JP2017137387A - Non-adsorbent adhesive coating agent, non-adsorbent laminate, and packaging bag - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packaging bag which stores a content containing a component that is easily adsorbed by a synthetic resin therein and lowers its absorption, and is also excellent in heat sealing suitability.SOLUTION: There is provided a laminate as a laminate structuring a packaging bag which is formed by laminating a sealant layer 3, an adhesive layer 2 and a base material layer 1 in this order, where the adhesive layer is formed from a coating film containing a main agent, a curing agent and polyester resin particles, and a ratio of the polyester resin particles in the adhesive layer is 20 mass% or more and 70 mass% or less; the adhesive layer contains the polyester resin particles, and accordingly the laminate has such properties as to hardly adsorb the component; and the polyester resin particles and the polyacrylonitrile resin particles do not need to be mixed in the sealant layer, and accordingly the sealant layer exhibits heat sealing suitability inherent in the sealant layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a technique for containing and packaging contents containing components that are easily adsorbed by a synthetic resin. Examples of such contents include foods and drinks including limonene and tocophenol acetate. In addition, anti-inflammatory analgesics including ketoprofen and the like. According to the packaging bag of the present invention, these contents can be accommodated and packaged to reduce the adsorption of these components that are easily adsorbed by the synthetic resin, and the decrease in the contents can be suppressed.

  A packaging bag described in Patent Document 1 is known as a packaging bag containing these contents including components that are easily adsorbed by a synthetic resin. In this packaging bag, polyester resin particles or polyacrylonitrile resin particles are blended in a sealant layer. By blending these particles, adsorption of the components can be prevented. For this reason, the decrease of these components contained in the contents is suppressed, and the deterioration of the contents over time is prevented.

JP 2012-184357 A

  However, polyester resin particles and polyacrylonitrile resin particles are resin particles with poor heat sealability, and since they are blended in the sealant layer, it was not possible to prevent deterioration of their heat sealability.

  Then, it aims at providing the packaging bag which accommodated the said content containing the component which is easy to adsorb | suck to a synthetic resin, and was excellent also in heat-sealability while reducing the adsorption | suction.

  In addition, the present invention also provides a non-adsorptive adhesive coating agent and a non-adsorptive laminate suitable for this packaging bag.

That is, the invention according to claim 1 is an adhesive coating agent comprising a main agent, a curing agent, a dispersion medium and polyester resin particles,
The non-adsorptive adhesive coating agent is characterized in that the ratio of the polyester resin particles in the solid content is 20% by mass or more and 70% by mass or less.

  Next, the invention according to claim 2 is the non-adsorptive adhesive coating agent according to claim 1, wherein the ratio of the polyester resin particles in the solid content is 50% by mass or more.

  Next, the invention described in claim 3 is the non-adsorptive adhesive coating according to claim 1 or 2, wherein the main agent is made of a polyester polyol and the curing agent is a polyisocyanate curing agent. It is an agent.

Next, the invention according to claim 4 is a laminate in which a sealant layer, an adhesive layer, and a base material layer are laminated in this order,
A non-adsorbent laminate, wherein the adhesive layer comprises a coating film containing a main agent, a curing agent and polyester resin particles, and the ratio of the polyester resin particles in the adhesive layer is 20% by mass or more and 70% by mass or less. It is.

  Next, the invention according to claim 5 is the non-adsorbent laminate according to claim 4, wherein the base material layer is made of a plastic film.

  Next, the invention according to claim 6 is the non-adsorbent laminate according to claim 4, wherein the base material layer has a gas barrier layer.

  Next, in the invention described in claim 7, the non-adsorptive layer according to any one of claims 4 to 6, wherein the dry thickness of the adhesive layer is 0.005 μm or more and 10 μm or less. It is a product.

  Next, the invention according to claim 8 is a packaging bag comprising the non-adsorbent laminate according to any one of claims 3 to 6.

  The adhesive coating agent according to any one of claims 1 to 3 can be used for the adhesive layer when the laminate is produced by bonding the sealant layer and the base material layer as described in claims 4 to 7. And this laminated body contains the polyester resin particle | grains whose adhesive layer is 20 mass% or more and 70 mass% or less, For this reason, this laminated body has a property which cannot adsorb | suck the said component easily. And since it is not necessary to mix | blend a polyester resin particle or a polyacrylonitrile resin particle with a sealant layer, the sealant layer original heat seal property is exhibited. In addition, if the ratio of the polyester resin particles is less than 20% by mass, the adsorptivity of the component is increased. Moreover, when more than 70 mass%, even when it is a case where a polyester resin particle and a polyacrylonitrile resin particle are not mix | blended with the sealant layer 3, heat seal performance falls.

  For this reason, if a packaging bag is comprised with this laminated body, the heat seal intensity | strength is high, Furthermore, the reduction | decrease of the said component by adsorption | suction can be suppressed, and the packaging bag excellent in long-term storage property can be obtained.

It is a section explanatory view of the layered product concerning the example of the present invention.

  Next, specific examples of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional explanatory view of a laminate according to a specific example of the present invention. As can be seen from this figure, the laminate of the present invention comprises three layers of a sealant layer 3, an adhesive layer 2, and a base material layer 1. It is composed. The adhesive layer 2 is for bonding and integrating the sealant layer 3 and the base material layer 1 and is located between the two.

  Although the base material layer 1 may be comprised with the single layer, it may have a multilayered structure. In this example, the base material layer 1 is composed of two layers of a plastic film 11 and a gas barrier layer 12. In addition to this, it is needless to say that a printed layer may be provided.

  Moreover, the adhesive layer 2 has a role of ensuring the non-adsorption performance of the laminate in addition to the role of bonding and integrating the sealant layer 3 and the base material layer 1. For this reason, it is necessary to be comprised with the coating film formed by apply | coating the adhesive coating agent mentioned later.

  The sealant layer 3 functions as a heat seal layer when a packaging bag is made with this laminate.

Therefore, first, the material and forming method of each layer will be described, and finally the usage method will be described.

(Base material layer 1)
As described above, the base material layer 1 may be composed of a single layer or may have a multilayer structure. When the base material layer 1 is constituted by a single layer, a plastic film can be used. As the plastic film, for example, a polyolefin film, a polyester film, a polyamide film, a polyimide film, or the like can be used. Examples of the polyolefin film include a polyethylene film and a polypropylene film. Examples of the polyester film include a polyethylene terephthalate film, a polybutylene terephthalate film, and a polyethylene naphthalate film. Examples of the polyamide film include nylon-6 film and nylon-66 film. What is necessary is just to select and use suitably from these various plastic films according to goods or the content.

  In particular, when a polypropylene film or polyethylene terephthalate is used as the base material layer 1, it is preferable in terms of film strength and price. Moreover, when using a polyamide film, there exists an effect of an improvement of mechanical strength and the tolerance with respect to the bag breakage by a stab or other external force can be provided.

  When the base material layer 1 has a multi-layer structure, it is desirable that one of these layers is composed of the plastic film 11. The other layers can be made of any material. For example, a plastic film, a coating film, paper, a metal foil, a vapor deposition layer, and the like. In order to prevent permeation of the components contained in the contents, it is desirable to have the gas barrier layer 12 having excellent barrier properties. For example, a metal foil, a metal vapor deposition film, an inorganic vapor deposition film, or the like. Moreover, a barrier coating film can also be formed on a metal vapor deposition film or an inorganic vapor deposition film. All of these metal foils, metal vapor deposition films, inorganic vapor deposition films, and barrier coating films are excellent in barrier properties for preventing permeation of the above components, and also in barrier properties for oxygen gas and water vapor.

  Aluminum foil or copper foil can be used as the metal foil. These metal foils can be laminated on the plastic film 11 with an adhesive.

  When a metal vapor deposition film or an inorganic vapor deposition film is used as the gas barrier layer 12, it is desirable to form an anchor coat layer on the plastic film 11 and then form the vapor deposition film on the anchor coat layer. For the anchor coat layer, for example, urethane acrylate can be used. And the paint which melt | dissolved this urethane acrylate etc. in the solvent can be coated on the plastic film 11, and it can dry-harden and can form an anchor-coat layer. Coating can be performed by a method such as gravure coating.

  An aluminum vapor deposition film can be used as the metal vapor deposition film. Moreover, as an inorganic vapor deposition film, the vapor deposition film of a silicon oxide or aluminum oxide can be used. These deposited films may have a thickness of 15 nm to 30 nm. In addition, when an inorganic vapor deposition film is used as the gas barrier layer 12, since this inorganic vapor deposition film is generally transparent, it has the advantage that the contents can be seen from the outside of the packaging bag. In addition, since no metal is used, it is suitable for heating with a microwave oven, and has an advantage in restoring the shape of the container when the packaging bag is pushed from the outside.

  Next, the barrier coating film formed on these deposited films is coated with a water-soluble polymer and a coating agent containing the following (a) or (b), heated and dried and cured. Can be formed.

(A) one or more alkoxides or hydrolysates thereof (b) tin chloride

  When this barrier coating film is formed on an inorganic vapor deposition film, a composite structure of these two layers forms a reaction layer of both layers at the interface between the inorganic vapor deposition film and the barrier coating film to form a dense structure. Alternatively, the barrier coating film by the coating method compensates for defects such as pinholes, cracks, grain boundaries, and the like formed in the inorganic compound layer by the vacuum deposition method, thereby realizing a high gas barrier property. In addition, since these layers all have flexibility that can resist deformation, they can also have suitability as packaging bags.

(Adhesive layer 2)
As described above, the adhesive layer 2 needs to be composed of a coating film formed by applying a specific adhesive coating agent. This adhesive coating agent is an adhesive coating agent containing a main agent, a curing agent, a dispersion medium and polyester resin particles, and the ratio of the polyester resin particles in the solid content is 20% by mass or more and 70% by mass or less. It is important to be. If it is more than this, uniform coating without unevenness becomes difficult, and even if the sealant layer 3 is not blended with polyester resin particles or polyacrylonitrile resin particles, the heat-sealing performance of the resulting laminate can be improved. descend. Moreover, when the ratio of the polyester resin particles is less than this, the adsorptivity of the component is increased. In addition, in order to reduce the adsorptivity of the said component, it is desirable for the ratio of the polyester resin particle to be 50 mass% or more.

  As the main component of the adhesive coating agent, a polyester polyol can be preferably used. As the polyester polyol, for example, a polyester polyol obtained by reacting at least one polybasic acid with at least one diol can be used. Examples of polybasic acids include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, spellic acid, azelaic acid, sebacic acid, and brassic acid, and aromatics such as isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. And dibasic acids such as group dibasic acids. Diols include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol and other aliphatic diols, cyclohexanediol, hydrogenated xylylene Examples thereof include alicyclic diols such as lenglycol and aromatic diols such as xylylene glycol.

  As the curing agent, a polyisocyanate curing agent can be preferably used. Examples of the polyisocyanate curing agent include 2,4- or 2,6-tolylene diisocyanate, xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, 2,2,4. -Or selected from 2,4,4-trimethylhexamethylene diisocyanate, 1,6-hexamethylene diisocyanate, methylcyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, etc. Is an isocyanate compound alone or at least one isocyanate compound selected from the above isocyanate compounds? Adducts made, biuret body, isocyanurate products thereof.

  The ratio between the main agent and the curing agent is a molar ratio of the functional group (A) in the main agent to the reactive functional group (B) in the curing agent, and (B) / (A) is 0.5 or more and 5.0 or less. It is preferably 0.8 or more and 3.5 or less. If (B) / (A) is not less than the lower limit, the main agent can be sufficiently cured, and if it is not more than the upper limit, the film can be prevented from becoming too hard and the adhesive layer from becoming brittle.

  The dispersion medium is a liquid that dissolves or disperses the main agent and the curing agent, and is not particularly limited as long as it can be dissolved and diluted. As the dispersion medium, an alcohol solvent, a ketone solvent, an ester solvent, a glycol solvent, or a hydrocarbon solvent can be used.

  Examples of alcohol solvents include methanol, ethanol, isopropanol, n-propanol, 1-butanol, and 2-butanol.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isophorone.

  Examples of the ester solvent include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, isobutyl acetate, and propylene glycol monomethyl ether acetate.

  Examples of glycol solvents include butyl cellosolve and propylene glycol monomethyl ether.

  Examples of the hydrocarbon solvent include toluene, xylene, n-hexane, and methylcyclohexane.

  These solvents can be used alone or in a mixture containing two or more thereof. Methyl ethyl ketone and ethyl acetate are preferable from the viewpoint of stability during dissolution and drying after coating.

  As the polyester resin particles, particles of polyethylene terephthalate resin, polymethylene terephthalate resin, polybutylene terephthalate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, or the like can be used. Moreover, the particle | grains of the copolyester resin which uses two components as a polyhydric alcohol, and the copolyester resin which uses two components as a polybasic acid may be sufficient.

  The polyester resin particles preferably have a cumulative 50% particle diameter (median value) of 0.05 μm or more from the small diameter side in the particle diameter measured by the microtrack particle size distribution measuring method. Moreover, it is desirable that this particle diameter is 10 micrometers or less.

  The adhesive coating agent can be produced by mixing these main agent, curing agent, dispersion medium and polyester resin particles. The adhesive coating agent may contain other particles in addition to the polyester resin particles. For example, polyacrylonitrile resin particles, silica particles, calcium carbonate particles, barium sulfate particles, and alumina particles. In addition, the adhesive coating agent may contain oils, waxes and the like.

  The solid content concentration of the adhesive coating agent is preferably 3 to 80% by mass, and more preferably 4 to 45% by mass. If the solid content concentration of the coating agent is equal to or higher than the lower limit value, the adhesive layer 2 having a sufficient thickness can be easily formed by one coating, and if the solid content concentration is equal to or lower than the upper limit value, the viscosity is appropriately lowered. Coating property is improved. The solid content concentration is a total mass ratio of the polymer (net amount) constituting the main agent in 100% by mass of the non-adsorbing adhesive coating agent, the curing agent (net amount), and the polyacrylonitrile resin particles (net amount). .

The thickness of the adhesive layer 2 is preferably 0.005 to 10 μm, and more preferably 0.01 to 5 μm. If the thickness of the adhesive layer 2 is equal to or greater than the lower limit value, the adhesive coating agent can be easily applied by a general-purpose coating apparatus. If the thickness is equal to or less than the upper limit value, the amount of the adhesive coating agent applied is reduced. Therefore, cost reduction can be realized. Further, since the dispersion medium is removed by drying, the adhesive layer 2 obtained by coating and drying is composed only of the solid content of the adhesive coating agent. For this reason, the ratio of the polyester resin particles in the adhesive layer 2 Is 20 mass% or more and 70 mass% or less.

(Sealant layer 3)
The sealant layer 3 functions as a heat seal layer when the packaging bag is made of a laminate, and is disposed in the innermost layer of the packaging bag. That is, it is possible to carry out bag making by stacking the two laminates with the sealant layers 3 facing each other and welding them together by heating and pressing.
As a material for the sealant layer, a polyolefin resin is generally used among thermoplastic resins. Specifically, a low density polyethylene resin (LDPE), a medium density polyethylene resin (MDPE), and a linear low density polyethylene resin. (LLDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-α olefin copolymer, ethylene resin such as ethylene-methacrylic acid resin copolymer, blend resin of polyethylene and polybutene, homopolypropylene resin ( PP), propylene-ethylene random copolymers, propylene-ethylene block copolymers, polypropylene resins such as propylene-α olefin copolymers, and the like can be used. It is also possible to use cycloolefin polymer (COP) or cycloolefin copolymer (COC). The sealant layer 3 can be formed by laminating and laminating materials previously formed on a film, or by laminating molten resin using an extruder to form a sealant layer.

(Packaging bag)
As described above, this laminated body can be used to make a bag to make a packaging bag. A sealant layer is disposed on the content side of the laminate, that is, the innermost layer of the packaging bag, the sealant layers are stacked so that the sealant layers face each other, and a bag is formed by heat sealing to obtain a packaging bag. Since the laminated body is non-adsorbing, the packaged bag is non-adsorbing.

  And after accommodating the content from the opening part of this packaging bag, an opening part can be sealed by heat seal and the content can be sealed. The content may be arbitrary, but when the component contains a component that is easily adsorbed by the synthetic resin, the features of the present invention can be utilized. Examples of such contents include foods and drinks containing limonene and tocophenol acetate as the above ingredients, pharmaceuticals containing methyl salicylate or l-menthol, dl-camphor, ketoprofen, flurbiprofen, loxoprofen sodium hydrate, etc. Examples include anti-inflammatory analgesics and the like.

Example 1
A substrate layer 1 was obtained by bonding a 7 μm thick aluminum foil to a 12 μm thick polyethylene terephthalate film. The adhesive is a two-component curable urethane adhesive.

  In addition, a linear low density polyethylene resin (LLDPE) film having a thickness of 50 μm was prepared as a film constituting the sealant layer 3.

  Polyethylene terephthalate resin was melt-spun at 280 ° C. from a nozzle having a diameter of 0.5 mm, and then freeze-pulverized to produce polyester resin particles. The median particle diameter of the polyester resin particles measured by the microtrack particle size distribution measurement method is 7 μm.

Then, an adhesive coating agent was prepared by mixing polyester polyol as a main agent, polyisocyanate as a curing agent, and ethyl acetate as a dispersion medium in the following ratio. In addition, the ratio of the polyester resin particle in solid content is 60.0 mass%.

-Adhesive coating agent composition Polyester polyol 7.3% by mass
Polyisocyanate 12.7% by mass
Ethyl acetate 50.0% by mass
Polyester resin particles 30.0% by mass.

  By using this adhesive coating agent as a material for the adhesive layer 2, applying and drying the aluminum foil surface of the base material layer 1 using a dry laminator, and laminating the sealant layer 3, the laminate according to Example 1 Manufactured.

(Example 2)
A laminate according to Example 2 was produced in the same manner as in Example 1 except that the blending amount of the polyester resin particles was reduced and the proportions of the main agent, the curing agent, and the dispersion medium were as follows. The ratio of the polyester resin particles in the solid content of the adhesive coating agent is 28.6% by mass.

-Adhesive coating agent composition Polyester polyol 9.1% by mass
Polyisocyanate 15.9% by mass
Ethyl acetate 62.5% by mass
Polyester resin particles 12.5% by mass.

(Comparative Example 1)
The laminated body which concerns on the comparative example 1 was manufactured similarly to Example 1 except the point which did not mix | blend the polyester resin particle with the adhesive coating agent. As a precaution, the adhesive coating agent composition is as follows.

-Adhesive coating agent composition Polyester polyol 10.4% by mass
Polyisocyanate 18.1% by mass
Ethyl acetate 71.5% by weight.

(Comparative Example 2)
A laminate according to Comparative Example 2 was produced in the same manner as Example 1 except that the blending amount of the polyester resin particles was increased and the proportions of the main agent, the curing agent and the dispersion medium were as follows. The ratio of the polyester resin particles in the solid content of the adhesive coating agent is 79.6% by mass.

-Adhesive coating agent composition Polyester polyol 5.6% by mass
Polyisocyanate 9.8% by mass
Ethyl acetate 38.5% by mass
Polyester resin particles 46.2% by mass.

(Evaluation)
About these Examples 1-2 and Comparative Examples 1-2, coating suitability, chemical | medical agent adsorption property, and heat seal suitability were evaluated.

First, the coating suitability was evaluated based on whether or not there was unevenness in the adhesive layer 2 obtained by applying each adhesive coating agent with a dry laminator. The case where there is no unevenness is ○, and the case where there is unevenness is ×.

  Further, the drug adsorption was evaluated as follows. That is, each laminate was used to prepare a 80 mm × 80 mm four-side sealed bag, and 20 ml of dl-α-tocophenol acetate was sealed in the packaging bag and sealed. Next, after storing for 1 week under the conditions of 40 ° C. and 75% RH, dl-α-tocophenol acetate was discharged, and the weight of the remaining packaging bag was compared with the weight before encapsulation to measure the amount of adsorption. Thus, the drug adsorptivity was evaluated by this amount of adsorption.

  Next, for heat sealability, the sealant layers 3 of the respective laminates are faced to each other, heat sealed under conditions of 170 ° C., 0.2 MPa, and 1 second, then cut into strips with a width of 15 mm, and Tensilon is used. The heat seal strength was measured. The measurement condition of the heat seal strength is 300 mm / min.

  The results are shown in Table 1.

  From this result, when the adhesive layer 2 does not contain polyester resin particles (Comparative Example 1), the drug adsorptivity is high. When a content containing such a component is packaged, the component is lost over time. Can be expected. On the other hand, when the polyester resin particles are included (Examples 1 and 2, Comparative Example 2), it can be understood that the drug adsorption is suppressed and the decrease in the components in the contents is small. When Examples 1 to 2 and Comparative Example 2 are compared with each other, it can be understood that the drug adsorption is suppressed as the ratio of the polyester resin particles increases. For this reason, the ratio of the polyester resin particles is desirably 50% by mass or more. However, when it is contained in a large amount (Comparative Example 2), it is difficult to apply the coating uniformly, and the heat sealability is also lowered.

1: Base material layer 11: Plastic film 12: Gas barrier layer 2: Adhesive layer 3: Sealant layer

Claims (8)

An adhesive coating agent comprising a main agent, a curing agent, a dispersion medium and polyester resin particles,
The ratio of the polyester resin particle in solid content is 20 mass% or more and 70 mass% or less, The non-adsorptive adhesive coating agent characterized by the above-mentioned.   The non-adsorptive adhesive coating agent according to claim 1, wherein the ratio of the polyester resin particles in the solid content is 50% by mass or more.   The non-adsorptive adhesive coating agent according to claim 1 or 2, wherein the main agent comprises a polyester polyol, and the curing agent is a polyisocyanate curing agent. A laminate in which a sealant layer, an adhesive layer, and a base material layer are laminated in this order,
A non-adsorbent laminate, wherein the adhesive layer comprises a coating film containing a main agent, a curing agent and polyester resin particles, and the ratio of the polyester resin particles in the adhesive layer is 20% by mass or more and 70% by mass or less. .   The non-adsorbent laminate according to claim 4, wherein the base material layer is made of a plastic film.   The non-adsorbent laminate according to claim 4, wherein the base material layer has a gas barrier layer.   The dry thickness of the said contact bonding layer is 0.005 micrometer or more and 10 micrometers or less, The nonadsorbent layered product in any one of Claims 4-6 characterized by the above-mentioned.   A packaging bag comprising the non-adsorbent laminate according to any one of claims 3 to 6.

Images