) based on known techniques within the scope of ordinary experiments by appropriately adjusting the content of the curing accelerator. When the curing reaction is performed at 25° C., the storage elastic modulus within 1 hour from the start of the curing reaction is within the desired range.

(tan δ when curing reaction is performed at 25°C)
In the two-component curable adhesive of the present embodiment, when the polyisocyanate composition (X) and the polyol composition (Y) are cured at 25° C., the tan δ after 1 hour from the start of the curing reaction is 50 or less. is preferably 15 or less, more preferably 8 or less, and particularly preferably 4 or less. Furthermore, tan δ after 1 hour is preferably 1.5 or less, most preferably 1.0 or less. A two-component curing adhesive having a tan δ of 50 or less one hour after the initiation of the curing reaction has much better reactivity and can be efficiently cured with a small amount of energy. Moreover, by using this to form an adhesive layer between the first film and the second film, a laminated film with better heat sealability can be obtained.

The tan δ of the two-component curing adhesive in the present invention is the ratio (G''/G') of the loss elastic modulus G'' to the storage elastic modulus G'. A tan δ of greater than 1.0 is an indicator of the dominance of the viscous component of the two-component curing adhesive. A tan δ of 1.0 or less is an index indicating that the elastic component of the two-component curing adhesive is dominant. Generally, in a two-component curing adhesive, tan δ gradually decreases as the curing reaction progresses. Therefore, if the tan δ after 1 hour from the start of the curing reaction is 1.0 or less when the two-component curing adhesive is cured at 25 ° C., the curing reaction is performed even though the temperature is about room temperature. It means that the curing reaction has progressed to the point where the elastic element predominates at 1 hour from the start.

Methods for measuring storage modulus and loss modulus are not particularly limited, and can be measured using known methods and commercially available devices. In the examples of the present invention described later, a storage modulus at an angular frequency of 10/s was measured using a rotational rheometer (trade name: MCR-102, manufactured by Anton Paar) in accordance with JIS-K7244-10 (2005). (G′) and loss modulus (G″) were measured to calculate tan δ (G″/G′).

When the polyisocyanate composition (X) and the polyol composition (Y) are cured at 25° C., the tan δ one hour after the start of the curing reaction can be controlled by adjusting the content of the curing accelerator. .
It should be noted that those skilled in the art can obtain the polyisocyanate composition (X) and the polyol composition (Y) based on known techniques within the scope of ordinary experiments by appropriately adjusting the content of the curing accelerator. When the curing reaction is performed at 25° C., the tan δ one hour after the initiation of the curing reaction is within the desired range.

(Polyisocyanate (A))
As the polyisocyanate (A), known ones can be used without particular limitation.
Examples of the polyisocyanate (A) include
tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate (hereinafter diphenylmethane diisocyanate may be simply referred to as "MDI"), 2,2'-MDI, 4,4'-MDI, 1,5-naphthalene diisocyanate , aromatic polyisocyanates such as triphenylmethane triisocyanate;
Aliphatic polyisocyanates such as xylylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl)cyclohexane, 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate ;
Compounds in which a portion of the isocyanate groups (hereinafter sometimes referred to as "NCO groups") of these polyisocyanates are modified with carbodiimide;
isocyanurate derived from these polyisocyanates; allophanate derived from these polyisocyanates; biuret derived from these polyisocyanates; adducts obtained by modifying these polyisocyanates with trimethylolpropane;
Polyisocyanate (A1), which is a reaction product (prepolymer) of various polyisocyanates and polyol components (hereinafter, this prepolymer polyisocyanate may be referred to as "polyisocyanate (A1)"), etc. is mentioned.

In the polyisocyanate (A1), specific examples of the polyol component to be reacted with the aromatic polyisocyanate and the aliphatic polyisocyanate 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, chain aliphatic glycols such as bishydroxyethoxybenzene; alicyclic glycols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; glycerin, trimethylolpropane, pentaerythritol Trifunctional or tetrafunctional aliphatic alcohol such as; Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of agents; propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, A polyester polyol (1) which is a reaction product of a polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound such as β-methyl-σ-valerolactone and the glycol or trifunctional or tetrafunctional aliphatic alcohol;

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. polyol (4);
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.

Among these polyisocyanates (A), 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.

From the viewpoint of the flexibility of the coating film after curing of the polyisocyanate (A1), 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.
As an example, 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.

As used herein, 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 μl)

In the polyisocyanate (A1), the polyisocyanate to be reacted with the polyol component preferably contains an aromatic polyisocyanate because of its excellent reactivity with the polyamine (C) described below. 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). From the viewpoint of storage stability, 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.

As the polyisocyanate to be reacted with the polyol component, at least one of aliphatic polyisocyanate and aliphatic polyisocyanate derivative is preferably used in combination 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.
When the polyisocyanate (A) is the polyisocyanate (A1), it preferably has a weight average molecular weight (Mw) in the range of 300 to 10,000.

The polyisocyanate (A) preferably has an isocyanate content of 5 to 20% by mass. The polyisocyanate composition (X) containing such a polyisocyanate (A) is preferable because it has an appropriate resin viscosity and is excellent in coatability.
The isocyanate content of polyisocyanate (A) is a value determined by a titration method using di-n-butylamine.

(Polyol (B))
Examples of the polyol (B) 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; A polyether polyol obtained by addition polymerization of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene in the presence of a polymerization initiator such as an aliphatic alcohol; Polyether urethane polyol polymerized with aromatic or aliphatic polyisocyanate; ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone A polyester polyol (1) which is a reaction product of a polyester obtained by and a polyhydric alcohol such as the glycol, glycerin, trimethylolpropane, pentaerythritol;

a 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;
A polyester polyurethane polyol obtained by polymerizing the polyester polyols (1) to (5) with an aromatic or aliphatic polyisocyanate;
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. , 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and other aliphatic dicarboxylic acids; terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6- Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis(phenoxy)ethane-p,p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, and dimer 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.
In the tertiary amine compound having a plurality of hydroxyl groups, 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.

Specific examples of tertiary amine compounds having a plurality of hydroxyl groups include polypropylene glycol ethylene diamine ether, tri(1,2-polypropylene glycol) amine, N-ethyldiethanolamine, N-methyl-N-hydroxyethyl-N-hydroxy ethoxyethylamine, pentakishydroxypropyldiethylenetriamine, tetrakishydroxypropylethylenediamine, N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, triethanolamine and the like.

A commercially available product may be used as the tertiary amine compound having a plurality of 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.

When the polyol (B) contains a tertiary amine compound having a plurality of hydroxyl groups, 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.

As polyol (B), these compounds can be used singly or in combination.
Polyol (B) preferably contains a polyol having a polyether skeleton, and more preferably contains a polyol having a polypropylene skeleton. Such 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. In addition, 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).

When the weight-average molecular weight (Mw) of the polyol (B) is 400 to 5000, the viscosity is in an appropriate range, 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.

(Polyamine (C))
The polyol composition (Y) preferably contains a polyamine (C). Polyamine (C) functions as a curing accelerator.
As 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-diaminopropane ,

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-aminoethyl)amine, bishexamethylenetriamine, etc., 1, 4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebiscyclohexylamine, norbornadiamine,

Bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, isophoronediamine, menzenediamine, etc., bis(aminoalkyl)benzene, bis(aminoalkyl)naphthalene, bis(cyanoethyl)diethylenetriamine, orthoxylylenediamine, metaxylylenediamine, para xylylenediamine, phenylenediamine, naphthylenediamine, diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4, 4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 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-amino propyl)-piperazine, piperazine-1,4-diazacycloheptane, 1-(2′-aminoethylpiperazine), 1-[2′-(2″-aminoethylamino)ethyl]piperazine, tricyclodecanediamine, Examples include polyureaamine, which is a reaction product of various polyamines described above and various isocyanate components described above.

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 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. When the above molar ratio is 0.001 or more, the workability of the laminated film produced using the two-component curing adhesive becomes favorable. When the molar ratio is 2.0 or less, the adhesion strength of the two-component curing adhesive becomes good.

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

Specific examples of 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. Among these, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are particularly highly soluble organic solvents.

The two-part curable adhesive of this embodiment can be diluted with a solvent to obtain a desired viscosity when it is required to lower the viscosity. In that case, a solvent may be used to dilute either one of the polyisocyanate composition (X) or the polyol composition (Y), or both.

Examples of organic solvents that may be contained in the two-component curing adhesive of the present embodiment 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. Among these, it is preferable to use ethyl acetate and/or methyl ethyl ketone (MEK), and it is particularly preferable to use ethyl acetate, from the viewpoint of the solubility of the polyisocyanate composition (X) and the polyol composition (Y).
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.

(catalyst)
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.

When 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 acts 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). Examples of 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.
As 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. Among these metal complex catalysts, iron acetylacetonate (Fe(acac) ₃ ) and/or manganese acetylacetonate (Mn(acac) ₂ ) are preferable from the viewpoint of toxicity and catalytic activity.

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. Of these, preferred organometallic catalysts are stannous dioctoate, dibutyltin dilaurate, bismuth neodecanoate, zinc neodecanoate, or mixtures thereof.

Examples of amine-based catalysts include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine. Among these, triethylenediamine and/or 2-methyltriethylenediamine are preferably used as the amine-based catalyst because of their excellent catalytic activity and industrial availability.

Other 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(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanolamine, 3-quinuclidinol, 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, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2 -methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperazine, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxy propyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole and the like.

Aliphatic cyclic amide compounds used as catalysts include, for example, δ-valerolactam, ε-caprolactam, ω-enanthrolactam, η-capryllactam, β-propiolactam and the like. Among these aliphatic cyclic amide compounds, ε-caprolactam can more effectively accelerate the curing of two-component curing adhesives.

The content of the catalyst in the two-component curing adhesive of the present 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.

(adhesion promoter)
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 coupling agents, aluminum coupling agents, epoxy resins, and the like.

Silane coupling agents include, for example, γ-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, Aminosilanes such as N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycides Epoxysilanes such as xypropyltrimethoxysilane and γ-glycidoxypropyltriethoxysilane; Vinylsilanes such as vinyltris(β-methoxyethoxy)silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane ; hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, and the like.

Examples of titanate-based coupling agents include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, tetrastearoxytitanium, and the like. can be mentioned.
Examples of aluminum-based coupling agents include acetoalkoxyaluminum diisopropylate.

As the epoxy resin, generally commercially available epi-bis type, novolac type, β-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 the present 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.

(pigment)
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 various pigments can be used. Pigments include, for example, 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 Raw Materials (edited by the Japan Paint Manufacturers Association). Examples include organic pigments such as pigments, luminescent pigments and pearlescent pigments, inorganic pigments, and plastic pigments.

Examples of organic pigments 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. 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;

Examples of 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.
Examples of plastic pigments include "Glandole 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 white 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. When 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.

(Additive)
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; polymethyl methacrylate-based organic fine particles; antifoaming agents; Deactivator; peroxide decomposer; flame retardant; reinforcing agent; plasticizer; lubricant; rust inhibitor; fluorescent whitening agent; is mentioned.

The two-component curing adhesive of the present embodiment is a two-component curing type using a curing reaction between a polyisocyanate composition (X) containing a polyisocyanate (A) and a polyol composition (Y) containing a polyol (B). When the polyisocyanate composition (X) and the polyol composition (Y) are cured at 25° C., the adhesive has a storage modulus of 10 Pa or more within 1 hour from the start of the curing reaction. Therefore, the two-component curing adhesive of this embodiment has good reactivity and can be efficiently cured with a small amount of energy. In addition, 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.

[Laminated film]
Next, the laminated film 11a of this embodiment will be described in detail.
As shown in FIG. 1, 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.

(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.
Examples of 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.
As the second film W2, for example, a sealant film such as an unstretched polypropylene (CPP) film or a linear low density polyethylene (LLDPE) film can be used.

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 uses the two-component curing adhesive of the present embodiment, which has good reactivity between the polyisocyanate composition (X) and the polyol composition (Y), and uses less energy. It can be produced efficiently in large quantities. Specifically, there is no need to heat the two-component curable adhesive in order to cure it, so the aging temperature can be set to room temperature (25°C), and the aging time can be shortened. can. In addition, the laminated film 11a of the present embodiment has good heat-sealing properties such that excellent bonding strength can be obtained by heat-sealing.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the present invention is not limited only to the following examples. In the following examples, "parts" and "%" are based on mass unless otherwise specified.

(Polyisocyanate composition (X-1))
[Production of polyisocyanate (A-1)]
A stirrer, a thermometer, a flask equipped with a nitrogen gas inlet tube, 4,4'-MDI: 40.2 parts, hexamethylene diisocyanate nurate (hereinafter abbreviated as "HDI nurate"): 10.0 parts was charged into a reaction vessel, stirred under nitrogen gas, and heated to 60°C. Into this flask were further added 37.9 parts of bifunctional polypropylene glycol having a number average molecular weight of 1000 (hereinafter abbreviated as "PPG") and 2,2,4-trimethyl-1,3-pentanediol: 2.5 parts. 0 part of the mixture was added dropwise in several portions, and the mixture was stirred at 80° C. for 5 to 6 hours for urethanization reaction to obtain a polyisocyanate. The obtained polyisocyanate was mixed with carbodiimide-modified isocyanate: 10.0 parts to obtain a polyisocyanate composition (X-1) comprising polyisocyanate (A-1).

The isocyanate content of the polyisocyanate composition (X-1) was measured by a titration method using di-n-butylamine. As a result, it was 14%.
Further, the melt shear viscosity at 40° C. was measured for the polyisocyanate composition (X-1). As a result, 1500mPa. was s.

(Polyisocyanate composition (X-2) (X-3))
2K-SF-220A (manufactured by DIC Corporation) was prepared as the polyisocyanate composition (X-2).
2K-SF-700A (manufactured by DIC Corporation) was prepared as the polyisocyanate composition (X-3).
The isocyanate content of each of the polyisocyanate compositions (X-2) and (X-3) was measured by a titration method using di-n-butylamine. As a result, the isocyanate content of the polyisocyanate composition (X-2) was 14% by mass. Further, the isocyanate content of the polyisocyanate composition (X-3) was 21% by mass.

(Polyol Compositions (Y-1) to (Y-7))
The polyol (B), polyamine (C) and additives shown in Table 1 were mixed in the proportions shown in Table 1 to obtain polyol compositions (Y-1) to (Y-7).

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, 40° C. melt shear viscosity 250 mPa s)
D-1000: Polypropylene glycol (manufactured by Mitsui Chemicals Polyurethanes, Inc., number average molecular weight of about 1,000, hydroxyl value of 112 mgKOH/g, 40° C. melt shear viscosity of 150 mPa s) Actcol D-1000
EXCENOL430: polypropylene glycol (manufactured by AGC; functional group 3, number average molecular weight of about 430, hydroxyl value of 400 mgKOH/g, melt shear viscosity of 350 mPa s at 25°C)
EDP-300: N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine (ADEKA Corporation)

"Polyamine (C)"
EC310: Polyoxypropylene polyamine (manufactured by BASF) Baxxdur EC310
"catalyst"
ε-caprolactam: 2-oxohexamethyleneimine (manufactured by Kanto Chemical Co., Ltd.)

(Polyol composition (Y-8) (Y-9))
HA-234B (manufactured by DIC Corporation) with a hydroxyl value of 90 mgKOH/g was used as the polyol component Y-8.
HA-700B (manufactured by DIC Corporation) with a hydroxyl value of 120 mgKOH/g was used as the polyol component Y-9.

The hydroxyl value was measured for the materials used in the polyol compositions (Y-1) to (Y-9). A hydroxyl value means the number of milligrams of potassium hydroxide corresponding to 1 g of the hydroxyl group of the sample. A method for measuring the hydroxyl value is not particularly limited, and it can be calculated using a known method. In this example, the hydroxyl value was measured according to the hydroxyl value measurement method of JIS-K0070.
The amine value was measured for the materials used in the polyol compositions (Y-1) to (Y-9). Amine number refers to milligrams of KOH equivalent to the amount of HCl required to neutralize 1 g of sample. The method for measuring the amine value is not particularly limited, and it can be calculated using a known method. In this example, it was measured according to the amine value standard test method of ASTM D2073.
Then, the sum of the hydroxyl value and the amine value contained in the polyol compositions (Y-1) to (Y-9) was determined.

"Two-component curing adhesive of Examples 1 to 16 and Comparative Example 1"
Polyisocyanates (X-1) to (X-3) and polyol compositions (Y-1) to (Y-9) were mixed at 25° C. in the proportions shown in Table 2 or Table 3, and mixed. The storage modulus and loss modulus after 1 hour at 25° C. (from the start of the curing reaction) were measured by the methods described below, and tan δ was determined. The results are shown in Tables 2 and 3.

The storage modulus and loss modulus were measured using a method in accordance with JIS-K7244-10 (2005). Specifically, the two liquids were mixed using a rotational rheometer (trade name; MCR-102, manufactured by AntonPaar) to determine the storage modulus (G') and the loss modulus (G") at an angular frequency of 10/s. was measured continuously for 1 hour, and tan δ was calculated by the following formula using the storage modulus (G') and the loss modulus (G").
tan δ = G''/G'(G' in the formula is the storage modulus. G'' is the loss modulus.)
A tan δ of greater than 1.0 is an indicator of the dominance of the viscous component of the two-component curing adhesive. A tan δ of 1.0 or less is an index indicating that the elastic component of the two-component curing adhesive is dominant.

"Laminate films of Examples 1 to 16 and Comparative Example 1"
Using the polyisocyanates (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-9) in the proportions shown in Table 2 or Table 3, by the method shown below, Using the manufacturing apparatus shown in FIGS. 2 to 4, laminated films of Examples 1 to 16 and Comparative Example 1 were produced.

Any one of polyisocyanates (X-1) to (X-3) was applied to a corona-treated polyamide film (first film) having a thickness of 15 μm (first application step). In the first coating step, the temperature of the polyisocyanate compositions (X-1) to (X-3) stored in the coating liquid tank was set to 40°C.
Simultaneously with the first coating step, one of the polyol compositions (Y-1) to (Y-9) was applied to a 60 μm-thick linear low-density polyethylene (LLDPE) film (second film) (second coating process).
In the first coating step and the second coating step, the total coating amount of the polyisocyanates (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-9) is 1.5. ˜2.0 g/m ² .

Then, the adhesive layer forming step was performed continuously from the first coating step and the second coating step. In the adhesive layer forming step, by laminating the first film and the second film, any of the polyisocyanates (X-1) to (X-3) applied on the first film and on the second film It was carried out by contacting any of the polyol compositions (Y-1) to (Y-9) applied to the surface to cause a curing reaction.

The ratio of the polyisocyanates (X-1) to (X-3) and the polyol compositions (Y-1) to (Y-9) is the isocyanate possessed by the polyisocyanates (X-1) to (X-3). The molar ratio [isocyanate group/(hydroxyl value + amine value)] of the group to the sum of the hydroxyl value and amine value of the polyol compositions (Y-1) to (Y-9) is 1.4 to 1. .6 range. In Tables 2 and 3, the above molar ratios are listed as NCO excess. The functional group content of the polyisocyanate compositions shown in Tables 2 and 3 is the isocyanate content (%) of the polyisocyanates (X-1) to (X-3). The functional group content of the polyol composition described in Table 2 or Table 3 is the sum of the hydroxyl value and amine value of the polyol composition (mgKOH/g).

The laminated films obtained after the adhesive layer forming step were aged by storing at 25° C. for 1 hour, 3 hours, 6 hours and 24 hours.
After that, two test pieces each having a length of 200 mm and a width of 15 mm were cut out from the laminated film, and laminated with the linear low-density polyethylene (LLDPE) film sides facing each other. 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.

"standard"
The heat-sealing strength was evaluated by evaluating the maximum load at which the heat-sealed portion breaks on a scale of 5 according to the following criteria, and 4 or more was accepted. Table 2 or Table 3 shows the evaluation results of the heat seal strength. 5: 50N/15mm or more 4: 40N/15mm to 49N/15mm
3: 30N/15mm to 39N/15mm
2: 20N/15mm to 29N/15mm
1:0~19N/15mm

As shown in Tables 2 and 3, after mixing the polyisocyanate (X) and the polyol composition (Y) at 25°C (from the start of the curing reaction), the storage elastic modulus after 1 hour at 25°C was For the laminated films of Examples 1 to 16 using a two-component curing adhesive of 10 Pas or more, the storage elastic modulus after 1 hour is less than 10 Pa of Comparative Example 1 using a two-component curing adhesive. Good heat-sealability was obtained as compared with the laminated film.
More specifically, for the laminated films of Examples 1 to 16, the evaluation of heat seal strength was "4" or "5" even when low-temperature and short-time aging was performed by storing at 25 ° C. for 6 hours. ”, and good heat-sealability was obtained.
On the other hand, the laminated film of Comparative Example 1 was evaluated as "1" for heat seal strength even after aging for 24 hours, indicating insufficient heat sealability.

In particular, after mixing the polyisocyanate (X) and the polyol composition (Y) at 25°C (from the start of the curing reaction), tan δ after 1 hour at 25°C is 1 or less. For the laminated films of Examples 4 to 7 using , the evaluation of heat seal strength is "4" or "5 ”, and good heat-sealability was obtained.

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 .

Claims (11)

A polyisocyanate composition (X) containing a polyisocyanate (A) and a polyol composition (Y) containing a polyol (B) are subjected to a curing reaction at 25° C., whereby the storage elastic modulus is reduced within 1 hour from the start of the curing reaction. A laminated film manufacturing apparatus for bonding a first film and a second film using a two-component curing adhesive having a viscosity of 10 Pa or more,
A first coating unit that applies the polyisocyanate composition (X) to the first film;
a second coating unit that applies the polyol composition (Y) to the second film;
a laminating device for laminating the polyisocyanate composition (X)-coated surface of the first film and the polyol composition (Y)-coated surface of the second film ,
The polyisocyanate (A) contains at least a reaction product of an aromatic polyisocyanate, an aliphatic polyisocyanate and a polyol,
The NCO excess expressed by [the isocyanate group of the polyisocyanate composition (X)/(the sum of the hydroxyl value and the amine value of the polyol composition (Y))] (molar ratio) is 1.4. The laminated film manufacturing apparatus , which is in the range of ~1.6 . 2. The laminated film manufacturing apparatus according to claim 1, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate, the aliphatic polyisocyanate is hexamethylene diisocyanate, and the polyol is polypropylene glycol. 3. The apparatus for producing a laminated film according to claim 1, wherein the polyisocyanate composition (X) further contains a carbodiimide-modified isocyanate. A polyisocyanate composition (X) containing a polyisocyanate (A) and a polyol composition (Y) containing a polyol (B) are subjected to a curing reaction at 25° C., whereby the storage elastic modulus is reduced within 1 hour from the start of the curing reaction. is a method of manufacturing a laminated film by bonding the first film and the second film together using a two-component curing adhesive having a viscosity of 10 Pa or more,
A first application step of applying the polyisocyanate composition (X) to the first film;
A two-liquid separate coating step consisting of a second coating step of coating the polyol composition (Y) on a 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 for curing reaction by contacting
The polyisocyanate (A) contains at least a reaction product of an aromatic polyisocyanate, an aliphatic polyisocyanate and a polyol,
The NCO excess expressed by [the isocyanate group of the polyisocyanate composition (X)/(the sum of the hydroxyl value and the amine value of the polyol composition (Y))] (molar ratio) is 1.4. A method for producing a laminated film , which is in the range of ~1.6 . 5. The method for producing a laminated film according to claim 4, wherein the aromatic polyisocyanate is diphenylmethane diisocyanate, the aliphatic polyisocyanate is hexamethylene diisocyanate, and the polyol is polypropylene glycol. The method for producing a laminated film according to claim 4 or 5, wherein the polyisocyanate composition (X) further contains a carbodiimide-modified isocyanate. Using a curing reaction between a polyisocyanate composition (X) containing a polyisocyanate (A) and applied to a first film and a polyol composition (Y) containing a polyol (B) and applied to a second film A two-component curing adhesive,
By subjecting the polyisocyanate composition (X) and the polyol composition (Y) to a curing reaction at 25° C., the storage elastic modulus becomes 10 Pa or more within 1 hour from the start of the curing reaction,
The polyisocyanate (A) contains at least a reaction product of an aromatic polyisocyanate, an aliphatic polyisocyanate and a polyol,
The NCO excess expressed by [the isocyanate group of the polyisocyanate composition (X)/(the sum of the hydroxyl value and the amine value of the polyol composition (Y))] (molar ratio) is 1.4. A two-part curable adhesive in the range of ~1.6 . 8. The two-part curable adhesive according to claim 7, wherein said aromatic polyisocyanate is diphenylmethane diisocyanate, said aliphatic polyisocyanate is hexamethylene diisocyanate, and said polyol is polypropylene glycol. The two-component curing adhesive according to claim 7 or 8, wherein the polyisocyanate composition (X) further contains a carbodiimide-modified isocyanate . The two-component curing adhesive according to any one of claims 7 to 9 , wherein tan δ is 8 or less 1 hour after the initiation of the curing reaction. Having an adhesive layer between the first film and the second film,
A laminated film, wherein the adhesive layer comprises a cured product of the two-component curing adhesive according to any one of claims 7 to 10 .

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