JP2002155260A - Adhesive for dry lamination and laminated packaging material using the same - Google Patents

Abstract

(57) [Problem] An adhesive for dry or non-solvent lamination and an adhesive for use in dry or non-solvent lamination, in which low-molecular-weight substances derived from the adhesive are less eluted and sometimes have little decomposition residue from a polymerization catalyst and a silane coupling agent. In providing packaging materials. The main agent is one or two selected from dimer fatty acids and their ester compounds, and one or two selected from aromatic dicarboxylic acids and their ester compounds used as needed; It is a polyester resin formed by reaction with two kinds of glycols, and the curing agent is one or two kinds selected from a diisocyanate adduct of trimethylolpropane, a burette or a trimer of the diisocyanate. An adhesive for dry lamination characterized by the above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an adhesive for dry or non-solvent lamination used for packaging materials such as foods, beverages, pharmaceuticals and electronic equipment parts, and more particularly to elution of low molecular weight substances derived from the adhesive. The present invention relates to an adhesive for dry or non-solvent lamination with a low content, a laminated packaging material using the same, and a packaging bag produced using the material.

[0002]

2. Description of the Related Art Conventionally, there are various laminating methods for laminating paper, aluminum foil, plastic film, various kinds of vapor-deposited films and the like, and dry or non-solvent laminating methods are often used for general packaging materials.

[0003] The dry lamination method is, for example, a first method.
Apply the organic solvent solution of the adhesive to the film-forming surface of the already formed plastic film or aluminum foil surface as the base material. Immediately after drying the organic solvent, the adhesive surface is uncured and slightly tacky (tack). In the state of being wrapped, the second base material is pressure-bonded and wound up, and the adhesive is cured and laminated, and when heat resistance is required in a retort packaging material or the like, if the packaging material is required to have heat resistance, It is suitably used when a "waist" is required or when the total thickness is limited. The advantage of this method is that the second base material does not require air permeability for evaporation, so it can be applied to a wide range of films and metal foils, and has high heat resistance, water resistance and chemical resistance. It can be used as a function. Furthermore, by using a film formed at a relatively low temperature,
The lamination can be performed without deteriorating the properties of the sealant layer as the second base material, and the dimensional change of the product is small. On the other hand, the non-solvent laminating method is a laminating method in which a non-solvent type adhesive is heated to a low viscosity, applied to a plastic film or an aluminum foil, and the second substrate is pressed, wound and cured without drying. . Since this method does not use an organic solvent, there are no problems such as the discharge environment, residual solvent odor, and recovery.

[0004] However, foods, beverages, pharmaceuticals, electronic parts and the like packaged by using a packaging material laminated by a dry or non-solvent lamination method having the above-mentioned advantages are used for dry or non-solvent lamination. Low molecular weight substances eluted from the adhesive,
Decomposition residues from polymerization / curing catalysts and silane coupling agents affect the odor, taste, and composition of the contents and internal solution, degrade the quality, and adversely affect the quality of the parts themselves was there.

In order to solve the problem, it is possible to use a melt extrusion lamination method, a heat lamination method, or the like which uses a small amount of an adhesive but changes the material composition, or uses no adhesive. However, these methods have problems in that the adhesive strength is insufficient, expensive production equipment is required, and the substrate (quality) such as a film to be laminated is limited.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and it is an object of the present invention to take account of decomposition residues from a polymerization catalyst and a silane coupling agent. The low-molecular-weight material derived from the adhesive, which accounts for the majority of the dissolution, is low in dry or non-solvent laminating adhesives and packaging materials using the same.
It is an object of the present invention to provide a low-elution packaging material that does not change the quality of beverages, pharmaceuticals, electronic device parts, and the like.

[0007]

Means for Solving the Problems To solve the above problems, first, the invention according to claim 1 is directed to an adhesive for dry lamination comprising at least a main agent and a curing agent, wherein the main agent is a dimer fatty acid. A polyester resin formed by the reaction of one or two selected from the ester compounds with one or two glycols, wherein the curing agent is an adduct of trimethylolpropane with a diisocyanate, or a burette of the diisocyanate An adhesive for dry lamination comprising one or two selected from a body or a trimer.

According to a second aspect of the present invention, in the first aspect of the present invention, the main agent comprises one or two kinds selected from dimer fatty acids and their ester compounds, and aromatic dicarboxylic acids and their ester compounds. 1 or 2 selected
An adhesive for dry lamination comprising a polyester resin formed by reacting a seed with one or two kinds of glycols.

The invention according to claim 3 is the invention according to claim 1 or 2, wherein the glycols are
CnH2n (OH) 2 (n = 2 to 20), diethylene glycol, dipropylene glycol, triethylene glycol, 3-aminopropanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, An adhesive for dry lamination, which is dimer acid reduced glycol, dimethylolpropionic acid, polyethylene glycol, polypropylene glycol, poly1,2-butylene glycol, or polytetramethylene ether glycol.

According to a fourth aspect of the present invention, in the adhesive for dry lamination according to any one of the first to third aspects, the diisocyanates are isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, and hexamethylene. Diisocyanate,
Hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate,
It is an adhesive for dry lamination that is hydrogenated diphenylmethane diisocyanate.

According to a fifth aspect of the present invention, there is provided an adhesive for dry lamination comprising at least a main component and a curing agent, wherein the main component is one or two selected from dimer fatty acids and ester compounds thereof, and one to two. Polyester diol resin formed by reaction with various glycols
Or a polyester urethane diol resin elongated by two or more diisocyanates, wherein the curing agent is one or two selected from a diisocyanate adduct of trimethylolpropane, a burette or trimer of the diisocyanate An adhesive for dry lamination characterized by comprising:

According to a sixth aspect of the present invention, there is provided an adhesive for dry or non-solvent lamination comprising at least a main component and a curing agent, wherein the main component is selected from the group consisting of dimer fatty acids, hydrogenated products thereof, and ester compounds and derivatives thereof. A polyester urethane diol resin obtained by extending a polyester diol resin obtained by a reaction of one or two selected fatty acids and one or two glycols with one or two diisocyanates, wherein the curing agent is A laminating adhesive comprising one or two selected from the group consisting of a diisocyanate adduct of trimethylolpropane and a burette or trimer of the diisocyanate.

According to a seventh aspect of the present invention, in the dry lamination adhesive according to the fifth or sixth aspect, the glycols are CnH2n (OH) 2 (n = 2 to 2).
20), diethylene glycol, dipropylene glycol, triethylene glycol, 3-aminopropanediol, 1,3-cyclohexanedimethanol, 1,4-
An adhesive for dry lamination, which is cyclohexanedimethanol, dimer acid reduced glycol, dimethylolpropionic acid, polyethylene glycol, polypropylene glycol, poly1,2-butylene glycol, or polytetramethylene ether glycol.

According to an eighth aspect of the present invention, in the dry lamination adhesive according to any one of the fifth to seventh aspects, the diisocyanates are isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, and hexamethylene. Diisocyanate,
Hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate,
It is an adhesive for dry lamination that is hydrogenated diphenylmethane diisocyanate.

According to a ninth aspect of the present invention, there is provided the adhesive for lamination according to any one of the fifth to eighth aspects, further comprising an aromatic dicarboxylic acid or an ester compound thereof or a derivative thereof as a component of the main agent. An adhesive for lamination containing one or two aromatic dicarboxylic acids selected from the group consisting of:

According to a tenth aspect of the present invention, there is provided the adhesive for dry lamination according to any one of the fifth to ninth aspects, wherein the polyester diol resin and the polyester urethane diol according to the fifth or sixth aspect are provided. The main ingredient is a mixture of resins at an appropriate mixing ratio,
An adhesive for dry lamination using the curing agent according to claim 5 or 6.

An eleventh aspect of the present invention is directed to a method for producing a film, comprising using the laminating adhesive according to any one of the first to tenth aspects, wherein at least two layers selected from paper, plastic film, various kinds of vapor-deposited films, and aluminum foil are used. It is a laminated packaging material characterized by laminating and laminating kinds or more.

The invention according to claim 12 is the invention according to claim 11.
In the laminated packaging material according to the present invention is a laminated packaging material obtained by laminating and laminating a barrier layer made of a plastic film or a metal foil on which a metal or a metal compound is deposited, and forming the laminated packaging material in a pouch shape, with respect to the inner surface area of the pouch. Filled with water of 0.5ml / cm2 or more and sealed.
This is a laminated packaging material in which a substance eluted in water is 2.0 µg / ml or less when subjected to a heat treatment at 80 to 140 ° C for 10 to 120 minutes.

The invention according to claim 13 is the invention according to claim 11.
In the laminated packaging material according to the present invention is a laminated packaging material obtained by laminating and laminating a barrier layer made of a plastic film or a metal foil on which a metal or a metal compound is deposited, and forming the laminated packaging material in a pouch shape, with respect to the inner surface area of the pouch. Filled with water of 0.5ml / cm2 or more and sealed.
A laminated packaging material in which a substance eluted in water is 0.5 μg / ml or less when subjected to a heat treatment at 40 to 80 ° C. for 30 to 120 minutes.

The invention according to claim 14 is the invention according to claim 11.
The laminated packaging material according to any one of to 13 is a food,
A packaging bag produced by using as a material for forming a low-elution package for packaging beverages, pharmaceuticals, electronic device parts, and the like.

[0021]

Embodiments of the present invention will be described below. First, a description will be given of a configuration example of a package using the laminating adhesive of the present invention. As shown in FIG. 1, an aluminum foil layer (50) is laminated on polyethylene terephthalate (hereinafter abbreviated as PET) (10). On that surface, a second substrate (40) made of a non-stretched polypropylene (hereinafter abbreviated as CPP) film or the like to be a sealant layer was laminated via an adhesive layer (1a) made of the laminating adhesive of the present invention. There is a packaging material (5), and the surface of the second substrate (40) is the inside of the package, and is the surface that the contents or the internal solution comes into contact with. The aluminum foil layer (50) of the packaging material (5) is a barrier layer against oxygen, water vapor, and the like for the outside air for foods, beverages, pharmaceuticals, and the like.

As shown in FIG. 2, a ceramic base film (30) is provided on a first substrate (10) made of a PET film or the like via an adhesive layer (1a) made of the laminating adhesive of the present invention. Is laminated, and the ceramic vapor-deposited layer (30) of the ceramic vapor-deposited film (30) is further laminated.
b) On the surface, the same laminating adhesive layer (1a) as above
Packaging material (5) obtained by laminating a second substrate (40) made of an LLDPE film or the like to be a sealant layer through
It can also be. The ceramic vapor-deposited film (30) of the packaging material (5) serves as a gas barrier layer for oxygen and water vapor of the outside air for foods, beverages, pharmaceuticals, and the like as contents. ) Is opaque whereas transparent packaging material (5) is used. In addition, ceramic vapor deposition layer (30
The material of b) is SiO2, SiO or Al2O.
3, AlO or the like is generally used.

By using the packaging material (5) obtained above to form a package for foods, beverages, pharmaceuticals, etc.,
A low-elution package with less low-molecular-weight substances eluted from the laminating adhesive layer (1a) can be obtained.

Next, as shown in FIG. 1, aluminum terephthalate (hereinafter referred to as VMP)
(10) and stretched nylon (hereinafter abbreviated as ONy) (20) Unstretched polyethylene which becomes a sealant layer on the surface where the aluminum foil layer (50) is laminated on a first substrate made of a film or the like. There is a packaging material (5) obtained by laminating a second substrate (40) composed of a film or the like via an adhesive layer (1a) composed of the laminating adhesive of the present invention. The surface of the material (40) is the inside of the package, and is the surface that electronic device parts and the like touch. The aluminum foil layer (50) of the packaging material (5) is a barrier layer for oxygen and water vapor in the outside air for electronic device parts and the like.

Further, as shown in FIG. 2, a ceramic vapor-deposited film (30) is placed on a first substrate (10) made of a PET film or the like via an adhesive layer (1a) made of the laminating adhesive of the present invention. ), And a second base made of an LDPE film or the like which becomes a sealant layer via the same laminating adhesive layer (1a) on the surface of the ceramic vapor deposition layer (30b) of the ceramic vapor deposition film (30). The packaging material (5) in which the material (40) is laminated can also be used. The ceramic vapor-deposited film (30) having the structure of the packaging material (5) is used as a gas barrier layer of oxygen and water vapor of the outside air for electronic device parts and the like as contents, and the aluminum foil layer (5
0) is opaque, whereas transparent packaging material (5) is used. The material of the ceramic vapor deposition layer (30b) is SiO2, SiO or Al2O3, Al
O and the like are generally used.

By using the packaging material (5) obtained above to form a package for electronic equipment parts, etc., it is transparent and excellent in gas barrier properties and is a low molecular weight substance eluted from the laminating adhesive layer (1a). It is possible to obtain a small low-elution package.

As shown in FIG. 3, PET, PBT, PEN, ONy,
Film base (30a) composed of OPP, EVOH, PVOH, LDPE, LLDPE, CPP film, etc.
A sol-gel coat layer (30c) provided on the surface of the ceramic vapor deposition layer (30b) to make it resistant to bending or the like may be used.

The adhesive for dry lamination of the present invention is an adhesive for dry lamination containing polyester diol as a main component, an adhesive for dry lamination containing polyester urethane diol as a main component, and two kinds thereof in an appropriate mixing ratio. This is a dry laminating adhesive whose main component is a mixture.

The adhesive for dry lamination of the present invention comprises a main agent and a curing agent. First, as the main agent, one or two selected from dimer fatty acids and their ester compounds, and an aromatic dicarboxylic acid used as required. A polyester diol resin formed by the reaction of one or two selected from acids and ester compounds thereof with one or two glycols, wherein the curing agent is a diisocyanate adduct of trimethylolpropane or the diisocyanate And one or two selected from burette bodies or trimers.

As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid and phthalic acid can be used. However, it is essential to use it in combination with dimer fatty acids and / or esters thereof.
A mixture of the two can be selected in consideration of proper adhesiveness and the like.

Glycols which react with components (single or mixed) selected from the above acids and esters thereof to form polyester diol resins are CnH2n
(OH) 2 (n = 2 to 20, preferably n = 2 to 1)
0), diethylene glycol, dipropylene glycol, triethylene glycol, 3-aminopropanediol, 1,3-cyclohexanedimethanol, 1,4-
One or two kinds can be appropriately selected from cyclohexane dimethanol, dimer acid reduced glycol, dimethylol propionic acid, polyethylene glycol, polypropylene glycol, poly 1,2-butylene glycol, and polytetramethylene ether glycol.

As described above, the number of each of the materials to be reacted is at most two or less, and by minimizing it, the generation of by-products can be reduced and the generation of low molecular weight substances can be prevented.

The curing agent is a diisocyanate adduct of trimethylolpropane, and the diisocyanate is used alone or as a mixture. It may also be a burette or trimer of the diisocyanates. This diisocyanate can be suitably selected from among isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane diisocyanate. A xylylene diisocyanate adduct of methylolpropane, a burette of tolylene diisocyanate, or the like can be used.

As described above, an adhesive for dry lamination in which the composition and the number of the main agent and the curing agent are limited and limited can be obtained as an adhesive for dry lamination with less elution of low molecular weight substances.

The adhesive for dry lamination of the present invention comprises a main ingredient and a curing agent. First, as the main ingredient L, one or two compounds selected from aromatic carboxylic acids, dimer fatty acids and their ester compounds, and glycol A polyester urethane diol resin obtained by reaction with one or two kinds of diisocyanates, wherein the curing agent is a diisocyanate adduct of trimethylolpropane, or It is characterized by comprising one or two kinds selected from burettes or trimers of the diisocyanates.

As the aromatic carboxylic acid, terephthalic acid, isophthalic acid and phthalic acid can be used.
However, it is indispensable to use it in combination with dimer fatty acids and / or esters thereof, and a mixture with the above-mentioned phthalic acids may be selected in consideration of suitable adhesiveness and the like.

Glycols which react with components (single or mixed) selected from the above acids and esters thereof to form polyester diol resins are Cn H2n
(OH) 2 (n = 2 to 20, preferably n = 2 to 1)
0), diethylene glycol, dipropylene glycol, triethylene glycol, 31-aminopropanediol, 1,3-cyclohexanedimethanol, 1,4-
One or two kinds can be appropriately selected from cyclohexane dimethanol, dimer acid reduced glycol, dimethylolpropionic acid, polyethylene glycol, polypropylene glycol, poly1,2-butylene glycol, and polytetramethylene ether glycolyl. .

The diisocyanates which extend the polyester diol resin are 1 to 4 of isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Two types can be appropriately selected.

As described above, by reducing the amount of each material to be reacted to at most two or less, the generation of by-products can be reduced, and the generation of low molecular weight substances can be prevented.

The curing agent is a diisocyanate adduct of trimethylolpropane, and the diisocyanate is used alone or as a mixture. It may also be a burette or trimer of the diisocyanates. The diisocyanates can be appropriately selected from isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane diisocyanate, for example, trimethylol. A xylylene diisocyanate adduct of propane, a burette of tolylene diisocyanate, or the like can be used.

As described above, by using a dry lamination adhesive in which the composition and the number of the main agent and the curing agent are limited, a dry lamination adhesive with less elution of low molecular weight substances can be obtained.

The adhesive for dry lamination of the present invention comprises a main agent and a curing agent. First, one or two compounds selected from aromatic carboxylic acids, dimer fatty acids and their ester compounds, and glycols as main agents. And a polyester urethane diol resin obtained by reaction with one or two of the above, and a polyester urethane diol resin obtained by elongating the polyester diol resin with one or two diisocyanates at an appropriate mixing ratio. Is characterized by comprising one or two selected from diisocyanate adducts of trimethylolpropane or burettes or trimers of the diisocyanates.

As the aromatic carboxylic acid, terephthalic acid, isophthalic acid and phthalic acid can be used.
However, it is indispensable to use it in combination with dimer fatty acids and / or esters thereof, and a mixture with the above-mentioned phthalic acids may be appropriately selected in consideration of adhesiveness and the like.

Glycols which react with components (single or mixed) selected from the above acids and esters thereof to form polyester diol resins are CnH2n
(OH) 2 (n = 2 to 20, preferably n = 2 to 1)
0), diethylene glycol, dipropylene glycol, triethylene glycol, 3-aminopropanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, dimer acid reduced glycol, dimethylolpropionic acid, polyethylene glycol, One or two types can be appropriately selected from polypropylene glycol, poly1,2-butylene glycol, and polytetramethylene ether glycol.

The diisocyanates which extend the polyester diol resin are 1 to 4 of isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate and hydrogenated diphenylmethane diisocyanate. Two types can be appropriately selected.

As described above, by minimizing the amount of each material to be reacted by at most two or less, the generation of by-products can be reduced, and the generation of low molecular weight substances can be prevented.

The curing agent is a diisocyanate adduct of trimethylolpropane, and the diisocyanate is used alone or as a mixture. It may also be a burette or trimer of the diisocyanate. The diisocyanates can be appropriately selected from isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane diisocyanate. A xylylene diisocyanate adduct of methylolpropane, a burette of tolylene diisocyanate, or the like can be used.

As described above, by using a dry lamination adhesive in which the composition and the number of the main agent and the curing agent are limited, it is possible to obtain a dry lamination adhesive with less elution of low molecular weight substances.

The adhesive of the present invention comprises a polyester or urethane diol resin-based adhesive for dry or non-solvent lamination, a polyester or diol resin-based adhesive for dry or non-solvent lamination, and two types thereof. It is an adhesive for dry or non-solvent laminating whose main component is one mixed at an appropriate compounding ratio.

The dry or non-solvent laminating adhesive of the present invention comprises a main agent and a curing agent. The main agent is selected from the group consisting of dimer fatty acids, hydrogenated products thereof, and ester compounds and derivatives thereof. A polyester urethane diol resin obtained by elongating a polyester diol resin produced by the reaction of one or two kinds of fatty acids with one or two kinds of glycols with one or two kinds of diisocyanates, wherein the curing agent is trimethylol; An adhesive for dry or non-solvent laminations comprising one or two isocyanates selected from the group consisting of adducts of propane diisocyanates or burettes or trimers of the diisocyanates.
Further, an adhesive for lamination for dry or non-solvent, which comprises the above-mentioned polyester diol resin as a main component, is also one of the present invention.

Further, the adhesive of the present invention is characterized in that, as a component of the main agent, one or two kinds of aromatic dicarboxylic acids selected from the group consisting of aromatic dicarboxylic acids or ester compounds or derivatives thereof are further included. The laminating adhesive described above.

As the aromatic dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid and the like can be used. However, it is indispensable to use the dimer fatty acids or their hydrogenated products or their ester compounds or derivatives in combination, and they can be appropriately selected in consideration of adhesiveness and the like.

The glycols which react with the above-mentioned fatty acids and aromatic acids or their components (single or mixed) selected from ester compounds or derivatives thereof to form polyester diol resins are CnH2n (OH) 2 (n =
2 to 10), diethylene glycol, dipropylene glycol, triethylene glycol, 3-aminopropanediol, 1,3-cyclohexanedimethanol, 1,
One or two types can be appropriately selected from 4-cyclohexanedimethanol, dimer acid reduced glycol, dimethylolpropionic acid, polyethylene glycol, polypropylene glycol, poly1,2-butylene glycol, and polytetramethylene ether glycol.

As described above, the materials to be reacted are at most two types, respectively, and by using as few combinations as possible, the generation of by-products can be reduced, and thus the generation of low molecular weight substances can be prevented. is there.

The curing agent is a diisocyanate adduct of trimethylolpropane, and the diisocyanate is used alone or in a mixture. It may also be a burette or trimer of the diisocyanates. The diisocyanates and diisocyanates that can be used as an extender for the polyester diol resin include isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane diisocyanate. The curing agent can be appropriately selected from the above. Examples of the curing agent include xylylene diisocyanate adduct of trimethylolpropane and trimer of isophorone diisocyanate.

As described above, the composition of the main agent and the curing agent and the limited number of dry or non-solvent laminating adhesives are limited to provide an adhesive for dry or non-solvent laminating with less elution of low molecular weight substances. can do.

Using the laminating adhesive of the present invention, a barrier layer composed of a plastic film or a metal foil on which a metal or a metal compound is vapor-deposited is laminated to form a laminated packaging material in a pouch shape. Fill with 0.5 ml / cm2 or more of water and seal, 80
It is used as a packaging bag for foods, beverages or pharmaceuticals in which the substance eluted in water is 2.0 μg / ml or less when subjected to a heat treatment at 140 ° C. for 10 to 120 minutes.

Further, a barrier layer made of a plastic film or a metal foil on which a metal or a metal compound is vapor-deposited by using the laminating adhesive of the present invention is laminated to form a laminated packaging material in a pouch shape. An electronic device which, when filled with 0.5 ml / cm 2 or more of water and sealed and subjected to a heat treatment at 40 to 80 ° C. for 30 to 120 minutes, a substance eluted in water is 0.5 μg / ml or less. Used as a packaging bag for parts.

When the above-mentioned adhesive for dry lamination is used, for example, as shown in FIG.
(0, 20) with an adhesive (1) for dry lamination by a gravure roll (62) by a gravure method at an application amount of 1.0 to 5.0 g / m2, and preferably by a smoothing roll (60). And dry. Immediately after drying, the second base material (40) or the ceramic vapor-deposited film (30) is pressure-bonded at the stage where the adhesive surface is uncured and somewhat tacky immediately after drying. ) Can be formed by laminating a resin by a kneelam method and laminating the resin.

[0060]

Next, the present invention will be specifically described with reference to examples.

Polyester diol resin-based dry laminating adhesives having the following 14 types of compositions 1) to 14) were experimentally produced. 1) Main agent: terephthalic acid, polyester diol resin of dimer acid and ethylene glycol, 1,4-butanediol Curing agent: trimethylolpropane xylerylene diisocyanate adduct 2) Main agent: isophthalic acid, dimer acid and 1,6 -Polyester diol resin with hexanediol Curing agent:
Isophorone diisocyanate adduct of trimethylolpropane 3) Main ingredient: polyester diol resin of dimer acid with 1,4-butanediol and neopentyl glycol
Curing agent: trimer of isophorone diisocyanate 4) Main agent: dimethyl isophthalate, polyester resin of dimer acid and hexylene glycol Curing agent: trimer of isophorone diisocyanate 5) Main agent: isophthalic acid, dimer acid and 1,6- Polyester diol resin with hexanediol and 1,4-cyclohexanedimethanol Curing agent: trimer of xylylene diisocyanate 6) Main ingredient: terephthalic acid, dimer acid and dimer acid reduced glycol, polyester diol with 1,6-hexanediol Resin Curing agent: Trimethylolpropane adduct of isophorone diisocyanate 7) Main ingredient: Polyester diol resin of dimer acid and 3-methylpentanediol Curing agent: Adduct of trimethylolpropane adduct of isophorone diisocyanate Mixture with hydrogenated diphenylmethane diisocyanate adduct 8) Base: hydrogenated dimer acid and ethylene glycol
Polyester diol resin with 1,4-cyclohexanedimethanol Curing agent: Trimethylolpropane adduct of isophorone diisocyanate and xylylene diisocyanate 9) Main agent: Polyester diol resin of hydrogenated dimer acid and ethylene glycol Curing agent: Trimethylolpropane Trimers of isophorone diisocyanate. 10) Main ingredient: polyester diol resin of dimer acid with ethylene glycol and dimethylol propionic acid
Curing agent: burette of hexamethylene diisocyanate 11) Main ingredient: dimethyl 2,6-naphthalenedicarboxylate, polyester diol resin of dimer acid and 2-methyl-1,3-propanediol Curing agent: trimer of isophorone diisocyanate 12) Main agent: dimethyl 2,6-naphthalenedicarboxylate, terephthalic acid, polyester diol resin of dimer acid and propylene glycol Curing agent: Trimethylolpropane adduct of isophorone diisocyanate and xylylene diisocyanate 13) Main agent: dimethyl biphenyl dicarboxylate Polyester diol resin of dimer acid and 1,4-butanediol, 1,6-hexanediol Curing agent: trimethylolpropane isophorone diisocyanate, xylylene diisocyanate Preparative adduct 14) base compound: biphenyl dicarboxylic acid dimethyl, terephthalic acid, dimer acid and ethylene glycol, 3-methylpentane diol and polyester diol resin curing agent: trimer of isophorone diisocyanate

Example 1 First, as shown in FIG. 1, a 12 μm-thick PET was used as a first substrate (10) on one side.
On the aluminum foil layer (50) surface on which an aluminum foil layer (50) having a thickness of 9 μm was laminated, 14 types of dry laminating adhesives 1) to 14) obtained above by the gravure method were respectively applied on average for 2 times. When the adhesive surface is still in a tacky state after being coated and dried at a coating amount of 0.5 g / m 2, a CPP film having a thickness of 60 μm is pressure-bonded thereon as a second base material (40) to form a packaging material (5). I got

Example 2 1) to 1) obtained above
As shown in FIG. 2, the 14 types of dry laminating adhesives of 4) were applied to a 12 μm-thick PET film by a gravure method at an average application amount of 3.5 g / m 2, and then dried. In the adhesive state, the base film (30a) surface of the ceramic vapor-deposited film (30) using the ONy film having a thickness of 15 μm as the base film (30a) is pressure-bonded from above, and the ceramic vapor-deposited film (30) The above-mentioned adhesives for dry lamination of 1) to 14) are similarly applied to the surface of the ceramic vapor-deposited layer (30b) made of Al2O3 and dried, and when the surface of the adhesive is still in an adhesive state, a 60 μm-thick LLDP is applied from above.
The E film was pressure-bonded as a second substrate (40) to obtain a packaging material (5).

Example 3 As shown in FIG. 1, a 12 μm thick VMPET was used as the first base material (10, 20).
And on one side of a 25 μm ONy laminate product, applied by an average amount of 3.5 g / m 2 by a gravure method and dried, and when the adhesive surface is still in an adhesive state, a 9 μm-thick aluminum foil is laminated thereon. An aluminum foil layer (50) was obtained, and on the surface of the aluminum foil layer (50), the 14 types of dry laminating adhesives 1) to 14) obtained above by the gravure method were each 3.0 g / average in average. m2
When the adhesive surface is still in a tacky state, an LDPE film having a thickness of 80 μm is melt-extruded as a second base material (40) from above, and then pressure-bonded to form a packaging material (5). Obtained.

Example 4 1) to 1) obtained above
As shown in FIG. 2, 14 types of dry laminating adhesives of 4) were applied to a PET film having a thickness of 12 μm by a gravure method at an average application amount of 3.0 g / m 2 and dried.
When the adhesive surface is still sticky, 15μm thick on it
Base film (30a) of ceramic vapor deposited film (30) using ONy film as base film (30a)
The surfaces are pressure-bonded, and a ceramic vapor-deposited film (3
0) Ceramic deposited layer made of Al2O3 (30b)
On the surface, the above-mentioned adhesives for dry lamination of 1) to 14) are applied and dried in the same manner, and when the adhesive surface is still in an adhesive state, an LDPE film having a thickness of 80 μm is formed thereon as a second substrate (40). Pressure bonding was performed to obtain a packaging material (5).

<Example 5> Except that the ceramic vapor-deposited film (30) in Example 2 was formed by applying a sol-gel coat layer (30c) by hybridizing (crosslinking reaction) with alkoxysilane using polyvinyl alcohol as a matrix. In the same manner as in Example 2, a packaging material (5) as shown in FIG. 3 was obtained.

<Example 6> Instead of the ceramic vapor-deposited film (30) in Example 2, ONy having a thickness of 15 μm was used.
A packaging material (not shown) was obtained in the same manner as in Example 2, except that the film was used.

<Example 7> Except that the ceramic vapor-deposited film (30) in Example 4 was obtained by applying a sol-gel coat layer (30c) by hybridizing (crosslinking reaction) with alkoxysilane using polyvinyl alcohol as a matrix. In the same manner as in Example 4, a packaging material (5) as shown in FIG. 3 was obtained.

<Embodiment 8> Instead of the ceramic vapor-deposited film (30) in Embodiment 4, ONy having a thickness of 15 μm was used.
A packaging material (not shown) was obtained by the same operation as in Example 4 except that the film was used.

<Comparative Example 1> FIG. 1 shows the same materials and operations as in Example 1 except that the adhesive for dry lamination was polyester LX-747A / KX-75 (manufactured by Dainippon Ink and Chemicals, Inc.). Laminate (5) having configuration as shown
I got

<Comparative Example 2> A packaging material (5) having a structure as shown in FIG. 2 was prepared by the same material and operation as in Example 2 except that the adhesive for dry lamination used in Comparative Example 1 was used.
I got

Comparative Example 3 As shown in FIG. 1, the same materials and operations as in Example 3 were used except that the adhesive for dry lamination was a polyester-based TM-210 / ADN-401B (manufactured by Toyo Morton Co., Ltd.). A laminate (5) having the following configuration was obtained.

<Comparative Example 4> A packaging material (5) having a structure as shown in FIG. 2 was prepared by the same material and operation as in Example 4 except that the adhesive for dry lamination used in Comparative Example 3 was used.
I got

<Comparative Example 5> A packaging material (5) having a structure as shown in FIG. 3 was prepared by the same material and operation as in Example 5 except that the adhesive for dry lamination used in Comparative Example 1 was used.
I got

<Comparative Example 6> A packaging material (not shown) was obtained by the same materials and operations as in Example 6, except that the adhesive for dry lamination used in Comparative Example 1 was used.

<Comparative Example 7> A packaging material (5) having a structure as shown in FIG. 3 was prepared by the same material and operation as in Example 7 except that the adhesive for dry lamination used in Comparative Example 3 was used.
I got

Comparative Example 8 A packaging material (not shown) was obtained by the same materials and operations as in Example 8 except that the adhesive for dry lamination used in Comparative Example 3 was used.

<Experimental Results> The laminates (5) obtained in Examples 1, 2, 5, and 6 and Comparative Examples 1, 2, 5, and 6 were
With the surface of the second base material (40) serving as the sealant layer as the inside,
A package (bag) having an inner surface area of 300 cm 2 was sealed with 200 ml of water as a content, and subjected to a pressure heat treatment at 120 ° C. for 60 minutes. As an evaluation of these packages, they were allowed to cool to room temperature after treatment, and the content of water was concentrated by liquid-liquid extraction or solid phase extraction or freeze-drying with an organic solvent, and then eluted with a gas chromatograph mass spectrometer. The measured low molecular weight substances were measured. The results are shown in Table 1 as Examples and Comparative Examples.

[0079]

[Table 1]

The laminates (5) obtained in Examples 3, 4, 7, and 8 and Comparative Examples 3, 4, 7, and 8 were coated with the second substrate (40) serving as a sealant layer facing inward. Surface area 32
00cm2 package (bag) and water as content
000 ml was sealed and left at 40 ° C. for 7 days. As an evaluation of these packages, they are allowed to cool to room temperature after storage, and the content of water is concentrated by liquid-liquid extraction or solid phase extraction or freeze-drying with an organic solvent, and then eluted with a gas chromatograph mass spectrometer. The measured low molecular weight substances were measured. The results are shown in Table 2 as Examples and Comparative Examples.

[0081]

[Table 2]

From the above Tables 1 and 2, the conventional dry laminating adhesive was compared with Examples 1 to 8 using the dry laminating adhesive having the composition of 1) to 14), which is one example of the present invention. In the packages of Comparative Examples 1 to 8 used, the elution of low-molecular-weight substances was all large. Examples 1 and 3 in which an aluminum foil layer (50) was laminated between a first substrate (10, 20) and a second substrate (40) and a gas barrier layer composed of a ceramic vapor-deposited film (30) were laminated. When Examples 2, 4, 5, and 7 were compared with Examples 6 and 8 in which ordinary films were laminated, it was found that the gas barrier layer contributed to the reduction of elution of low molecular weight substances.

Next, when the above-mentioned adhesive for non-solvent lamination is used, the viscosity is reduced by heating, and for example, 1.0 to 3.0 g / m 2 is applied to the first base material.
2. At the stage where the adhesive surface is uncured and somewhat tacky, the second substrate or the above-mentioned ceramic vapor-deposited film is pressure-bonded, and the second substrate is formed by a Neelham method. Can be laminated (not shown).

Polyester diol resin-based non-solvent laminating adhesives having the following four types of compositions 15) to 18) were trial-produced. 15) Main ingredient: polyester diol resin of terephthalic acid, dimer acid and ethylene glycol, 1,4-butanediol Curing agent: xylylene diisocyanate adduct of trimethylolpropane 16) Main ingredient: isophthalic acid, dimer acid and 1,6 Polyester diol resin with hexanediol Curing agent: Isophorone diisocyanate adduct of trimethylolpropane 17) Main ingredient: Polyester diol resin of dimer acid and 1,4-butanediol, neopentyl glycol Curing agent: Trimer of isophorone diisocyanate 18) Main agent: dimethyl isophthalate, polyester diol resin of dimer acid and hexylene glycol Curing agent: trimer of isophorone diisocyanate

<Example 9> From the above 15) to 1)
8) The four types of adhesives for non-solvent lamination
On the coated surface of a ceramic vapor-deposited film having a sol-gel coat layer based on a 12 μm-thick PET film as a first substrate, an average coating amount of 2.0 g / m 2 is applied. An ONy film having a thickness of 15 μm is laminated. 15) on the ONy film surface
4) Non-solvent laminating adhesives are applied at an average application amount of 2.0 g / m 2, respectively, and when the adhesive surface is still in an adhesive state, a 60 μm thick CPP film is applied to the second base material. To obtain a packaging material (not shown).

Example 10 The four types of adhesives for non-solvent lamination obtained in 15) to 18) obtained above were applied to a PET film having a thickness of 12 μm at an average application amount of 2.0 g / m 2. When the surface is still in an adhesive state, the coated surface of a ceramic vapor-deposited film having a sol-gel coat layer based on an ONy film having a thickness of 15 μm thereon is pressure-adhered, and the above-mentioned 15) to 18) is further adhered to the ONy surface.
The adhesive for non-solvent lamination was similarly applied, and when the surface of the adhesive was still in an adhesive state, a CPP film having a thickness of 60 μm was adhered thereon as a second base under pressure to obtain a packaging material.

Comparative Example 9 A laminate was obtained by the same materials and operation as in Example 9 except that the adhesive for non-solvent lamination was a polyester AD-N401A / B (manufactured by Toyo Morton Co., Ltd.).

Comparative Example 10 Example 1 was repeated except that the non-solvent laminating adhesive used in Comparative Example 9 was used.
A packaging material was obtained by the same materials and operations as in Example 0.

<Experimental Results> The laminates obtained in Examples 9 and 10 and Comparative Examples 9 and 10 were converted into a package (bag) having an inner surface area of 300 cm 2 with the second base material surface serving as a sealant layer as the inner side. 200ml of water was sealed and sealed.
A pressure heating treatment was performed at 20 ° C. for 60 minutes. As an evaluation of these packages, they were allowed to cool to room temperature after treatment, and the content of water was concentrated by liquid-liquid extraction or solid phase extraction or freeze-drying with an organic solvent, and then eluted with a gas chromatograph mass spectrometer. The measured low molecular weight substances were measured. The results are shown in Table 3 as Examples and Comparative Examples.

[0090]

[Table 3]

From Table 3 above, it can be seen that 1 is an example of the present invention.
In contrast to Examples 9 and 10 using the non-solvent laminating adhesives having the compositions of 5) to 18), the packages of Comparative Examples 9 and 10 using the conventional non-solvent laminating adhesive have low molecular weight substances. Elution increased in each case. In the case of Example 10 in which a gas barrier layer made of a ceramic vapor-deposited film was laminated between the first base material and the second substrate, and in Example 9 in which the first substrate was equipped with a ceramic vapor-deposited film, the intermediate gas barrier layer was low. This contributed to the reduction of the elution of the molecular weight substance.

Next, a polyester urethane diol resin-based adhesive for dry lamination having 14 kinds of compositions of the following 19) to 32) was produced as a trial. 19) Main agent: terephthalic acid, polyester urethane diol resin comprising a polyester compound of ethylene glycol and 1,4-butanediol with isoglycone diisocyanate and isophorone diisocyanate Curing agent: trimethylolpropane adduct of isophorone diisocyanate and xylylene diisocyanate 20) Main agent: polyester urethane diol resin composed of a polyester compound of isophthalic acid, dimer acid and 1,6-hexanediol and hydrogenated diphenylmethane diisocyanate Curing agent: burette of hexamethylene diisocyanate 21) Main agent: dimer acid and 1,4- Polyester urethane diol resin consisting of polyester compound with butanediol and neopentyl glycol and hydrogenated diphenylmethane diisocyanate Curing agent: Trimer of isophorone diisocyanate 22) Main agent: Polyester urethane diol resin comprising dimethyl isophthalate, polyester compound of dimer acid and hexylene glycol and hydrogenated xylylene diisocyanate Curing agent: Xylylene diisocyanate addition of trimethylolpropane Body 23) Main agent: Polyester urethane diol resin consisting of xylylene diisocyanate and polyester compound of isophthalic acid, dimer acid and 1,6-hexanediol, 1,4-cyclohexanedimethanol
Isophorone diisocyanate and xylylene diisocyanate adduct of trimethylolpropane 24) Main ingredient: terephthalic acid, dimer acid and dimer acid reduced glycol, polyester urethane diol resin comprising polyester compound of 1,6-hexanediol and tolylene diisocyanate Curing agent: Tolylene diisocyanate adduct of trimethylolpropane 25) Main ingredient: Polyester urethane diol resin composed of polyester compound of isophthalic acid, dimer acid, 1,6-hexanediol and diphenylmethane diisocyanate Curing agent: Burette of hexamethylene diisocyanate 26) Main ingredient : Polyester comprising a polyester compound of dimer acid and ethylene glycol and hydrogenated diphenylmethane diisocyanate Resin diol resin Curing agent: Trimer of isophorone diisocyanate 27) Main ingredient: Polyester urethane diol resin composed of a polyester compound of dimer acid and ethylene glycol and dimethylol propinic acid and hydrogenated diphenylmethane diisocyanate Curing agent: Isophorone of trimethylol propane Diisocyanate adduct 28) Main agent: Polyester urethane diol resin composed of polyester compound of dimer acid and 3-methylpentanediol and diphenylmethane diisocyanate
Curing agent: burette of hexamethylene diisocyanate 29) Main agent: methyl 2,6-naphthalenedicarboxylate,
Polyester urethane diol resin composed of hydrogenated dimer acid, polyester compound of 1,4-butanediol and hydrogenated diphenylmethane diisocyanate Curing agent: burette of hexamethylene diisocyanate 30) Main agent: methyl 2,6-naphthalenedicarboxylate
Dimer acid and ethylene glycol, 2-methyl-1,3
Polyester urethane diol resin comprising a polyester compound with propanediol and isophorone diisocyanate Curing agent: trimer of isophorone diisocyanate 31) Main agent: methyl 2,6-naphthalenedicarboxylate,
Polyester urethane diol resin consisting of a polyester compound of dimer acid and ethylene glycol or dimethylolpropionic acid and hydrogenated diphenylmethane diisocyanate Curing agent: Trimethylolpropane adduct of isophorone diisocyanate 32) Main ingredients: dimethyl biphenyldicarboxylate, dimer acid and neopentyl Polyester urethane diol resin consisting of polyester compound with glycol and isophorone diisocyanate Curing agent: burette of hexamethylene diisocyanate

<Embodiment 11> Using the fourteen types of adhesives for dry lamination obtained in 19) to 32) obtained above, using the same materials and operations as in Embodiment 1, the structure shown in FIG. A packaging material (5) was obtained.

<Example 12> The structure shown in FIG. 2 was obtained by using the same materials and operations as in Example 2 except that the 14 types of dry laminating adhesives 19) to 32) obtained above were used. (5) was obtained.

<Example 13> Except for using the 14 types of dry laminating adhesives 19) to 32) obtained above, the same material and operation as in Example 3 were used to construct the structure shown in FIG. (5) was obtained.

<Example 14> A packaging material (not shown) was prepared by using the same materials and operations as in Example 4 except that the 14 types of dry laminating adhesives 19) to 32) obtained above were used. I got

<Example 15> Using the fourteen types of dry laminating adhesives 19) to 32) obtained above, using the same material and operation as in Example 5, the structure shown in FIG. A packaging material (5) was obtained.

<Example 16> A packaging material (not shown) was prepared by using the same materials and operations as in Example 6, except that the fourteen types of adhesives for dry laminating obtained from 19) to 32) were used. I got

<Example 17> Except for using the 14 types of dry laminating adhesives 19) to 32) obtained above, the same materials and operations as in Example 7 were used to construct the structure shown in FIG. (5) was obtained.

<Example 18> A packaging material (not shown) was prepared by using the same materials and operations as in Example 8, except that the 14 types of adhesives for dry lamination obtained in 19) to 32) obtained above were used. I got

Comparative Example 11 The adhesive for dry lamination was a polyester urethane diol resin-based A-515.
A laminate (5) having a configuration as shown in FIG. 1 was obtained by using the same materials and operations as in Example 11 except that / A-50 (manufactured by Takeda Pharmaceutical Company Limited) was used.

<Comparative Example 12> A packaging material (5) having a structure as shown in FIG. 2 was obtained by the same material and operation as in Example 12 except that the adhesive for dry lamination used in Comparative Example 11 was used. Was.

<Comparative Example 13> A packaging material (5) having a structure as shown in FIG. 3 was obtained by the same material and operation as in Example 13 except that the adhesive for dry lamination used in Comparative Example 11 was used. Was.

Comparative Example 14 A packaging material (not shown) was obtained in the same manner as in Example 14 except that the adhesive for dry lamination used in Comparative Example 11 was used.

<Comparative Example 15> A packaging material (5) having a structure as shown in FIG. 1 was prepared by the same material and operation as in Example 15 except that the adhesive for dry lamination used in Comparative Example 11 was used. Obtained.

<Comparative Example 16> A packaging material (5) having a structure as shown in FIG. 2 was obtained by the same material and operation as in Example 16 except that the adhesive for dry lamination used in Comparative Example 11 was used. Was.

<Comparative Example 17> A packaging material (5) having a structure as shown in FIG. 3 was obtained by the same material and operation as in Example 17 except that the adhesive for dry lamination used in Comparative Example 11 was used. Was.

<Comparative Example 18> A packaging material (not shown) was obtained in the same manner as in Example 18 except that the adhesive for dry lamination used in Comparative Example 11 was used.

<Experimental Results> The above Examples 11, 12, 1
The second base material (40) that becomes the sealant layer by using the laminate (5) obtained in 5, 16 and Comparative Examples 11, 12, 15, 16
A package (bag) with an inner surface area of 300 cm2 with the surface inside.
And sealed with 200 ml of water
A pressure heating treatment was performed at 60 ° C. for 60 minutes. As an evaluation of these packages, they were allowed to cool to room temperature after treatment, and the content of water was concentrated by liquid-liquid extraction or solid phase extraction or freeze-drying with an organic solvent, and then eluted with a gas chromatograph mass spectrometer. The measured low molecular weight substances were measured. The results are shown in Table 4 as Examples and Comparative Examples.

[0110]

[Table 4]

The laminates (5) obtained in Examples 13, 14, 17, and 18 and Comparative Examples 13, 14, 17, and 18
Was made into a package (bag) having an inner surface area of 3200 cm 2 with the surface of the second base material (40) serving as a sealant layer on the inside, and 1000 ml of water as a content was sealed and left at 40 ° C. for 7 days. As an evaluation of these packages, they are allowed to cool to room temperature after storage, and the content of water is concentrated by liquid-liquid extraction or solid phase extraction or freeze-drying with an organic solvent, and then eluted with a gas chromatograph mass spectrometer. The measured low molecular weight substances were measured. The results are shown in Table 5 as Examples and Comparative Examples.

[0112]

[Table 5]

From Tables 4 and 5 above, the conventional dry laminating adhesive was compared with Examples 11 to 18 using the dry laminating adhesive having the composition of 19) to 32), which is one example of the present invention. In the packages of Comparative Examples 11 to 18 used, the elution of the low-molecular-weight substance was all large. Examples 11 and 13 in which an aluminum foil layer (50) was laminated between a first substrate (10, 20) and a second substrate (40).
When Examples 12, 14, 15, and 17 in which a gas barrier layer composed of a ceramic vapor-deposited film (30) is laminated and Examples 16 and 18 in which a normal film is laminated are compared,
The gas barrier layer contributed to the reduction of elution of low molecular weight substances.

Further, an adhesive for dry lamination of a polyester-based and polyester-urethane-based mixture having the following four compositions 33) to 36) was prepared. 33) Main agent: Mixture of polyester phthalic resin, polyester diol resin composed of dimer acid and 1,6-hexanediol, and polyester urethane diol resin obtained by extending polyester compound composed of dimer acid and ethylene glycol with isophorone diisocyanate Curing agent: trimethylolpropane Isophorone diisocyanate, xylylene diisocyanate adduct 34) Main ingredient: Polyester diol resin composed of dimer acid and ethylene glycol, 2-methyl-1,3-propanediol and hydrogenated polyester compound composed of dimer acid, ethylene glycol and dimethylolpropionic acid Mixture of polyester urethane diol resin extended with added diphenylmethane diisocyanate Curing agent: View of hexamethylene diisocyanate 35) Main ingredient: Polyester diol resin composed of dimer acid and propylene glycol, neopentyl glycol and terephthalic acid, and polyester urethane diol resin obtained by extending polyester compound composed of dimer acid and ethylene glycol with isophorone diisocyanate Curing agent: Isophorone Triisomer of diisocyanate 36) Main ingredient: dimethyl 2,6-naphthalenedicarboxylate, polyester diol resin composed of dimer acid and 1,4-butanediol, hydrogenated polyester compound composed of dimer acid, ethylene glycol and dimethylolpropionic acid Mixture of polyester urethane diol resin extended with xylylene diisocyanate Curing agent: xylylene diisocyanate adduct of trimethylolpropane

<Example 19> Using the four types of dry laminating adhesives 33) to 36) obtained above,
Using the same materials and operations as in Example 1, a packaging material (5) having a configuration as shown in FIG. 1 was obtained.

<Example 20> The structure shown in FIG. 2 was obtained by using the same materials and operations as in Example 2 except that the four types of dry laminating adhesives 33) to 36) obtained above were used. (5) was obtained.

<Example 21> Using the four types of dry laminating adhesives 33) to 36) obtained above,
A packaging material (5) having a configuration as shown in FIG. 1 was obtained by the same materials and operations as in Example 3.

<Example 22> The same material and operation as in Example 4 were carried out except that the four types of dry laminating adhesives 33) to 36) obtained above were used. A packaging material (5) having the configuration shown was obtained.

<Example 23> The structure shown in FIG. 3 was obtained by using the same materials and operations as in Example 5 except that the four types of dry laminating adhesives 33) to 36) obtained above were used. (5) was obtained.

Example 24 A packaging material (not shown) was prepared in the same manner as in Example 6, except that the four types of dry laminating adhesives 33) to 36) obtained above were used. I got

<Example 25> The structure shown in Fig. 3 was obtained by using the same materials and operations as in Example 7 except that the four types of dry laminating adhesives 33) to 36) obtained above were used. (5) was obtained.

<Example 26> A packaging material (not shown) was prepared in the same manner as in Example 8, except that the four types of dry laminating adhesives 33) to 36) obtained above were used. I got

Comparative Example 19 A polyester obtained by extending a polyester diol resin composed of adipic acid and 1,6-hexanediol and isophthalic acid as main ingredients and a polyester diol resin composed of terephthalic acid and ethylene glycol and neopentyl glycol with xylylene diisocyanate. A material similar to that of Example 17 was obtained by mixing a urethanediol resin, using a silane coupling agent and an epoxy resin, and using a dry laminating adhesive consisting of trimethylolpropane and xylylene diisocyanate as a curing agent. Or by operation
A packaging material (5) having a configuration as shown in FIG. 1 was obtained.

<Comparative Example 20> A packaging material having a structure as shown in the side sectional view of FIG. 2 was manufactured by the same material and operation as in Example 20 except that the adhesive for dry lamination used in Comparative Example 19 was used. 5) was obtained.

<Comparative Example 21> A packaging material (5) having a structure as shown in FIG. 1 was prepared using the same materials and operations as in Example 21 except that the dry laminating adhesive used in Comparative Example 19 was used. Obtained.

<Comparative Example 22> A packaging material (5) having a structure as shown in FIG. 2 was obtained by the same material and operation as in Example 22 except that the adhesive for dry lamination used in Comparative Example 19 was used. Was.

<Comparative Example 23> A packaging material (5) having a structure as shown in FIG. 3 was obtained by the same material and operation as in Example 23 except that the adhesive for dry lamination used in Comparative Example 19 was used. Was.

Comparative Example 24 A packaging material (not shown) was obtained in the same manner as in Example 24 except that the adhesive for dry lamination used in Comparative Example 19 was used.

<Comparative Example 25> A packaging material (5) having a structure as shown in FIG. 3 was obtained by the same material and operation as in Example 25 except that the adhesive for dry lamination used in Comparative Example 19 was used. Was.

<Comparative Example 26> A packaging material (not shown) was obtained in the same manner as in Example 26 except that the dry laminating adhesive used in Comparative Example 19 was used.

<Experimental results> Examples 19, 20, and 2
The laminate (5) obtained in each of Comparative Examples 3 and 24 and Comparative Examples 19, 20, 23, and 24 is used as a second base material (40) serving as a sealant layer.
A package (bag) having an inner surface area of 300 cm 2 with the surface facing the inside, 200 ml of water as a content was sealed and sealed.
A pressure heating treatment was performed at 20 ° C. for 60 minutes. As an evaluation of these packages, they were allowed to cool to room temperature after treatment, and the content of water was concentrated by liquid-liquid extraction or solid phase extraction or freeze-drying with an organic solvent, and then eluted with a gas chromatograph mass spectrometer. The measured low molecular weight substances were measured. The results are shown in Table 6 as Examples and Comparative Examples.

[0132]

[Table 6]

The laminates (5) obtained in Examples 21, 22, 25 and 26 and Comparative Examples 21, 22, 25 and 26
Was made into a package (bag) having an inner surface area of 3200 cm 2 with the surface of the second base material (40) serving as a sealant layer on the inside, and 1000 ml of water as a content was sealed and left at 40 ° C. for 7 days. As an evaluation of these packages, they are allowed to cool to room temperature after storage, and the content of water is concentrated by liquid-liquid extraction or solid phase extraction or freeze-drying with an organic solvent, and then eluted with a gas chromatograph mass spectrometer. The measured low molecular weight substances were measured. Table 7 shows the results as examples and comparative examples.
It was shown to.

[0134]

[Table 7]

From the above Tables 6 and 7, it can be seen that the conventional dry laminating adhesive is different from Examples 19 to 26 using the dry laminating adhesive having the composition of 33) to 36) which is an example of the present invention. In the packages of Comparative Examples 17 to 24 used, the elution of low-molecular-weight substances was all large. Examples 19 and 21 in which an aluminum foil layer (50) was laminated between a first substrate (10, 20) and a second substrate (40).
And Examples 20, 22, 23, and 25 in which a gas barrier layer made of a ceramic vapor-deposited film (30) was laminated, and Examples 24 and 26 in which a normal film was laminated.
The gas barrier layer contributed to the reduction of elution of low molecular weight substances.

[0136]

According to the present invention having the above-described structure, the following effects can be obtained. That is, in an adhesive for dry or non-solvent lamination comprising at least a main agent and a curing agent, the main agent is one or two selected from the group consisting of dimer fatty acids or hydrogenated products thereof, or ester compounds or derivatives thereof. Polyester diol resin or polyester diol formed by reacting fatty acids, and, if necessary, one or two aromatic dicarboxylic acids selected from the group consisting of aromatic dicarboxylic acids and ester compounds and derivatives thereof with glycols A polyester urethane diol resin obtained by extending a resin with one or two diisocyanates, or a resin in which a polyester diol resin and a polyester urethane diol resin are mixed at an appropriate mixing ratio, wherein the curing agent is trimethylol Isocyanates adduct of bread, or consist burette body or trimer of the isocyanates, the glycols, CnH2n (OH) 2 (n = 2~1
0), diethylene glycol, dipropylene glycol, triethylene glycol, 3-aminopropanediol, 1,3-cyclohexanedimethanol, 1,4-
Cyclohexanedimethanol, dimer acid reduced glycol, dimethylolpropionic acid, polyethylene glycol, polypropylene glycol, poly1,2-butylene glycol, and polytetramethylene ether glycol. Further, diisocyanates for extending the polyester diol resin and diisocyanates used for the curing agent include isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane. Diisocyanate.

By selecting each composition and the number thereof (the smaller the number, the smaller the occurrence of by-products can be prevented), the adhesive for dry or non-solvent lamination with less elution of low molecular weight substances It can be.

Therefore, using the adhesive for dry and non-solvent lamination of the present invention, excellent practical effects as applications such as low-elution packages in which the quality of foods, beverages, pharmaceuticals and electronic equipment parts can be guaranteed. Demonstrate.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing an embodiment of a laminated packaging material using an adhesive for dry lamination according to the present invention in a side cross section.

FIG. 2 is an explanatory view showing another embodiment of the laminated packaging material using the adhesive for dry lamination of the present invention in a side cross section.

FIG. 3 is an explanatory view showing, in a side cross section, still another embodiment of the laminated packaging material using the adhesive for dry lamination of the present invention.

FIG. 4 is an explanatory view illustrating an apparatus for producing the laminated packaging material of the present invention.

[Explanation of symbols]

 1a {adhesive layer for dry lamination 5} packaging material 10, 20 {first substrate 40} second substrate 30} ceramic deposited film 30a {substrate film of ceramic deposited film 30b} ceramic Vapor deposition layer 30c sol-gel coat layer 50 aluminum foil layer 60 smoothing roll 62 gravure roll 64 doctor blade 70 pressure roll

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 3E064 BA17 BA27 BA28 BA29 BA30 BA36 BA40 BA55 BB03 BC08 BC18 EA18 HN05 3E086 AA23 AD01 BA04 BA13 BA14 BA15 BB41 BB71 BB74 BB90 CA01 CA11 CA28 CA31 4J040 ED041 EF111 EF111 EF291 EF291 MA09 MA10 NA06 NA08

Claims (14)

[Claims] 1. An adhesive for dry lamination comprising at least a main agent and a curing agent, wherein the main agent comprises one or two kinds selected from dimer fatty acids and ester compounds thereof and one or two kinds of glycols. Dry lamination comprising a polyester resin formed by a reaction, wherein the curing agent comprises one or two selected from diisocyanate adducts of trimethylolpropane, burettes or trimers of the diisocyanates. Adhesive. 2. The method according to claim 1, wherein the main components are one or two selected from dimer fatty acids and their ester compounds, one or two selected from aromatic dicarboxylic acids and their ester compounds, and one or two glycols. 2. The adhesive for dry lamination according to claim 1, wherein the adhesive comprises a polyester resin formed by a reaction with a resin. 3. The glycols are Cn H2n (O
H) 2 (n = 2 to 20), diethylene glycol, dipropylene glycol, triethylene glycol, 3-
Aminopropanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, dimer acid reduced glycol, dimethylolpropionic acid, polyethylene glycol, polypropylene glycol, poly1,2-butylene glycol, polytetra 3. The adhesive for dry lamination according to claim 1, which is methylene ether glycol. 4. The method according to claim 1, wherein said diisocyanates are isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane diisocyanate. The adhesive for dry lamination according to claim 1. 5. An adhesive for dry lamination comprising at least a main agent and a curing agent, wherein the main agent comprises one or two kinds selected from dimer fatty acids and ester compounds thereof and one or two kinds of glycols. A polyester urethane diol resin obtained by extending a polyester diol resin formed by a reaction with one or two kinds of diisocyanates, wherein the curing agent is a diisocyanate adduct of trimethylolpropane, a burette or trimer of the diisocyanate 1 or 2 selected from
An adhesive for dry lamination, comprising a seed. 6. An adhesive for dry or non-solvent lamination comprising at least a main agent and a curing agent, wherein the main agent is selected from the group consisting of dimer fatty acids, hydrogenated products thereof, and ester compounds and derivatives thereof. A polyester urethane diol resin obtained by elongating a polyester diol resin obtained by the reaction of two kinds of fatty acids with one or two kinds of glycols with one or two kinds of diisocyanate, wherein the curing agent is diisocyanate of trimethylolpropane An adhesive for lamination, comprising one or two members selected from the group consisting of adducts, burettes and trimers of the diisocyanates. 7. The glycols may be Cn H2n (O
H) 2 (n = 2 to 20), diethylene glycol, dipropylene glycol, triethylene glycol, 3-
Aminopropanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, dimer acid reduced glycol, dimethylolpropionic acid, polyethylene glycol, polypropylene glycol, poly1,2-butylene glycol, polytetramethylene ether 7. The adhesive for dry lamination according to claim 5, which is a glycol. 8. The method according to claim 5, wherein the diisocyanates are isophorone diisocyanate, xylylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, norbornene diisocyanate, and hydrogenated diphenylmethane diisocyanate. The adhesive for dry lamination according to claim 1. 9. The method according to claim 5, wherein the main component further comprises one or two aromatic dicarboxylic acids selected from the group consisting of aromatic dicarboxylic acids or their ester compounds or derivatives thereof. The adhesive for lamination as described in the above item. 10. The curing agent according to claim 5 or claim 6, wherein a mixture of the polyester diol resin and the polyester urethane diol resin according to claim 5 or 6 at an appropriate mixing ratio is used as a main ingredient. The adhesive for dry lamination according to any one of claims 5 to 9, wherein an adhesive is used. 11. Using the laminating adhesive according to any one of claims 1 to 10, laminating at least two or more selected from paper, plastic film, various vapor-deposited films, aluminum foil and the like. A laminated packaging material characterized by being laminated by stacking. 12. A laminated packaging material obtained by laminating and laminating a barrier layer composed of a plastic film or a metal foil on which a metal or a metal compound is vapor-deposited. .5m
Fill with 1 / cm2 or more of water and seal, 80-140 ° C
The laminated packaging material according to claim 11, wherein the substance eluted into water when subjected to the heat treatment for 10 to 120 minutes is 2.0 µg / ml or less. 13. A laminated packaging material obtained by laminating and laminating a barrier layer made of a plastic film or a metal foil on which a metal or a metal compound is vapor-deposited. .5m
The laminated packaging according to claim 11, wherein the substance eluted in the water is 0.5 µg / ml or less when filled with water of 1 / cm2 or more, sealed, and subjected to a heat treatment at 40 to 80 ° C for 30 to 120 minutes. material. 14. A laminated packaging material according to any one of claims 11 to 13, wherein the laminated packaging material is prepared as a material for forming a low-elution package for packaging foods, beverages, pharmaceuticals, electronic device parts and the like. A packaging bag characterized by: