JP6268886B2 - Laminate - Google Patents

Description

  The present invention relates to a laminate used for a packaging bag for sealing and packaging contents having fluidity such as liquid, powdered fluid, and solid-liquid mixture, and a lid material.

  In recent years, foods such as yogurt, ketchup, mayonnaise, etc. are filled and sealed in packaging bags, filled in containers and sealed with lids, and these foods do not adhere to packaging bags, containers and lids when used, Attempts have been made to examine packaging materials that have little residue, are easy to pour, or have little scattering of contents when opened.

  The packaging bag provided with such an adhesion preventing function has a water-repellent layer or an oil-repellent layer provided on the innermost layer surface on the contents side of the packaging material.

JP 2002-37310 A JP2011-93315

  If the viscosity of the content filled in the packaging material is high and the content is a component that easily adheres to the packaging material, some of the content remains inside the packaging material, and the entire content cannot be used up. There is a problem.

  For these problems, the main reason is that the contents are components that are likely to adhere to the material inside the packaging bag, so it is difficult to improve with a device related to the shape of the packaging bag. .

  Patent Document 1 describes a polyolefin packaging material in which the heat seal layer contains at least one of a nonionic surfactant or a hydrophobic additive having an adhesion preventing effect. However, the problem of non-adhesiveness, that is, oil repellency is insufficient and the contents remain inside the packaging material, especially for the contents having a large amount of oil component, cannot be improved.

  In addition, since the heat sealing property is hindered, the sealing condition must be set to a severe condition such as a high temperature, and the packaging material shrinks.

  In Patent Document 2, hydrophobic oxide fine particles are attached to the surface of a thermoplastic resin layer corresponding to a heat seal layer to impart non-adhesiveness, but the hydrophobic oxide fine particles are fixed to the heat seal surface. No specific method has been presented, and in this configuration, the hydrophobic oxide fine particles fall off and there is a sanitary problem that the contents and the like enter the food.

  In addition, since hydrophobic oxide fine particles are used, the content remains particularly inside the packaging material because it is non-adhesive, that is, the oil repellency is insufficient with respect to the content having a large oil component, as in Patent Document 1. It does not improve the problem.

Moreover, since the hydrophobic oxide fine particles are embedded in the heat seal layer in the heat seal portion, there is a problem that the cohesive force in the heat seal layer is weakened and the heat seal strength is deteriorated.

  In addition, 0.5 to 100 μm filled particles are included in the heat seal layer, and by providing a concavo-convex structure, the falling of the hydrophobic oxide fine particles is reduced by the point contact, but the filled particles are heat sealed. Since the heat seal layer is melted by heat at the time of sealing because it is contained in the layer, there is a sanitary problem that the packed particles move or drop off at the same time and enter the food such as contents.

  The present invention has been made in view of the above problems, and provides a packaging material having an oil repellency function in which contents containing an oil component do not adhere to or remain in the packaging bag and the seal strength does not deteriorate. Is an issue.

The invention according to claim 1 is composed of, in order, a base material, an anchor coat layer made of a thermosetting resin , a heat seal layer, and an oil repellent layer, and the oil repellent layer is made of inorganic oxide particles having a hydrophilic surface. It is the laminated body characterized by these.
Invention of Claim 2 consists of a base material, an anchor-coat layer, a heat seal layer, and an oil-repellent layer in order, the said oil-repellent layer consists of inorganic oxide particles with a hydrophilic surface, and the said anchor-coat layer is average A laminate comprising a composition particle having a particle diameter of 1 to 100 μm and a thermosetting resin, wherein the oil-repellent layer is composed of inorganic oxide particles having a hydrophilic surface.
The invention according to claim 3 is characterized in that the composition particles include at least one of fluororesin, silicone, silica, metal oxide, nylon, polyethylene, polystyrene, polypropylene, polyester, and acrylic resin. The laminate according to claim 2.

According to a fourth aspect of the present invention, the oil repellent layer includes a component obtained by mixing the inorganic oxide particles and an inorganic binder, and the inorganic binder is represented by M (OR) n (M = metal element). 2. The laminate according to claim 1, comprising at least one of a metal alkoxide, a hydrolyzate of the metal alkoxide, or a composite thereof.

According to the laminate of claim 1, since the oil repellent layer is made of hydrophilic inorganic fine particles, the non-adhesiveness of the content containing the oil component can be obtained.
According to the laminate of claim 2, the surface of the oil-repellent layer can be provided with an uneven shape such as a fractal structure by containing composition particles having a large average particle diameter of 1 to 100 μm in the anchor coat layer. it can. When the surface has such a concavo-convex shape, the repellency of the droplet can be improved more effectively.
Note that the fractal structure is a theoretical surface shape in which the surface length and surface area are infinite when a fine concavo-convex shape is engraved on the surface of a finite plane or solid shape. It is.
In the case of the present application, even if the circumferential length or surface area of the surface is not infinite, it is sufficient if the level at which the repellency of the droplet can be improved more effectively.
Furthermore, since particles having an average particle diameter of 1 to 100 μm are included in the anchor coat layer and have a concavo-convex structure, the composition particles can be stuck into the heat seal object at the heat seal portion and can give an anchoring effect. Seal strength does not deteriorate.
In addition, since the anchor coat layer used in the laminate uses a thermosetting resin binder, the anchor coat layer does not melt even when subjected to heat at the time of heat sealing. Therefore, particles having an average particle diameter of 1 to 100 μm are anchor coat layers. It stays inside and does not fall out.
According to the laminate of claim 3, the particles contained in the anchor coat layer used in the laminate are at least fluororesin, silicone, silica, metal oxide, nylon, polyethylene, polystyrene, polypropylene, polyester, and acrylic resin. Since it contains one, the one higher than the softening point of the heat seal object can be selected, and the composition particles can be stuck into the heat seal object and give a throwing effect, thereby deteriorating the heat seal strength. No

According to the laminate of claim 4 , since the oil repellent layer used in the laminate contains the inorganic oxide particles and the inorganic binder, the cohesion between the inorganic oxide particles is improved. The inorganic oxide particles in the oil layer do not fall off and the oil repellent layer does not collapse, and both good oil repellency and adhesion with the heat seal layer can be achieved.

It is sectional drawing of the layer structure of the laminated body concerning 1st embodiment of this invention. It is sectional drawing of the layer structure of the laminated body concerning 2nd embodiment of this invention. It is sectional drawing which shows one Embodiment of the laminated body of FIG.

  An example of a typical embodiment of the laminate of the present invention will be described below with reference to the drawings as necessary.

  The content to be filled in the packaging material of the present invention is not particularly limited, but is suitable for foods such as pudding, high lipid type yogurt, milk, seasonings such as mayonnaise, chili oil, dressing, spices, etc. Can be used.

  The laminate of the present invention is formed from a laminate having oil repellency including a substrate, an anchor coat layer, a heat seal layer, and an oil repellent layer.

  The layer structure of the laminate having oil repellency in the packaging material of the present invention is shown in FIG. As shown in FIG. 1, at least the base material 10, the anchor coat layer 20, the heat seal layer 30, and the oil repellent layer 40 are laminated in this order, and the water repellent layer 40 is provided on the outermost surface inside the packaging material. Well, for example, an adhesive or the like is inserted between any layers in order to bond the layers, or a printed layer or another water repellent layer is further laminated on the surface of the base material layer used as a packaging material It does not prevent you from doing.

  As the base material 10 of the laminated body used for forming the packaging bag of the present invention, it is only necessary to have required quality such as strength and processing suitability. For example, paper, plastic film, aluminum foil and the like can be used. As the paper, high-quality paper, special quality paper, coated paper, art paper, cast-coated paper, imitation paper, craft paper, and the like can be used. As the plastic film, stretched / non-stretched films such as polyolefin, acid-modified polyolefin, polyester, polyamide, polyethylene terephthalate, and cellophane can be used. Moreover, when barrier property etc. are requested | required, barrier base materials, such as aluminum foil, an aluminum vapor deposition film, and an inorganic oxide vapor deposition film, can be used. Further, these papers, plastic films and the like may be laminated and used via an adhesive layer or the like.

Anchor coat layer, which anchor coat function of heat seal layer, for example, acrylic resins, polyurethane resins, epoxy resins, melamine resins, phenol resins, silicone resins, polyester resins, thermosetting resins polyether resins, and preferable. A one-component curable type or a two-component curable type that reacts with a curing agent such as isocyanate may be used.

  In addition, as shown in FIG. 2, in the case where composition particles having an average particle diameter of 1 to 100 μm for forming an uneven structure in the anchor coat layer are included, by using a thermosetting resin, particles can be obtained even in an overheating process such as a sealing process in a filling process. Is firmly fixed to the anchor coat layer, and the composition particles can be prevented from falling off even in the packaging material manufacturing process and the contents filling process.

  As the material of the composition particles included in the anchor coat layer, fluororesin, silicone, silica, metal oxides such as alumina and magnesia, nylon, PE, polystyrene (PS), PP, polyester, acrylic resin, and the like are used. be able to. A plurality of types may be selected from these materials, and a plurality of particles made of different materials may be mixed and used.

  The fluororesin is polytetrafluoroethylene (PTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / ethylene copolymer (ETFE). ), Polychlorotrifluoroethylene (PCTFE), EFEP, and the like.

Silicone is a powder obtained by coating the surface of a spherical silicone rubber powder with a silicone resin, a powder of silicone rubber having a structure in which dimethylpolysiloxane is crosslinked, or a polyorgano having a crosslinked structure represented by (RSiO _3/2 ) n. Silsesquioxane cured powder is good.

  The acrylic particles are preferably polymethyl methacrylate, polybutyl methacrylate, polyacrylate ester, crosslinked polymethyl methacrylate, crosslinked polybutyl methacrylate, and crosslinked polyacrylate ester.

  It is desirable to select the composition particles contained in the anchor coat layer according to the sealing conditions at the time of filling and the material of the container to be a heat seal target. In particular, in order for the composition particles to penetrate into the heat sealing object by sealing, the softening point is preferably higher than the heat sealing temperature and higher than the softening point of the heat sealing object.

  The size of the composition particles contained in the anchor coat layer is preferably 1 micrometer (μm) or more and 100 μm or less, and preferably 10 μm or more and 50 μm or less. If the average particle diameter is smaller than 1 μm, it will be difficult to provide sufficient irregularities on the surface of the irregular layer. Further, if the average particle diameter is larger than 100 μm, it becomes difficult to impart unevenness at a high density, the oil repellency function cannot be improved, and the greatly protruding composition particles fall off due to external stress such as friction. It becomes easy to do.

The thickness of the thermosetting resin component in the anchor coat layer is preferably in the range of 0.1 μm to 5 μm. If it is 0.1 μm or less, the adhesion to the substrate and the adhesion to the heat seal layer may be impaired.

When the anchor coat layer includes particles having an average particle diameter of 1 to 100 μm for forming a concavo-convex structure, if it is 5 μm or more, the composition particles forming the concavo-convex are buried, and the oil repellency function by a sufficient concavo-convex structure is not good. There is a fear.

  In order that the composition particles of the anchor coat layer have an uneven structure effectively, the average particle diameter of the particles is smaller than the total thickness of the binder resin, the heat seal layer, and the oil repellent layer of the anchor coat layer. The average particle diameter is preferably 1.5 times or more with respect to the total thickness of the binder resin of the anchor coat layer, the heat seal layer, and the oil repellent layer.

  In addition, when the surface roughness Rz (JIS B0601 1994) of the oil repellent layer surface has irregularities of 5 μm or more, the water repellent effect is more stably exhibited.

  Although there is no restriction | limiting in particular about the formation method of an anchor coat layer, When a composition particle | grain with an average particle diameter of 1-100 micrometers for forming an uneven | corrugated structure in an anchor coat layer is included, a composition particle is mixed with a thermosetting resin, for example It can form by apply | coating the made material on a base material, and heating and hardening a thermosetting resin. Depending on the relationship between the amount of the thermosetting resin and the diameter of the mixed particles, some of the composition particles may be exposed from the thermosetting resin. It is supported by the resin and held on the substrate with sufficient strength.

In the present invention, the average particle diameter refers to an average diameter obtained by converting individual composition particles into spherical particles, and is defined as being measured by a Coulter method or a laser scattering method. Also, JIS
Since the content of B0601 varies slightly from year to year, the present invention follows that of 1994.

  The heat seal layer is preferably a heat seal varnish or a hot melt agent, and can be appropriately selected depending on the form used, the material of the adherend, the filling conditions, the required quality of seal strength and opening strength, and the like. When using a heat seal varnish that dissolves and coats in a solvent, the components are polyacrylate resin, urethane resin, melamine resin, amino resin, epoxy resin, polyethylene resin, styrene resin, polypropylene resin, polyester resin, cellulose resin, vinyl chloride Resin, polyvinyl alcohol resin, ethylene vinyl acetate copolymer, and mixed materials thereof are used.

  When hot melt is used, polyacrylate resin, EVA resin, vinyl acetate resin, ethylene resin, polyester resin, modified polyolefin and the like can be used. The modified polyolefin is preferably a polyolefin modified with an unsaturated carboxylic acid or an anhydride thereof, because higher adhesion can be obtained. Polyethylene, polypropylene, or the like can be used as the polyolefin.

  Alternatively, a heat-adhesive polyolefin resin may be used. In that case, a low-density polyethylene resin (LDPE), a linear low-density polyethylene resin (LLDPE), a polypropylene resin (PP), an ethylene-methacrylic acid copolymer resin ( EMAA), ethylene-acrylic acid copolymer resin (EAA), ethylene-vinyl acetate copolymer resin (EVA), ionomer resin (IO), ethylene-methyl acrylate copolymer resin (EMA), ethylene-ethyl acrylate copolymer resin ( EEA), ethylene-butyl acrylate copolymer resin (EBA) and the like, and mixed components thereof can be used.

  The thickness of the heat seal layer is preferably in the range of 0.1 μm to 50 μm. If the thickness is 0.1 μm or less, sufficient seal strength cannot be obtained. On the other hand, when the thickness is 50 μm or more, the uneven structure formed by the anchor coat layer made of the thermosetting resin and the particles is filled, and the oil repellency function by the sufficient uneven structure cannot be reproduced.

  The oil repellent layer is inorganic oxide particles having a hydrophilic surface, and various inorganic oxides such as silica, alumina, magnesia, and titanium oxide can be used. Among them, silica is preferable for improving the adhesion to the inorganic binder, and synthetic silica obtained from a dry process such as a combustion method or an arc method, a wet process such as a precipitation method or a gel method, or natural silica may be used.

  The inorganic oxide particles are not hydrophobized on the surface. If the average particle diameter of the inorganic oxide particles is 5 nanometers (nm) or more and 10 μm or less, it is preferable that the inorganic oxide particles are more uniformly distributed on the surface. There is no particular limitation on the variation in the average particle diameter, but the presence of particles of various sizes can easily form a fractal structure.

  In the case where composition particles having an average particle diameter of 1 to 100 μm for forming an uneven structure in the anchor coat layer are included, it is desirable to make them smaller than the composition particles of the anchor coat layer. The average particle diameter means a particle diameter in a state where inorganic oxide particles are aggregated, and can be measured by a Coulter method, a dynamic scattering, or a laser scattering method.

  When the oil-repellent layer is configured to include inorganic oxide particles and an inorganic binder, the inorganic oxide particles are more firmly fixed in the oil-repellent layer, and wear resistance against physical contact is improved.

As the inorganic binder, it is preferable to use a metal alkoxide. Metal alkoxides are tetraethylorthosilicate (Si (OC ₂ H ₅ ) ₄ ) (TEOS), triisopropylaluminum (Al (OC ₃ H ₇ ) ₃ ), etc. General formula M (OR) n (where M is Si , Ti, Al, a metal such as Zr, R is one represented by _{CH 3, C 2 H 5 C} m H 2m + 1 (m = 1~3) in the alkyl group represented like, n represents a natural number of 1 to 4) It is. Among them, the characteristics of metal alkoxides in which M is Si, Al, Ti are excellent. Besides this, in order to increase the cohesive strength of the inorganic binder layer and the adhesion between the inorganic binder layer and the adjacent layer, a silane coupling agent is added in the inorganic binder layer, and the reaction of the inorganic binder is controlled. A catalyst or the like may be used. The functional group of the silane coupling agent preferably has any one of vinyl, epoxy, styryl, methacryl, acrylic, amino, ureido, mercapto, sulfide, and isocyanate.

  The oil-repellent layer is made by mixing a metal alkoxide or a mixture of a metal alkoxide and a silane coupling agent directly or in advance with a hydrolytic reaction with a hydrophobic particle to create a composite solution, and using this composite solution, thermoplasticity It can be formed by coating on the resin layer. The coating method when applying the coating includes various known methods such as roll coating, direct gravure coating, reverse gravure coating, bar coating, kiss reverse coating, die coating, doctor blade coating, brush coating, dip coating, spray coating, and spin coating. It can be appropriately selected and used.

  The weight ratio of the oil-repellent particles and the metal oxide contained in the inorganic binder in the composite solution is preferably 5:95 to 95: 5. When the weight ratio of the hydrophilic particles is lower than 5%, the area where the hydrophilic surface covers the outermost layer becomes small, and sufficient oil repellency cannot be obtained. On the other hand, if it is 95% or more, the hydrophilic particles come out on the outermost surface without being bonded to the binder, so that the hydrophobic particles fall off due to external stress such as friction and vibration, and the oil repellency is likely to be impaired.

  The film thickness of the oil repellent layer is preferably in the range of 0.1 μm to 10 μm. When it is 0.1 μm or less, the amount of oil-repellent particles appearing on the outermost surface is reduced, and the oil repellency is lowered. On the other hand, if it is 10 microns or more, the oil repellent layer becomes too thick and is liable to cause a sealing hindrance at the time of heat sealing and cannot be sealed sufficiently. In addition, when the anchor coat layer includes particles having an average particle diameter of 1 to 100 μm for forming an uneven structure, if the oil repellent layer is too thick, the unevenness caused by the anchor coat layer is offset, and sufficient oil repellent function is achieved. May not be expressed.

  The oil repellent layer is preferably provided so as to cover 30% or more, more preferably 70% or more of the heat seal layer in a plan view of the laminate (when viewed in the thickness direction). When the coating area ratio is less than 30%, the area where the contents come into contact with the oil repellent surface increases, and sufficient oil repellent performance cannot be exhibited. In addition, the oil repellent layer may not be provided in a portion or the like that is previously known not to come into contact with the contents, for example, by being adhered to the container body by heat sealing.

  As described above, according to the laminate of the present embodiment, the anchor coat layer is provided on one surface of the base material facing the contents (hereinafter sometimes referred to as “opposing surface”), and further Since the heat seal layer and the oil repellent layer are provided on the anchor coat layer, an oil repellent effect is obtained.

  When the anchor coat layer includes particles having an average particle diameter of 1 to 100 μm for forming an uneven structure, the oil repellent effect by the uneven structure is combined with the oil repellent effect by the hydrophilic fine particles of the oil repellent layer. Higher oil repellency can be realized.

  In addition, when the anchor coat layer includes composition particles having an average particle diameter of 1 to 100 μm for forming a concavo-convex structure, the particles are supported on the base material by the thermosetting resin in the anchor coat layer. On the other hand, even when the heat seal process is performed and the heat seal layer is softened, the heat seal layer hardly moves in the thickness direction. Therefore, the composition particles are buried in the thermoplastic resin, the relatively large unevenness is damaged, the occurrence of defects such as composition particles falling off the cover material is suitably suppressed, and before and after heat sealing treatment Stable water repellency can be exhibited. Furthermore, the composition particles can be suitably prevented from falling off against stresses or the like acting from the outside in various processes such as conveyance other than the heat sealing process.

  Furthermore, since the composition particles are supported by the thermosetting resin, the particles are heated even when the specific gravity value of the particles and the thermoplastic resin is approximated when the heat seal layer is formed on the anchor coat layer. The composition particles do not move from the heat seal layer by moving above the seal layer. Therefore, since the oil repellent layer is always in contact with the heat seal layer, the oil repellent layer is surely bonded to the heat seal layer, and the hydrophilic particles of the oil repellent layer are less likely to fall off.

  As shown in FIG. 3, when using the laminated body 50 as a lid | cover material, if it joins with respect to the container main body 60 by heat sealing and the internal space of a container main body is sealed, the packaging container of this invention will be completed. The material of the container body is not particularly limited, and a plastic container such as polypropylene, polyethylene, or polystyrene, or a composite container in which paper or a plastic film is bonded can be used. In addition, there is no problem even if an oil repellent layer is present in the heat sealed portion of the laminate. In this case, in the heat sealing process, the oil-repellent layer at the portion to be joined to the container body is cracked by a seal bar or the like at the time of heat sealing, and a part of the heat seal layer or one of the resin of the container body is formed from the crack. The part passes through the crack and the laminate and the container body are joined.

  Further, as shown in FIG. 3, since the composition particles applied to the anchor coat layer are stuck into the container by heat sealing and a physical sealing property due to the anchoring effect is also exhibited, there is no problem in the heat sealing property.

  The laminated body of this invention is further demonstrated using an Example and a comparative example. In addition, each following Example is an illustration of the structure of this invention to the last, and, thereby, the technical scope of this invention is not limited at all.

<Example 1>
As a base material layer, 25 μm of polyethylene terephthalate (hereinafter referred to as PET) and 7 μm of aluminum foil (hereinafter referred to as AL foil) were bonded together by a dry lamination method.

  An anchor coat layer having a thickness of 2 μm after drying is applied to the AL foil surface by a gravure method by applying a thermosetting resin coating agent composed of a main component of a two-component curable polyester resin dissolved in ethyl acetate and an isocyanate curing agent. Got.

  An acrylic heat-sealable thermoplastic resin was applied on the anchor coat layer by gravure coating to a thickness of 2 μm after drying to form a heat-seal layer.

  Next, an oil repellent layer having a thickness of 0.5 μm after drying a coating agent obtained by dispersing silica particles (fumed silica) having an average surface diameter of 20 nm produced by a dry method in ethanol by a gravure method is formed. The laminated body of Example 1 was obtained.

  The following tests were performed on the obtained laminate to evaluate its performance.

a. Oil Repellency Test (A) 5 microliters of oleic acid was allowed to stand on the oil repellent layer surface of the laminate, the contact angle was measured, and the following criteria were evaluated.

Contact angle 110 ° <: ○
Contact angle 90-110 °: △
Contact angle <90 °: ×
that's all.

  (B) 5 microliters of oleic acid was allowed to stand on the oil-repellent layer surface of the laminate, and the angle at which the oleic acid began to move (falling angle) was measured by gradually inclining the laminate, and evaluated according to the following criteria. .

Falling angle 10 °>: ○
Falling angle: 10-30 °: △
Rolling angle 30 ° <: ×
that's all.

b. Heat sealability (A) The water repellent layer surface of the laminate and the polypropylene sheet are heat sealed at 200 ° C., 0.2 MPa, 1.5 seconds, and the heat seal strength of a 15 mm wide test piece is measured by a tensile test method. And evaluated according to the following criteria.

10N <: ○
5-10N: △
<5N: ×
that's all.

  (B) Heat sealing is performed under the conditions of (A) above, and a cross section in which the laminate and the polypropylene are heat sealed is taken out, and the particles in the anchor coat layer are contained in the container at a magnification of 50 to 100 times with an optical microscope. Check visually that it is stuck.

Stuck in: ○
Not pierced: ×
that's all.

c. Abrasion resistance test Using a Gakushin tester (conforming to JIS K5701-1), a SUS 200 g load friction element was placed on the oil repellent layer surface of the laminate and reciprocated 100 times. 5 microliters of oleic acid was allowed to stand and the contact angle was measured.

Contact angle 110 ° <: ○
Contact angle 90-110 °: △
Contact angle <90 °: ×
that's all.

<Example 2>
Silica sol binder comprising a dispersion of silica particles (fumed silica) having an average surface diameter of 20 nm, which is produced by a dry process, dispersed in ethanol and a silica sol solution prepared by hydrolyzing tetraethoxysilane (TEOS). The resulting oil repellent was applied onto the heat seal layer, and a laminate was obtained in the same manner as in Example 1 except that the oil repellent layer was formed by coating the entire surface with a thickness of 1 μm after drying. .

<Example 3>
It was prepared in the same manner as in Example 2 except that the average primary particle diameter of the hydrophilic silica fine particles used for the oil repellent coating agent for the oil repellent layer was 200 nm.

<Example 4>
It was prepared in the same manner as in Example 2 except that the average primary particle diameter of the hydrophilic silica fine particles used in the oil repellent coating agent for the oil repellent layer was 2000 nm.

<Example 5>
It was prepared in the same manner as in Example 2 except that the average primary particle diameter of the hydrophilic silica fine particles used for the oil repellent coating agent for the oil repellent layer was 5000 nm.

<Example 6>
It was prepared in the same manner as in Example 2 except that the method for producing hydrophilic silica fine particles used for the oil repellent coating agent of the oil repellent layer was a wet method.

<Example 7>
It was prepared in the same manner as in Example 2 except that the hydrophilic inorganic oxide particles used for the oil repellent coating agent of the oil repellent layer were titanium oxide (TiO ₂ ).

<Example 8>
It was prepared in the same manner as in Example 2 except that the solvent used for the dispersion of hydrophilic silica used for the oil repellent coating agent of the oil repellent layer was methanol ethyl acetate.

<Example 9>
It was prepared in the same manner as in Example 2 except that the solvent used in the dispersion of hydrophilic silica used in the oil repellent coating agent for the oil repellent layer was ethyl acetate.

<Example 10>
It was prepared in the same manner as in Example 2 except that the silica sol solution used for the oil repellent coating agent for the oil repellent layer was prepared by hydrolyzing triisopropylaluminum (TIPA).

<Example 11>
It was created in the same manner as in Example 2 except that the resin component used for the heat seal layer was a thermoplastic resin mainly composed of an ethylene elastomer resin.

<Example 12>
A laminate was obtained in the same manner as in Example 2 except that the resin component of the anchor coat layer was a thermosetting resin composed of a main component of a two-component curable polyurethane resin in which ethyl acetate was dissolved and an isocyanate curing agent.

<Example 13>
A thermosetting resin 10 having a mean particle diameter of 20 μm composed of an acrylic resin is added to a thermosetting resin coating agent composed of a main component of a two-part curable polyester resin in which an anchor coat layer is dissolved in ethyl acetate and an isocyanate curing agent. A laminate was obtained in the same manner as in Example 2 except that the composition was dispersed and adjusted at a ratio of 10 parts by weight of the composition particles to parts by weight.

<Example 14>
A laminate was obtained in the same manner as in Example 13 except that particles having an average particle diameter of 50 μm of the composition particles made of an acrylic resin used for the anchor coat layer were used.

<Example 15>
A laminate was obtained in the same manner as in Example 13 except that the composition particles used for the anchor coat layer were nylon resin.

<Example 16>
It was produced in the same manner as in Example 2 except that the average primary particle diameter of the hydrophilic silica particles used for the oil repellent coating agent of the oil repellent layer was 15 μm (15000 nm).

< Comparative Example 3 >
It was prepared in the same manner as in Example 13 except that the resin component used for the anchor coat layer was a thermoplastic resin mainly composed of an acrylic resin dissolved in ethyl acetate.

<Example 18>
It was created in the same manner as Example 13 except that the average particle size of the composition particles made of acrylic resin used for the anchor coat layer was 0.8 μm.

<Example 19>
It was prepared in the same manner as in Example 13 except that the average particle diameter of the composition particles made of acrylic resin used for the anchor coat layer was 120 μm.

<Comparative Example 1>
It was prepared in the same manner as in Example 2 except that the silica particles used in the oil repellent coating agent for the oil repellent layer were trimethylsilyl-treated hydrophobic silica particles.

<Comparative example 2>
An oil repellent layer was prepared in the same manner as in Example 2 except that silica particles were not used for the oil repellent coating agent.

From Table 1, the laminates produced in Examples 1 to 19 have no problems in all items of oil repellency, heat sealability, and wear resistance as compared with the laminates produced in Comparative Example 1 or 2. It was confirmed that it can be used as a packaging material without any problems and exhibits an oil repellent effect.

  According to the present invention, by providing an oil-repellent layer on a laminate, it is possible to provide a laminate in which the contents can be used without waste without the contents adhering to and remaining on a packaging material such as a packaging bag or a lid. it can.

DESCRIPTION OF SYMBOLS 10 Base material 20 Anchor coat layer 21 Composition particle 30 Heat seal layer 40 Water repellent layer 50 Laminated body 50 Container body

Claims (4)

A laminate comprising , in order, a base material, an anchor coat layer made of a thermosetting resin , a heat seal layer, and an oil repellent layer, wherein the oil repellent layer is made of inorganic oxide particles having a hydrophilic surface.   In order, a base material, an anchor coat layer, a heat seal layer, an oil repellent layer, the oil repellent layer is composed of inorganic oxide particles having a hydrophilic surface, and the anchor coat layer is composed of composition particles having an average particle diameter of 1 to 100 μm. A laminate comprising a thermosetting resin and the oil repellent layer comprising inorganic oxide particles having a hydrophilic surface.   The laminate according to claim 2, wherein the composition particles include at least one of fluororesin, silicone, silica, metal oxide, nylon, polyethylene, polystyrene, polypropylene, polyester, and acrylic resin. . The oil repellent layer includes at least a component obtained by mixing the inorganic oxide particles and an inorganic binder, and the inorganic binder is M (OR) n (where M is a metal element, R is C _m H _{2m + 1} (where m = 1 to 3), any one of the metal alkoxides represented by n = 1 to 4), a hydrolyzate of the metal alkoxides, or a composite thereof . The laminate according to Item 1 .

Images