WO2003101859A1

WO2003101859A1 - Packaging bag material for hardenable composition

Info

Publication number: WO2003101859A1
Application number: PCT/JP2003/007035
Authority: WO
Inventors: Masahisa Kakinuma; Shigeru Ushiki; Hideaki Kojima; Kuniaki Fusegawa; Akira Sasaki; Minoru Murata; Takafumi Someya
Original assignee: Taiyo Ink Manufacturing Co., Ltd.; Fujimori Kogyo Co., Ltd.
Priority date: 2002-06-04
Filing date: 2003-06-03
Publication date: 2003-12-11
Also published as: CN1659086A; JPWO2003101859A1; AU2003241986A8; TW200400110A; CN100355564C; AU2003241986A1; JP4423190B2; TWI292739B; KR20050007582A

Abstract

A packaging bag material having a structure obtained by laminating of a sealant layer (1) constituted of a synthetic resin layer having an inside surface capable of heat sealing and a barrier layer (3) including a metal thin-film layer (7) with an extruded polyethylene layer (2) interposed therebetween. A synthetic resin layer (6) that is detachable from the polyethylene layer is disposed at an interface between the extruded polyethylene layer and at least one of the sealant layer and the barrier layer. Preferably, the metal thin-film layer is an aluminum foil or aluminum vapor deposition layer. The packaging bag material of this structure is especially suitable for use as a packaging bag material for hardenable compositions, such as resist inks, adhesives, paints, printing inks and the like.

Description

Description Packaging bag material for curable composition

The present invention relates to a packaging bag material for a curable composition such as various active energy ray-curable resist inks, adhesives, coatings, and printing inks, and in particular, to ensure the stability of the curable composition over time and to transport the curable composition during transportation. Packaging materials that ensure the safety and quality of products and are environmentally friendly. Background art

Conventionally, resist curable compositions such as heat, infrared, visible, ultraviolet, and electron beam curable resist ink materials and adhesives, paints, printing inks, etc. are used to prevent leakage of contents. It is used in a steel or plastic container that has airtightness, gas barrier properties against oxygen and water vapor, gases such as solvents and various volatile components, and light shielding properties to prevent deterioration of the contents. I have.

According to such a container, it is surely effective in the sealing property, gas barrier property, light shielding property and the like. However, the steel container and the plastic container have an increased weight and capacity of empty containers, and therefore, the environmental burden has been reduced today because it is required to reduce the weight and capacity of empty containers after use in consideration of the environment. large.

On the other hand, for example, in the field of food packaging, as a packaging form that can significantly reduce the weight and capacity of empty containers, a synthetic resin sheet with gas barrier properties and light shielding properties provided by selecting and coloring synthetic resin types is used. In some cases, foodstuffs are packed in a packaging bag made of a laminated sheet provided with a metal thin film layer having a gas barrier property and a light shielding property.

However, when such a packaging bag is used as a packaging bag for a curable composition, a packaging bag consisting only of a synthetic resin sheet has sufficient gas barrier properties and light shielding properties. Can not get. In addition, since a packaging bag made of a laminated sheet provided with a metal thin film layer to improve gas barrier properties and light-shielding properties is flexible, the bent metal thin film is used during transportation and work. Bending marks and cracks are formed in the layer, and fragments of the metal thin film layer are mixed into the contents from the cracks.Especially in packaging bags filled with curable compositions related to electronic components such as resist ink materials, conductive The quality cannot be maintained due to slight contamination.

Therefore, in a packaging bag made of a laminated sheet provided with a metal thin film layer, even if the metal thin film layer is damaged or damaged, conductive materials may be mixed into the contents before use. There is a need for a means for checking whether or not this is the case.

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of conventional packaging bags, and its main purpose is to package a curable composition such as a resist ink, an adhesive, a paint, a printing ink, and the like. In particular, as a bag material, it has excellent gas barrier properties and excellent light-shielding properties. The purpose is to provide packaging materials that ensure quality, can significantly reduce the volume of used packaging containers, and are environmentally friendly. Disclosure of the invention

To achieve the above object, according to the present invention, a sealant layer made of a heat-sealable synthetic resin layer and a barrier layer including a metal thin film layer are laminated via an extruded polyethylene layer. A packaging bag material having a structure consisting of: a synthetic resin layer that is peelable in relation to the polyethylene layer at an interface between the extruded polyethylene layer and at least one of the sealant layer and the barrier layer. The present invention provides a curable composition packaging bag material provided with:

In a preferred embodiment, the metal thin film layer in the barrier layer is an aluminum foil or an aluminum vapor-deposited layer.

According to the packaging bag material of the curable composition according to the present invention, gas barrier properties ゃ It has excellent curability and can secure the long-term stability of the curable composition during storage, and can confirm the contamination of the thin metal film layer with simple operations to ensure the quality of the curable composition and protect the environment. It is possible to provide a packaging bag that is also considered.

As a preferable embodiment of the packaging bag, a packaging form in which a radical polymerizable composition and air are contained in a packaging bag produced using the above-described packaging bag material is preferable. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a partial schematic sectional view showing a sectional structure of a preferred embodiment of the packaging bag material of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

The packaging bag material of the present invention has a structure in which a sealant layer having a heat-sealable synthetic resin layer on its inner surface and a barrier layer including a metal thin film layer are laminated via an extruded polyethylene layer. Has the first characteristic.

With such a configuration, the packaging bag material of the present invention has excellent light-shielding properties and gas barrier properties as a packaging bag, can secure stability over time, and is easy to handle because it is a flexible bag. In addition, the packaging container after use can be significantly reduced in weight, making it ideal as an environmentally friendly packaging bag material.

Further, the packaging bag material of the present invention has a synthetic resin layer which can be peeled off in relation to the polyethylene layer at an interface between at least one of the sealant layer and the barrier layer and the extruded polyethylene layer. The point has a second feature.

With such a configuration, the packaging bag material of the present invention can be easily peeled off at the interface, so that a bent mark and a crack are formed in the bent portion of the metal thin film layer during transportation or work. In this case, it is checked whether or not fragments of the metal thin film layer have mixed into the contents from the cracks before using the interface between the extruded polyethylene layer and at least one of the sealant layer and the barrier layer. It can be easily confirmed by peeling. The packaging bag material of the present invention is suitable as a packaging bag material for curable compositions such as various active energy ray-curable resist inks, adhesives, paints, printing inks, etc. due to the above-mentioned characteristics, and in particular, resist inks and the like. When containing the radically polymerizable composition of the present invention, the packaging form in which air is contained together with the radically polymerizable composition in the packaging bag (for example, the state in which air enters without filling the package bag with vacuum when filling the composition) In such a case, the polymerization of the radically polymerizable composition is suppressed by oxygen inhibition, whereby the storage stability of the radically polymerizable composition can be ensured. This is because the radical reaction caused by heat, ultraviolet rays, etc. is suppressed by oxygen radicals contained in the air, thereby preventing the polymerization of the curable resin and monomer components in the composition and preventing the polymer from being polymerized. . As a result, the radically polymerizable composition such as a resist ink can be kept stable for a long time without gelling of the radically polymerizable composition in the storage.

As for the amount of air, the effect can be seen at 1% or more with respect to the volume of the radically polymerizable composition to be filled, but if it exceeds 50%, the volume of the package itself increases, which is not preferable because it is not suitable for packing. . The preferred amount of air is in the range of 5% to 30%.

Hereinafter, each layer constituting the packaging bag material of the present invention will be described.

First, as the above-mentioned sealant layer, the inner surface may be formed of a heat-sealable synthetic resin layer, and a single synthetic resin layer or a laminate formed of a plurality of different synthetic resin layers may be used. it can.

As the heat-sealable synthetic resin, any heat-sealable synthetic resin can be used. For example, polyolefins such as polyethylene, polypropylene, polybutene, and polypentene; polyesters such as polyethylene terephthalate and polybutylene terephthalate; and high molecular weight thermoplastic resins such as polyamides such as nylon are available. These synthetic resins can be used in any combination. In addition, these synthetic resins are made to have any density or crystallinity at the time of resin synthesis, such as low, medium, and high.

On the other hand, the barrier layer must include at least one thin metal layer. this By providing a barrier layer including a metal thin film layer as described above, gas barrier properties and light shielding properties are imparted or improved, polymerization of the curable composition by ultraviolet rays or the like, volatilization of a solvent, and gelation, deterioration, and discoloration resulting from the volatilization. Can be prevented. As the metal thin film layer to be used, a foil-deposited layer of aluminum, stainless steel, iron, copper, nickel, lead, etc. can be used, but an aluminum foil or an aluminum-deposited layer is preferable because it is inexpensive and has excellent light shielding performance. .

It is preferable that a metal thin film layer such as an aluminum foil is not exposed to the outermost part. Therefore, it is preferable to provide a protective layer as an outer layer of the barrier layer. Polyolefin, polyester, polyamide, and the like can be used as the protective layer. These are preferably formed into a film or a sheet and stretched to improve strength. In particular, polyester is excellent in preventing the metal thin film layer such as aluminum foil from being damaged during transportation, and this effect is particularly great when a polyester layer is arranged on the contact surface side with aluminum LU.

As described above, the packaging bag material of the present invention has a structure in which the sealant layer and the barrier layer are laminated via an extruded polyethylene layer, and any one of the sealant layer and the barrier layer At least one of the interfaces with the extruded polyethylene layer is provided with a synthetic resin layer capable of being peeled off in relation to the polyethylene layer (hereinafter referred to as a PE-peelable synthetic resin layer). You.

As the PE-peelable synthetic resin layer, polyolefins other than polyethylene, polyamides such as nylon, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and films thereof can be suitably used. It is preferable that such a film is stretched to easily form a laminate that can be easily peeled. In particular, biaxially stretched polyethylene terephthalate is more preferable because it can be easily formed into a laminate that can be easily peeled, has excellent strength, and is inexpensive. It is desirable that the PE-peelable synthetic resin layer is not subjected to an adhesion improving treatment such as a corona treatment on the interface side with the extruded polyethylene layer.

Easy to PE provided on at least one of the sealant layer and the barrier layer By extruding and laminating polyethylene on the releasable synthetic resin layer, the extruded polyethylene layer can be releasably adhered and the strength can be improved.

Extrusion lamination of polyethylene is performed by using dry lamination or extrusion lamination alone or in combination as appropriate, and is provided on at least one of the sealant layer and the barrier layer manufactured by laminating by a known method. It can be easily carried out on the synthetic resin layer by a conventionally known extrusion laminating method ゃ dry laminating method.

As for the total thickness of the packaging bag material of the present invention, the larger the thickness, the better the gas barrier properties, light shielding properties, and abrasion resistance. However, if the total thickness is more than 300, the sheet becomes harder and difficult to handle. If the thickness is less than 30 m / m, the abrasion resistance and the like will decrease, and holes will be formed during transportation, making the composition unsuitable for packaging of curable compositions such as resist ink. Therefore, the total thickness of the packaging bag material is preferably 30 to 300 im.

Regarding the thickness of each layer, the thickness of the sealant layer (when the sealant layer is composed of a plurality of layers, the total thickness thereof) is desirably in the range of 5 to 100 zm, and preferably 15 ~ 80〜m. If the thickness of the sealant layer is less than 5 m, the adhesive strength will be weak. On the other hand, if it is greater than 100 zm, it will be difficult to secure the total thickness, which is not practical.

Further, the thickness of the paria layer (the total thickness thereof when it is composed of a plurality of layers) is desirably in the range of 10 to 200 m, preferably 15 to 80 / m. When the thickness of the barrier layer is less than 10 m, cracks are liable to be formed in the metal thin film layer. On the other hand, when the thickness of the barrier layer is more than 200 m, it is difficult to secure the total thickness, which is not practical. The thickness of the metal thin film layer in the barrier layer is desirably in the range of 5 to 100 / m, preferably 5 to 40 m. The thicker the metal thin film layer is, the more excellent the gas barrier property, the light shielding property and the abrasion resistance are. However, if the thickness is more than 100 / m, the packaging bag material itself is not preferred, which is not preferable. The upper limit is naturally limited by the total thickness of the packaging bag material. on the other hand, If the thickness of the metal thin film layer is smaller than 5 / m, holes (pinholes) are easily formed in the metal thin film layer itself during transportation, and the expected effect is reduced, so that the meaning of the use is reduced.

The thickness of the extruded polyethylene layer is desirably in the range of 1 to 60 μm, preferably 5 to 40 zm. If the thickness of the extruded polyethylene layer is less than 1 zm, the adhesive strength will be weak. On the other hand, if it is more than 60 zm, it will be difficult to secure the total thickness, which is not practical.

Further, the thickness of the PE-peelable synthetic resin layer is desirably in the range of 5 to 100 m, preferably 10 to 40 m. When the thickness of the PE resin layer that is easily peelable from PE is thinner, the strength of the bag at the time of peeling is low, and the bag is easily broken.On the other hand, when the thickness is more than 100 m, the total thickness is reduced. It is not practical because it is difficult to secure.

The thickness of each layer of the laminate can be appropriately set within the above range and the range of the total thickness.In addition, by appropriately selecting the combination and thickness of each layer of the laminate, the bag breaking strength at the time of transportation is improved. be able to.

The shape of the packaging bag made from the packaging bag material of the present invention described above may be any of a flat bag, a standing type, and a gazette type, but is preferably a flat bag that is easily squeezed. In addition, in order to facilitate squeezing, a material such as a spout (projecting discharge port) may be bonded with a heat seal.

The packaging bag filled with the curable composition can be safely transported by using a steel container or a plastic container as the outer container and randomly packing a plurality of the packaging bag units. And the breaking strength is obtained.

Next, preferred embodiments of the packaging bag material of the present invention will be described more specifically, while describing embodiments shown in the accompanying drawings.

FIG. 1 shows an example of a cross-sectional structure of a packaging bag material in which a sealant layer 1 and a barrier layer 3 are laminated via an extruded polyethylene layer 2.

The sealant layer 1 placed inside the packaging bag to be produced is directed from inside to outside. The heat-sealable polyethylene layer 4, the adhesive layer 5, and the polyester layer 6 as a synthetic resin layer that is easily peelable from PE, while the barrier layer 3 is also made of aluminum foil 7, It is composed of an adhesive layer 8 and a polyester layer 9 as a protective layer.

The sealant layer 1 may be obtained by co-extrusion, but is preferably laminated by an adhesive layer 5 as shown. As the adhesive that can be used, an adhesive that is usually used for dry lamination, such as a urethane-based adhesive, may be used. The innermost layer (polyethylene layer 4) is preferably a low-elution type polyethylene film in order to prevent components contained in the resin from migrating to the curable composition and the like.

On the other hand, the barrier layer 3 is formed by bonding and laminating an aluminum foil 7 and a polyester layer 9 with an adhesive layer 8, and the adhesive used may be the same as described above.

Instead of the aluminum box and the polyester laminated sheet, a polyester film obtained by vapor-depositing aluminum on a polyester film may be used.

The packaging bag material having the above structure is heat-sealed with the heat-sealable polyethylene layer 4 inside, and the bag is made into a polyester layer 6 as a PE-peelable synthetic resin layer and a polyester layer 6 on it. Since the adhesive force is weak at the interface between the laminated extruded polyethylene layers 2, the laminated portion of the extruded polyethylene layer 2 and the barrier layer 3 can be manually peeled off at this interface. Therefore, if the aluminum foil 8 between the layers is damaged during transportation, it is easy to peel off the laminated part and see if there are holes or not, and if there is any fragment of aluminum foil 8 in the contents. Can be confirmed.

In addition, the polyester layer 6 as the PE easily peelable synthetic resin layer may be laminated on the surface of the aluminum foil 7, or may be arranged on both sides of the extruded polyethylene layer 2. In the former case, the barrier layer can be peeled between the polyester layer on the aluminum foil side and the extruded polyethylene layer, and in the latter case, the barrier layer and the extruded polyethylene layer can be peeled off. Even in this case, the laminated portion including the metal thin film layer (aluminum foil) can be peeled off. Hereinafter, test examples that specifically confirm the effects of the present invention will be described. Test example 1

Taiyo Ink Manufacturing Co., Ltd. The main ingredients of resist ink (PSR-400Z26), curing agent (CA-400Z26K), and the following solvents were prepared from the following packaging bag materials. It was filled in a packaging bag, allowed to stand at 50 ° C, and after a lapse of a predetermined number of days, the weight change (weight loss%) was measured. Tables 1 to 3 show the results.

Solvent used:

<Solvent> Ipsol # 150 (made by Idemitsu Petrochemical Co., Ltd.)

Solvent B> Danol D PM (dipropylene glycol monomethyl ether, manufactured by Dow Chemical Company),

<Solvent C> methoxypropanol (propylene glycol monomethyl ether, manufactured by Daicel Chemical Industries, Ltd.),

<Solvent D> Juicazole C A (diethylene glycol monoethyl acetate, manufactured by Osaka Organic Chemical Company)

Composition of packaging bag material:

<Packaging bag material A> From inside, polyethylene (40) m) / urethane-based adhesive (1〃m) Biaxially stretched polyethylene terephthalate (12 押し m) Z extruded polyethylene (10mm) / Biaxially stretched polyethylene terephthalate rate (1 2 ju), total thickness Ί5 τα

<Packaging bag material Β> From inside, polyethylene (25 / m) Ζ Urethane adhesive (1〃m) / biaxially stretched polyethylene terephthalate (12 zm) No extruded polyethylene (10 zm) / Metal foil (9〃m) / Urethane adhesive (1 nm) / Biaxially oriented polyethylene terephthalate (12 jum), total thickness 70 / m table 1

As is clear from the results shown in Tables 1 to 3 above, in packaging bag material A in which the barrier layer does not contain a metal thin film (aluminum foil), a weight loss considered to be caused by solvent evaporation was observed. In the case of packaging bag material B using a barrier layer including a metal thin film layer, weight loss hardly occurred.

Test example 2

A packaging bag material having the following configuration was prepared, and a test of peeling by hand at an interface indicated by “/” was performed. Table 4 shows the results of the peelability.

<Packaging bag material C> From inside, polyethylene Z / Z urethane adhesive / Al Mini foil / urethane adhesive / biaxially stretched polyethylene terephthalate

<Packaging bag material D> From inside, polyethylene / urethane adhesive Z biaxially stretched polyethylene terephthalate /// extruded polyethylene / aluminum foil urethane adhesive / biaxially stretched polyethylene terephthalate

<Packaging bag material E> From the inside, polyethylene nourethane adhesive / biaxially oriented polypropylene /// extruded polyethylene / aluminum foil / polyethylene adhesive nonaxially oriented polyethylene terephthalate

<Packaging bag material F> From inside, polyethylene urethane-based adhesive Z biaxially stretched 6-thick / unextruded // extruded polyethylene / aluminum foil / urea-based adhesive / biaxially stretched polyethylene terephthalate

As is clear from the results shown in Table 4, it can be seen that releasability can be obtained at the interface between the PE easily peelable resin layer and the extruded polyethylene.

Test example 3

A radical polymerizable resist ink (the main ingredient of the resist ink manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR-400 Z26) is filled into a plurality of packaging bags made from the packaging bag material B, and the temperature is reduced to 50 ° C. After a predetermined number of days, the air in the bag was sucked out with a syringe, and the volume was recorded. Thereafter, it was opened, and the viscosity of the resist ink was measured with an EHD type viscometer to determine the viscosity increase rate. Table 5 shows the results. Table 5

As is clear from the results shown in Table 5 above, the packaging bag filled with the radical-polymerizable resist ink having an air content of less than 1% has the same excess as that of the air content of 1% or more. In days, the rate of increase in viscosity becomes extremely high. Industrial applicability

As described above, according to the packaging bag material of the curable composition according to the present invention, the curable composition has excellent gas barrier properties and light-shielding properties, can maintain the storage stability of the curable composition over time during storage, and can have a metal thin film layer. The quality of the curable composition can be ensured by being able to confirm the contamination of the debris by simple operations, and it is possible to provide environmentally friendly packaging bags, especially resist inks, adhesives, and paints. It is useful as a packaging bag material for curable compositions such as printing inks.

Claims

The scope of the claims

1. A packaging bag material having a structure in which a sealant layer made of a heat-sealable synthetic resin layer and a barrier layer containing a metal thin film layer are laminated via an extruded polyethylene layer. At least one of the sealant layer and the barrier layer, at the interface between the extruded polyethylene layer and a synthetic resin layer which is peelable in relation to the polyethylene layer, is provided. Packaging bag material.

2. The packaging bag material according to claim 1, wherein the metal thin film layer in the barrier layer is an aluminum foil or an aluminum vapor-deposited layer.

3. The package according to claim 1, wherein the heat-sealable synthetic resin layer is at least one layer of a thermoplastic resin selected from the group consisting of polyolefin, polyester and polyamide. Bag material.

4. The synthetic resin layer, which can be peeled off in relation to the polyethylene layer, is made of at least one stretched film of a thermoplastic resin selected from the group consisting of polyolefins, polyamides and polyesters other than polyethylene. The packaging bag material according to claim 1 or 2, wherein

5. The packaging bag material according to claim 1, wherein a synthetic resin protective layer is further formed outside the metal thin film layer.

6. A heat-sealable polyethylene layer Z adhesive layer / polyester layer as easily peelable synthetic resin layer z extruded polyethylene layer metal thin film layer / adhesive layer protective layer The packaging bag material according to 1 or 2.