WO2020246241A1 - Reactive adhesive agent, laminated film, and packaging body - Google Patents

Abstract

Provided are a reactive adhesive agent, a laminated film using the same, and a packaging body, the reactive adhesive agent containing a polyol composition (A) and a polyisocyanate composition (B), wherein: the polyol composition (A) contains a polyester polyol (A1) that is a reaction product obtained by collectively charging polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid, and/or a polyester polyurethane (A2) that is a reaction product of the polyester polyol (A1) and an isocyanate compound; and the content of metal elements derived from the polyethylene terephthalate is less than 50 ppm.

Description

Reactive adhesives, laminated films, and packaging

The present invention relates to a reactive adhesive, a laminated film and a package made by using the reactive adhesive.

Conventionally, various plastic films have been laminated together, and a laminate obtained by laminating (laminating) a plastic film and a metal vaporized film or a metal foil has been used for various purposes such as packaging materials for foods, pharmaceuticals, daily necessities, and barriers. Decorations used for outdoor industrial applications such as materials, roofing materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automobile parts, signs, stickers, injection molding simultaneous decoration methods, etc. It is used for various purposes.
For these laminates, various plastic films, metal-deposited films, or metal foils are appropriately combined according to the required characteristics for each application, and an adhesive corresponding to the required characteristics is selected. For example, in the case of foods and daily necessities, in order to protect the contents from various distribution, storage such as refrigeration, heat sterilization, etc., functions such as strength, crack resistance, retort resistance, heat resistance, and content resistance Is required. Alternatively, in outdoor industrial applications, weather resistance and hydrolysis resistance are required to maintain adhesiveness for a long period of time even in an open-air environment.
Furthermore, these laminates are rarely distributed in the form of sheets, for example, they may be in the form of bags with heat-sealed edges, or may be molded by thermoforming, and heat-sealing and molding processability are required. It may be done.

As an adhesive used for such a laminate, there is a reactive adhesive (also referred to as a two-component adhesive) that reacts a hydroxyl group with an isocyanate. For example, a reaction of a polyester polyol made from polyethylene terephthalate as a raw material and an isocyanate is reacted. Sexual adhesives are known (see, for example, Patent Documents 1 and 2). For example, Patent Document 1 describes reactivity containing a polyester polyol obtained by decomposing polyethylene terephthalate by a reaction with a low molecular weight polyol and then condensing this decomposition product with a polybasic acid, and a polyisocyanate curing agent. Adhesives are disclosed. Further, Patent Document 2 discloses that a polyol compound obtained by depolymerizing polyester (a) with a polyol (b) having two or more hydroxyl groups in one molecule is used as a raw material for an adhesive. ..

Polyethylene terephthalate (hereinafter sometimes referred to as PET) used as a raw material here is a raw material for PET bottles (sometimes referred to as PET bottles), and a recycling method has now been established. Currently available PETs include PETs (sometimes called virgin PETs) immediately after the chemical reaction of terephthalic acid and ethylene glycol, commercially available unused PET bottles, PET films, and other PET products. There are various types such as crushed leftovers from manufacturing and recycled PET collected from waste and washed. However, depending on the PET used, there is a problem that the storage stability of the obtained adhesive is lowered.

JP-A-2002-3815 JP-A-2010-248345

An object to be solved by the present invention is to provide a reactive adhesive between a polyester polyol made of polyethylene terephthalate having excellent storage stability and an isocyanate.

When the present inventors focused on the metal elements contained in PET, they found that the storage stability was lowered when PET containing a large amount of metal elements was used as a raw material, and as a result of diligent studies, polyethylene terephthalate was used. It has been found that in a reactive adhesive using a polyester polyol as a raw material, a reactive adhesive having a metal element content in a specific range solves the above-mentioned problems.

That is, the present invention is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) is polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid. A metal derived from polyethylene terephthalate, which contains a polyester polyol (A1), which is a reaction product of the batch preparation with, and / or a polyester polyurethane polyol (A2), which is a reaction product of a polyester polyol (A1) and an isocyanate compound. Provided is a reactive adhesive having an element content of less than 50 ppm.

Further, the present invention is a laminated film formed by laminating an adhesive layer between a first plastic film and a second plastic film, wherein the adhesive layer is the reaction according to any one of claims 1 to 4. Provided is a laminated film which is a layer of a sex adhesive.

The present invention also provides a package obtained by molding the above-mentioned laminated film into a bag shape.

The reactive adhesive of the present invention has excellent storage stability because the amount of metal elements is below a specific range.

The present invention is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) contains polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid. Containing polyester polyol (A1) and / or polyester polyurethane polyol (A2), which is a reaction product of a polyester polyol (A1) and an isocyanate compound, which is a reaction product of the batch preparation of
The content of the metal element derived from polyethylene terephthalate is less than 50 ppm.

(Metallic element)
Specifically, the metal elements in the present invention include silver (Ag), aluminum (Al), barium (Ba), calcium (Ca), cadmium (Cd), cobalt (Co), chromium (Cr), and copper ( Cu), iron (Fe), gallium (Ga), indium (In), potassium (K), lithium (Li), magnesium (Mg), manganese (Mn), sodium (Na), nickel (Ni), lead ( Pb), strontium (Sr), titanium (Ti), tallium (Tl), zinc (Zn). The element symbols are shown in parentheses.

Specifically, the content of metal elements in the present invention is calculated from the total value (ppm) of metal elements in PET measured by the following method and the amount of PET charged.

<Measurement method>
ICP-OES (or ICP-AES) measurement was performed by microwave decomposition pretreatment. The decomposition conditions were followed by taking a general resin analysis application by the manufacturer as an example.

<Calculation method of the content of metal elements in the polyol composition (A)>
Calculated by equation (1) when the content of metal elements contained in PET is M ₁ ppm, the total amount of raw materials charged during the synthesis of the polyol composition (A) is M ₂ g, and the amount of PET charged is M ₃ g. did.

The content of the metal element derived from polyethylene terephthalate in the present invention is preferably less than 50 ppm, more preferably less than 30 ppm, and most preferably less than 20 ppm with respect to the solid content of the polyol composition (A). preferable.
Further, the content of the metal element in polyethylene terephthalate in the present invention is preferably less than 100 ppm, and most preferably less than 50 ppm.

The reason why the storage stability of the reactive adhesive of the present invention is stabilized by setting the content of the metal element derived from the PET pellet to less than 50 ppm with respect to the solid content of the polyol composition (A) is not clear. In some cases, compounds containing metal elements and metal ions may act as reaction catalysts, which react with hydroxyl groups, carbonyl groups, isocyanate groups, moisture, etc. in reactive adhesives during synthesis or storage. It is presumed that it may unintentionally increase the reactivity of sexual groups and protons and cause thickening of the reactive adhesive.

(Polyform composition (A))
The polyester polyol (A1) contained in the polyol composition (A) used in the present invention is a reaction product obtained by collectively charging polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid.

(Polyester polyol (A1))
The polyethylene terephthalate (hereinafter sometimes referred to as PET) used in the present invention can be obtained by polycondensation of terephthalic acid or dimethyl terephthalate and ethylene glycol, and if necessary, isophthalic acid, phthalic anhydride, adipic acid, etc. Those modified with substances such as cyclohexanedicarboxylic acid, 1,3-butanediol, and cyclohexanedimethanol can also be used. Further, commercially available unused PET bottles, PET films, other crushed leftovers from the production of PET products, recycled PET collected from waste and washed, and the like can be used. These are available in the market as washed and pelletized. Above all, it is preferable to use virgin PET, preforms before PET bottle molding, unused PET bottles, PET films, and other crushed leftovers from the production of PET products.

The intrinsic viscosity (IV) of PET is preferably 0.50-0.80 dL / g. Within this range, the polycondensation reaction between PET and other raw materials can be carried out at 250 ° C. or lower. Further, this range is also preferable from the viewpoint of developing the adhesive strength, durability and heat resistance of the reactive adhesive containing the PET-containing polyester polyol.

The polyhydric alcohol used in the present invention is not particularly limited, and known polyhydric alcohols can be used.
For example, 1,2-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,3-butanediol, 2, Aliphatic diols such as 2,4-trimethyl-1,3-pentanediol; 1,3-bis (2-hydroxypropyl) cyclopentane, 1,3-bis (2-hydroxybutyl) cyclopentane, 1,4- Aliphatic diols such as bis (2-hydroxypropyl) cyclohexane and 1,4-bis (2-hydroxybutyl) cyclohexane; 1,4-bis (2-hydroxypropyl) benzene, 1,4-bis (2-hydroxy) Aromatic diols such as butyl) benzene;

2,2-Bis (4-hydroxyphenyl) propane (hereinafter abbreviated as "bisphenol A"), 2,2-bis (4-hydroxyphenyl) butane (hereinafter abbreviated as "bisphenol B"), bis (4- 1,2-propylene oxide and 1,2-butylene are added to bisphenols such as hydroxyphenyl) methane (hereinafter abbreviated as "bisphenol F") and bis (4-hydroxyphenyl) sulfone (hereinafter abbreviated as "bisphenol S"). An alkylene oxide adduct of bisphenol obtained by adding an alkylene oxide having a secondary hydroxyl group such as an oxide; ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,3 -Butandiol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, trimethylol Aliphatic polyols such as ethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol; ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol;

Modifications obtained by ring-opening polymerization of the aliphatic polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Polyether polyol; lactone-based polyester polyol obtained by polycondensation reaction of the aliphatic polyol with various lactones such as ε-caprolactone; bisphenol such as bisphenol A, bisphenol F, bisphenol S; bisphenol A, bisphenol F, etc. Examples thereof include an ethylene oxide adduct of bisphenol obtained by adding ethylene oxide to bisphenol.

Each of these may be used alone, or two or more types may be used in combination. Among them, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neo Aliphatic polyols such as pentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, trimethylolpropane, glycerin, hexanetriol and pentaerythritol are preferred. 6-Hexanediol is preferred.

The polybasic acid used in the present invention is not particularly limited, and a known polybasic acid can be used.
For example, aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexahydro. Aliphatic dicarboxylic acids such as phthalic acid and 1,4-cyclohexanedicarboxylic acid; maleic acid, maleic anhydride, citraconic acid, dimethylmaleic acid, cyclopentene-1,2-dicarboxylic acid, 1-cyclohexene-1,2- An aliphatic unsaturated dicarboxylic acid such as dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, fumaric acid, mesaconic acid, itaconic acid, glutaconic acid; 1,2,5-hexanetricarboxylic acid, 1,2, Examples thereof include aliphatic tricarboxylic acids such as 4-cyclohexanetricarboxylic acid; aromatic tricarboxylic acids such as trimellitic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and dimeric acid. Each of these may be used alone, or two or more types may be used in combination. Of these, dimer acid is preferable.

The production method in which PET, the polyhydric alcohol, and the polybasic acid are collectively charged and reacted can be arbitrarily produced by a known polycondensation reaction method. Specifically, PET, the polyhydric alcohol, and the polybasic acid are produced. The acid and the acid are put into a production apparatus, and the temperature is raised to 180 ° C. or higher while stirring in a nitrogen atmosphere. It may be carried out at. When the PET, polyhydric alcohol and polybasic acid described in the present application are used, the vacuum dehydration reaction can be applied at a reaction temperature of 230 ° C. or lower, and the reaction time can be set to about 5 hours. The progress of the polycondensation reaction can be confirmed by measuring the acid value, hydroxyl value, viscosity or softening point. As the manufacturing apparatus used at this time, for example, a batch type manufacturing apparatus such as a reaction vessel equipped with a nitrogen inlet, a thermometer, a stirrer, a rectification tower, etc. can be preferably used, and a degassing port is provided. An extruder, a continuous reactor, a kneader, etc. can also be used. Further, if necessary, an esterification catalyst (tin compound, titanium compound, zirconium compound, etc.) can be used to promote the esterification reaction.
The polyol obtained by the method of transesterifying PET in a polyhydric alcohol and the method of polycondensing the ester exchange reaction product with polybasic acid is adhered to the polyol because the ethylene terephthalate unit is decomposed into pieces. Even if it is used as an agent, the appearance, adhesive strength, heat resistance and content resistance at the time of high-speed coating, which are the objects of the present application, cannot be achieved.

(Preferable combination of raw materials)
As the polyester polyol (A1), a polyester polyol using 1,6-hexanediol as the polyhydric alcohol and dimer acid as the polybasic acid is preferable. At this time, the weight fraction of 1,6-hexanediol is preferably 5 to 20% by mass, and more preferably 6 to 18% by mass, as a ratio of the polyester polyol (A1) to the charged raw material. preferable. The weight fraction of the dimer acid is preferably 5 to 20% by mass, more preferably 6 to 18% by mass, as a ratio of the polyester polyol (A1) to the charged raw material.

Further, in the PET, the ratio of the polyester polyol (A1) to the charged raw material, that is, the total amount of the polyhydric alcohol and the polybasic acid is 5 to 50% by mass with respect to 100% of the total amount of the polyhydric alcohol and the polybasic acid. Is preferable, and more preferably 8 to 48% by mass.

In the present application, as a raw material for a polyester polyol (A1), a long-chain unsaturated dibasic acid such as dimer acid, 1,6-hexanediol and another monomer are synthesized together with PET to provide adhesive strength to a substrate. It is possible to obtain an adhesive having better heat resistance and content resistance. Although the reason for this is not clear, this composition makes it possible to carry out the reaction temperature at 220 ° C., which makes it difficult for the ethylene terephthalate unit in the obtained reaction product to be decomposed by the long-chain unsaturated group. It is presumed that the molecular weight remains as it is, which contributes to the appearance, adhesive strength, heat resistance and content resistance during high-speed coating. With trihydric alcohol (trimethylolpropane) as the polyhydric alcohol, the ethylene terephthalate unit in PET may be sufficiently decomposed, and the reaction temperature must be higher than 220 ° C. Therefore, it is preferable that the polyhydric alcohol is a dihydric alcohol such as 1,6-hexanediol.

(Acid value, hydroxyl value)
The polyester polyol (A1) preferably has an acid value of 5.0 or less from the viewpoint of hydrolysis resistance, and more preferably 3.0 or less from the viewpoint of adhesive reactivity. Further, from the viewpoint of high-speed coatability, the hydroxyl value is preferably 50 or less, more preferably 40 or less.
In the present invention, the acid value and the hydroxyl value are measured by the following methods and show values converted into solid content unless otherwise specified.

(Acid value)
Weigh 5 to 10 g of polyester polyol in a 100 ml Erlenmeyer flask. Let the weighed amount be (S). This is dissolved in 30 ml of tetrahydrofuran. After adding 2 to 3 drops of phenolphthalein as an indicator to this, titration is performed with a 0.1 mol / L potassium hydroxide alcohol solution. The acid value is calculated by the following formula from the titration amount (V) at that time, with the point showing a slight crimson color lasting for 30 seconds as the end point. The titer of the 0.1 mol / L potassium hydroxide alcohol solution is (F).
Acid value = (V x F x 5.61) / S

(Hydroxy group value)
Weigh 6-10 g of polyester polyol in a 300 ml Erlenmeyer flask. Let the weighed amount be (S). To this, 25 ml of a pre-prepared acetylating agent is added and dissolved. A cooling tube is attached to the mouth of the Erlenmeyer flask, and the acetylation reaction is carried out at 100 ° C. for 1 hour. Add 10 ml of ion-exchanged water and cool to room temperature. After adding 2 to 3 drops of phenolphthalein as an indicator to this, titration is performed with a 0.5 mol / L potassium hydroxide alcohol solution. The hydroxyl value is calculated by the following formula from the titration amount (V) at that time, with the point showing a slight crimson color lasting for 30 seconds as the end point. At the same time, a blank test is performed, and the titration amount at that time is defined as (B). Let (F) be the titer of the 0.5 mol / L potassium hydroxide alcohol solution. Separately, the acid value is measured.
Hydroxy group value = ((BV) x F x 28.05) / S + acid value

(Molecular weight)
The number average molecular weight of the polyester polyol (A1) is not particularly limited, but is usually preferably adjusted in the range of 2000 to 12000, more preferably 3000 to 8000, from the viewpoint of appropriate resin viscosity at the time of coating. ..

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8220GPC manufactured by Tosoh Corporation
Column; TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran Tetrahydrofuran flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

(Polyester polyurethane polyol (A2))
The polyester polyol (A1) is a polyester polyurethane polyol (A2) in which polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid are collectively charged and reacted, and then further reacted with an isocyanate compound described later. May be good. At this time, the isocyanate compound is preferably isophorone diisocyanate.

The polyester polyurethane polyol (A2) preferably has an acid value of 5.0 or less from the viewpoint of hydrolysis resistance, and more preferably 3.0 or less from the viewpoint of adhesive reactivity. Further, from the viewpoint of heat resistance and physical property resistance, the hydroxyl value is preferably 30 or less, more preferably 25 or less.

(Other polyols)
In the present invention, in addition to the polyester polyol (A1), the polyhydric alcohol itself and polyester polyols, polyether polyols, polyurethane polyols, and polyethers that do not use polyethylene terephthalate as a raw material are used as long as the effects of the present invention are not impaired. A polymer polyol selected from ester polyols, polyester (polyester) polyols, polyether (polyester) polyols, polyesteramide polyols, acrylic polyols, polycarbonate polyols, polyhydroxylalkanes, castor oil or a mixture thereof may be used in combination.

When other polyols are used in combination, the proportion of the polyester polyol (A1) in the polyol composition (A) is preferably 1 to 50% by mass, and more preferably 1 to 40% by mass.

(Polyisocyanate composition (B))
The polyisocyanate composition (B) used in the present invention is a composition containing a polyisocyanate compound as a main component. As the polyisocyanate compound used in the present invention, known ones can be used without particular limitation, and they can be used alone or in combination of two or more. For example, polyisocyanates having an aromatic structure in the molecular structure such as tolylene diisocyanate, diphenylmethane diisocyanate, polyether diphenylmethane diisocyanate, 1,5-naphthalenediocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, and NCO groups of these polyisocyanates. Partially modified with carbodiimide;

Alphanate compounds derived from these polyisocyanates; polyisocyanates having an alicyclic structure within the molecular structure of isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,3- (isocyanatomethyl) cyclohexane, etc.; Linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate, and alphanate compounds thereof; isocyanurates of these polyisocyanates; allophanates derived from these polyisocyanates; Bullet form derived from these polyisocyanates; Trimethylol propane-modified adduct form;

Examples thereof include polyisocyanate which is a reaction product of the above-mentioned various polyisocyanate compounds and a polyhydric alcohol.

In the polyisocyanate which is a reaction product of the various polyisocyanate compounds and the polyhydric alcohol, the polyhydric alcohol is a polyhydric alcohol which is a raw material of the polyol composition (A), the polyester polyol (A1), and the like. Polyester polyol (A1-2), polyester polyol not using polyethylene terephthalate as a raw material, polyether polyol, polyurethane polyol, polyether ester polyol, polyester (polyester) polyol, polyether (polyester) polyol, polyesteramide polyol, acrylic polyol , Polyester polyols, polyhydroxyl alkanes, castor oil or polymer polyols selected from mixtures thereof and the like can be used. Above all, it is preferable to use polyisocyanate, which is a reaction product of the various polyisocyanates described above and the polyester polyol (A1), from the viewpoint of adhesive strength, heat resistance and content resistance.
The reaction ratio between the polyisocyanate compound and the polyhydric alcohol is such that the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group to the hydroxyl group is in the range of 1.0 to 5.0, and the adhesive coating film aggregates. It is preferable from the viewpoint of the balance between force and flexibility.

The polyisocyanate compound preferably has an average molecular weight in the range of 100 to 1000 from the viewpoint of adhesive strength, heat resistance and content resistance.

(solvent)
The reactive adhesive used in the present invention is an adhesive that cures by a chemical reaction between an isocyanate group and a hydroxyl group, and can be used as a solvent-type or solvent-free type adhesive. The "solvent" of the solvent-free adhesive in the present invention refers to a highly soluble organic solvent capable of dissolving the polyisocyanate compound or polyol compound used in the present invention, and is "solvent-free". Means that it does not contain these highly soluble organic solvents. Specific examples of the highly soluble organic solvent include toluene, xylene, methylene chloride, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, and the like. Examples thereof include toluol, xylene, n-hexane and cyclohexane. Among them, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate and ethyl acetate are known as highly soluble organic solvents.
On the other hand, the adhesive of the present invention may be appropriately diluted with the highly soluble organic solvent according to the desired viscosity when there is a demand for low viscosity or the like. In that case, either one of the polyisocyanate composition (B) or the polyol composition (A) may be diluted, or both may be diluted. Examples of the organic solvent used in such a case include methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, cyclohexane and the like. Can be mentioned. Among these, ethyl acetate and methyl ethyl ketone (MEK) are preferable from the viewpoint of solubility, and ethyl acetate is particularly preferable. The amount of the organic solvent used depends on the required viscosity, but is often in the range of approximately 20 to 50% by mass.

In the reactive adhesive used in the present invention, the blending ratio of the polyisocyanate composition (B) and the polyol composition (A) is in the polyisocyanate compound contained in the polyisocyanate composition (B). The equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group to the hydroxyl group in the polyol compound contained in the polyol composition (A) is in the range of 0.6 to 5.0 for adhesive strength and heat sealing. It is preferable from the viewpoint of excellent heat resistance at the time, and particularly preferably in the range of 1.0 to 3.5 from the viewpoint that these performances become remarkable.

(Aliphatic cyclic amide compound)
As described in detail, the reactive adhesive of the present invention contains the polyol composition (A) and the polyisocyanate composition (B) as essential components, and further comprises an aliphatic cyclic amide compound. By mixing with either one of the polyol composition (A) and the polyisocyanate composition (B), or by blending as a third component at the time of coating, an aromatic amine is formed in the laminated package. Elution of typified harmful low molecular weight chemical substances into the contents can be effectively suppressed.

Examples of the aliphatic cyclic amide compound used here include δ-valerolactam, ε-caprolactam, ω-enantol lactam, η-caprilactam, β-propiolactam and the like. Among these, ε-caprolactam is preferable because it is excellent in the effect of reducing the elution amount of low molecular weight chemical substances. The blending amount thereof is preferably in the range of 0.1 to 5 parts by mass of the aliphatic cyclic amide compound per 100 parts by mass of the polyol component A.

(catalyst)
In the present invention, by using a catalyst, elution of harmful low molecular weight chemical substances such as aromatic amines into the contents can be effectively suppressed in the laminated package.
The catalyst used in the present invention is not particularly limited as long as it is for promoting the urethanization reaction, and for example, a metal catalyst, an amine catalyst, diazabicycloundecene (DBU), and an aliphatic cyclic amide compound. , A catalyst such as a titanium chelate complex can be used.

Examples of the metal-based catalyst include a metal complex system, an inorganic metal system, and an organic metal system. Specific examples of the metal complex system include Fe (iron), Mn (manganese), Cu (copper), and Zr (zirconium). ), Th (thorium), Ti (titanium), Al (aluminum), Sn (tin), Zn (zinc), Bi (bismus) and Co (cobalt), which is a metal acetylacetonate salt selected from the group. For example, iron acetylacetoneate, manganese acetylacetoneate, copper acetylacetoneate, zirconia acetylacetonate and the like can be mentioned. Among these, iron acetylacetoneate (Fe (acac) ₃ ) is used in terms of toxicity and catalytic activity. ) Or manganese acetylacetoneate (Mn (acac) ₂ ) is preferable.

Examples of the inorganic metal catalyst include catalysts selected from Fe, Mn, Cu, Zr, Th, Ti, Al, Sn, Zn, Bi, Co and the like.

Organic metal catalysts include stanus diacetate, stanus dioctate, stanus dilaurate, stanus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, etc. Examples thereof include nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, and bismuth neodecanoate. Of these, preferred compounds are organotin catalysts, more preferably stanas dioctate and dibutyl tin dilaurate.

The tertiary amine catalyst is not particularly limited as long as it is a compound having the above structure, and examples thereof include triethylenediamine, 2-methyltriethylenediamine, quinuclidine, and 2-methylquinuclidine. Among these, triethylenediamine and 2-methyltriethylenediamine are preferable because they have excellent catalytic activity and are industrially available.

Other tertiary amine catalysts include N, N, N', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N', N ", N. "-Pentamethyldiethylenetriamine, N, N, N', N", N "-Pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N', N", N "-Pentamethyldipropylenetriamine, N, N, N', N'-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N'-(2-hydroxy) Ethyl) ethylenediamine, N, N-dimethyl-N'-(2-hydroxyethyl) propanediamine, bis (dimethylaminopropyl) amine, bis (dimethylaminopropyl) isopropanolamine, 3-quinuclidinol, N, N, N', N'-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, N-methyl-N '-(2-Dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholin, N-ethylmorpholin, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2 -Methyl imidazole, 1-dimethylaminopropyl imidazole, N, N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) imidazole, 1- (2-hydroxy) Examples thereof include propyl) imidazole, 1- (2-hydroxyethyl) -2-methylimidazole, 1- (2-hydroxypropyl) -2-methylimidazole and the like.

Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enantol lactam, η-caprilactam, β-propiolactam and the like. Among these, ε-caprolactam is more effective in promoting curing.

The titanium chelate complex is a compound whose catalytic activity is enhanced by irradiation with ultraviolet rays, and a titanium chelate complex having an aliphatic or aromatic diketone as a ligand is preferable from the viewpoint of excellent curing promoting effect. Further, in the present invention, a ligand having an alcohol having 2 to 10 carbon atoms in addition to the aromatic or aliphatic diketone is preferable because the effect of the present invention becomes more remarkable.
In the present invention, the catalyst may be used alone or in combination.

..
The mass ratio of the catalyst is preferably in the range of 0.001 to 80 parts, preferably in the range of 0.01 to 70 parts, assuming that the mixed solution of the polyisocyanate composition (B) and the polyol composition (A) is 100 parts. More preferred.

The reactive adhesive of the present invention may be used in combination with a pigment, if necessary. In this case, the pigments that can be used are not particularly limited, and for example, the extender pigments, white pigments, black pigments, gray pigments, and red pigments described in the 1970 edition of the Paint Raw Material Handbook (edited by the Japan Paint Industry Association). Examples thereof include organic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments and pearl pigments, inorganic pigments, and plastic pigments. Various specific examples of these colorants are listed, and examples of organic pigments include various insoluble azo pigments such as Bentzin Yellow, Hansa Yellow, and Lake 4R; and solubility of Lake C, Carmine 6B, Bordeaux 10, and the like. Azo pigments; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorinated dyeing lakes such as rhodamine lake and methyl violet lake; various medium dye dye pigments such as quinoline lake and fast sky blue; anthracinone Various building dye dyes such as system pigments, thioindigo pigments, perinone pigments; various quinacridone pigments such as Cincasia Red B; various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as chromoftal Pigments; aniline black and the like.

Inorganic pigments include, for example, various chromates such as yellow lead, zinc chromate, molybdate orange, etc .; various ferrussian compounds such as navy blue; titanium oxide, zinc flower, mapicoero, iron oxide, red iron oxide, chrome oxide. Various metal oxides such as green and zirconium oxide; various sulfides or seleniums such as cadmium ero, cadmium red and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue Sirates; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder. Pigments; flake pigments of these metals; mica flake pigments; mica flake pigments coated with metal oxides, metallic pigments such as mica-like iron oxide pigments and pearl pigments; graphite, carbon black and the like.

Examples of extender pigments include precipitated barium sulfate, powder, precipitated calcium carbonate, calcium bicarbonate, bentonite, alumina white, silica, hydrous fine powder silica (white carbon), ultrafine powder anhydrous silica (aerosil), and silica sand (silica). Sand), talc, precipitated magnesium carbonate, bentonite, clay, silica, ocher and the like.

Further, examples of the plastic pigment include "Grandol PP-1000" and "PP-2000S" manufactured by DIC Corporation.

As the pigment used in the present invention, titanium oxide as a white pigment, an inorganic oxide such as zinc oxide, and carbon black as a black pigment are more preferable because they are excellent in durability, weather resistance, and design.

The mass ratio of the pigment used in the present invention is 1 to 400 parts by mass, particularly 10 to 300 parts by mass with respect to 100 parts by mass of the total of the isocyanate component B and the polyol component A, such as adhesiveness and blocking resistance. It is more preferable because it is excellent in.

(Adhesion promoter)
In addition, an adhesion accelerator can be used in combination with the reactive adhesive used in the present invention. Examples of the adhesion accelerator include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and epoxy resins.

Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) -γ. Aminosilanes such as -aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-gly Epoxysilanes such as sidoxylpropyltriethoxysilane; vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-mercapto Propyltrimethoxysilane and the like can be mentioned.

Examples of the titanate-based coupling agent include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxy. Titanium and the like can be mentioned.

Further, as the aluminum-based coupling agent, for example, acetalkoxyaluminum diisopropylate and the like can be mentioned.

Examples of epoxy resins include commercially available EPIS type, Novorak type, β-methylepicro type, cyclic oxylane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, and many. Various epoxy resins such as valent carboxylic acid ester type, aminoglycidyl type, resorcin type, triglycidyltris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylic glycidyl Compounds such as ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butyl phenyl glycidyl ether, adipate diglycidyl ester, o-phthalic acid diglycidyl ester, glycidyl methacrylate, butyl glycidyl ether, etc. Can be mentioned.

(Other additives)
If necessary, the reactive adhesive used in the present invention may contain other additives other than the above. Examples of the additive include a leveling agent, inorganic fine particles such as colloidal silica and alumina sol, polymethylmethacrylate-based organic fine particles, antifoaming agent, anti-sagging agent, wet dispersant, viscosity modifier, ultraviolet absorber, and metal. Inactivating agents, peroxide decomposing agents, flame retardants, reinforcing agents, plasticizers, lubricants, rust preventives, fluorescent whitening agents, inorganic heat ray absorbers, flameproofing agents, antistatic agents, dehydrating agents, Known and commonly used thermoplastic elastomers, antistatic agents, phosphoric acid compounds, melamine resins, or reactive elastomers can be used. The content of these additives can be appropriately adjusted and used within a range that does not impair the function of the reactive adhesive used in the present invention.

These adhesion promoters and additives may be mixed with either the component of the polyisocyanate composition (B) or the polyol composition (A), or may be blended and used as a third component at the time of application. it can. Usually, a premix in which components other than the polyisocyanate composition (B) are mixed in advance with the polyol composition (A) is prepared, and the premix and the polyisocyanate composition (B) are mixed immediately before construction. Mix and prepare.

(Laminate)
The laminate of the present invention can be obtained, for example, by laminating a plurality of films or papers by a dry laminating method or a non-solvent laminating method using the adhesive of the present invention.
The film to be used is not particularly limited, and a film suitable for the intended use can be appropriately selected. For example, for food packaging, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE: high density polyethylene film) and polypropylene film (CPP: unstretched). Polypropylene film, OPP: biaxially stretched polypropylene film) and other polyolefin films, polyvinyl alcohol films, ethylene-vinyl alcohol copolymer films and the like can be mentioned.

The film may be stretched. As a stretching treatment method, the resin is melt-extruded by an extrusion film forming method or the like to form a sheet, and then simultaneous biaxial stretching or sequential biaxial stretching is performed. Further, in the case of sequential biaxial stretching, it is common to first perform longitudinal stretching treatment and then lateral stretching. Specifically, a method of combining longitudinal stretching using the speed difference between rolls and transverse stretching using a tenter is often used.

Alternatively, a film in which a metal oxide such as aluminum or a metal oxide such as silica or alumina is laminated, or a barrier film containing a gas barrier layer such as polyvinyl alcohol, an ethylene / vinyl alcohol copolymer, or vinylidene chloride is used in combination. May be good. By using such a film, it is possible to obtain a laminated body having a barrier property against water vapor, oxygen, alcohol, an inert gas, a volatile organic compound (fragrance) and the like.

If necessary, various surface treatments such as flame treatment and corona discharge treatment may be applied to the surface of the film so that an adhesive layer without defects such as film breakage and repelling is formed.

Alternatively, the laminate of the present invention is obtained by applying the adhesive of the present invention as an adhesive (anchor coating agent) to a film with a laminator, performing a curing reaction, and then laminating a polymer material melted by an extruder. Can be obtained (extruded lamination method). As the film, the same film as that used in the above-mentioned dry laminating method and non-solvent laminating method can be used. As the polymer material to be melted, a polyolefin resin such as a low density polyethylene resin, a linear low density polyethylene resin, or an ethylene-vinyl acetate copolymer resin is preferable.

As a more specific structure of the laminated body,
(1) Base film 1 / Adhesive layer 1 / Sealant film (2) Base film 1 / Adhesive layer 1 / Metal vapor deposition unstretched film (3) Base film 1 / Adhesive layer 1 / Metal vapor deposition stretched film (4) Transparent vapor-deposited stretched film / adhesive layer 1 / sealant film (5) Base film 1 / adhesive layer 1 / base film 2 / adhesive layer 2 / sealant film (6) Base film 1 / adhesive layer 1 / metal vapor-deposited stretched film / Adhesive layer 2 / Sealant film (7) Base film 1 / Adhesive layer 1 / Transparent vapor-deposited stretched film / Adhesive layer 2 / Sealant film (8) Base film 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Sealant Film (9) Base film 1 / Adhesive layer 1 / Base film 2 / Adhesive layer 2 / Metal layer / Adhesive layer 3 / Sealant film (10) Base film 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Examples thereof include, but are not limited to, a base film 2 / an adhesive layer 3 / a sealant film.

Examples of the base film 1 used in the configuration (1) include an OPP film, a PET film, and a nylon film. Further, as the base film 1, a film having a gas barrier property and a coating for improving ink acceptability when providing a printing layer described later may be used. Examples of commercially available products of the coated base film 1 include K-OPP film and K-PET film. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealant film include a CPP film and an LLDPE film. A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side (when a coated base film 1 is used, the surface of the coating layer on the adhesive layer 1 side). The printing layer is formed by various printing inks such as gravure ink, flexo ink, offset ink, stencil ink, and inkjet ink by a general printing method conventionally used for printing on a polymer film.

Examples of the base film 1 used in the configurations (2) and (3) include an OPP film and a PET film. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. As the metal-deposited unstretched film, a VM-CPP film obtained by subjecting a metal vapor deposition such as aluminum to a CPP film is used, and as a metal vapor deposition stretched film, a VM-OPP film obtained by subjecting an OPP film to a metal vapor deposition such as aluminum is used. Can be done. A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as in the configuration (1).

Examples of the transparent vapor-deposited stretched film used in the configuration (4) include a film obtained by subjecting silica or alumina vapor deposition to an OPP film, PET film, nylon film or the like. A film coated on the vapor-deposited layer may be used for the purpose of protecting the inorganic vapor-deposited layer of silica or alumina. The adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those in the configuration (1). A printing layer may be provided on the surface of the transparent vapor-deposited stretched film on the adhesive layer 1 side (in the case of using a coating on the inorganic thin-film film, the surface on the adhesive layer 1 side of the coating layer). The method of forming the print layer is the same as that of the configuration (1).

Examples of the base film 1 used in the configuration (5) include a PET film and the like. Examples of the base film 2 include a nylon film and the like. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those in the configuration (1). A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as in the configuration (1).

Examples of the base film 1 of the configuration (6) include those similar to the configurations (2) and (3). Examples of the metal-deposited stretched film include a VM-OPP film and a VM-PET film in which an OPP film or a PET film is vapor-deposited with a metal such as aluminum. At least one of the adhesive layer 1 and the adhesive layer 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those in the configuration (1). A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as in the configuration (1).

Examples of the base film 1 of the configuration (7) include a PET film and the like. Examples of the transparent vapor-deposited stretched film include those having the same structure as (4). At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those in the configuration (1). A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as in the configuration (1).

Examples of the base film 1 of the configuration (8) include a PET film and the like. Examples of the metal layer include aluminum foil. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those in the configuration (1). A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as in the configuration (1).

Examples of the base film 1 of the configurations (9) and (10) include a PET film and the like. Examples of the base film 2 include a nylon film and the like. Examples of the metal layer include aluminum foil. At least one layer of the adhesive layers 1, 2, and 3 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those in the configuration (1). A printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side in the same manner as in the configuration (1).

When the laminate of the present invention contains at least one of a metal vapor-deposited film, a transparent vapor-deposited film, and a metal layer, the metal-deposited layer, the transparent vapor-deposited layer, and the adhesive layer in contact with the metal layer are the cured coating film of the adhesive of the present invention. Is preferable.

When the adhesive of the present invention is a solvent type, the adhesive of the present invention is applied to a film material as a base material using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like. The other base material is bonded to obtain the laminate of the present invention. It is preferable to perform an aging treatment after laminating. The aging temperature is preferably room temperature to 80 ° C., and the aging time is preferably 12 to 240 hours.

When the adhesive of the present invention is a solvent-free type, the adhesive of the present invention which has been preheated to about 40 ° C. to 100 ° C. is applied to the film material as a base material using a roll such as a gravure roll. , Immediately attach the other base material to obtain the laminate of the present invention. It is preferable to perform an aging treatment after laminating. The aging temperature is preferably room temperature to 70 ° C., and the aging time is preferably 6 to 240 hours.

When the adhesive of the present invention is used as an adhesive auxiliary, the adhesive auxiliary of the present invention is applied to a film material as a base material using a roll such as a gravure roll, and the organic solvent is volatilized by heating in an oven or the like. After that, the laminate of the present invention is obtained by laminating the polymer material melted by an extruder.

The amount of adhesive applied is adjusted as appropriate. In the case of a solvent-based adhesive, for example, the solid content is adjusted to be 1 g / m ² or more and 10 g / m ² or less, preferably 1 g / m ² or more and 5 g / m ² or less. In the case of a solvent-free adhesive, the amount of the adhesive applied is, for example, 1 g / m ² or more and 10 g / m ² or less, preferably 1 g / m ² or more and 5 g / m ² or less.

When the adhesive of the present invention is used as an adhesive auxiliary, the coating amount is, for example, 0.03 g / m ² or more and 0.09 g / m ² or less (solid content).

The laminate of the present invention may further contain another film or base material in addition to the above-mentioned configurations (1) to (10). As the other base material, in addition to the above-mentioned stretched film, unstretched film, and transparent vapor-deposited film, a porous base material such as paper, wood, and leather described later can also be used. The adhesive used when laminating other substrates may or may not be the adhesive of the present invention.

As the paper, a known paper base material can be used without particular limitation. Specifically, it is produced by a known paper machine using natural fibers for papermaking such as wood pulp, but the papermaking conditions are not particularly specified. Examples of natural fibers for papermaking include wood pulp such as coniferous tree pulp and broadleaf tree pulp, non-wood pulp such as Manila hemp pulp, sisal hemp pulp, and flax pulp, and pulp obtained by chemically modifying these pulps. As the type of pulp, chemical pulp, ground pulp, chemigrand pulp, thermomechanical pulp, etc. by a sulfate cooking method, an acidic / neutral / alkaline sulfite cooking method, a soda salt cooking method, or the like can be used.

In addition, various commercially available high-quality papers, coated papers, backing papers, impregnated papers, cardboards, paperboards, etc. can also be used. Further, a printing layer may be provided on the outer surface or the inner surface side of the paper layer, if necessary.

The "other layer" may contain known additives and stabilizers such as antistatic agents, easy-adhesive coating agents, plasticizers, lubricants, antioxidants and the like. The "other layer" is a pretreatment in which the surface of the film is corona-treated, plasma-treated, ozone-treated, chemical-treated, solvent-treated, etc., in order to improve the adhesion when laminated with other materials. You may.

The laminate of the present invention can be used for various purposes such as packaging materials for foods, pharmaceuticals and daily necessities, lid materials, paper straws and paper napkins, paper spoons, paper plates, paper cups and other paper tableware, wall materials and roofs. Materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automobile parts, signboards, stickers, and other outdoor industrial applications, decorative sheets used for simultaneous injection molding decoration methods, etc. It can be suitably used as a packaging material such as liquid laundry detergent, liquid kitchen detergent, liquid bath detergent, liquid soap for bath, liquid shampoo, and liquid conditioner.

<Packaging material>
The laminate of the present invention can be used as a multi-layer packaging material for the purpose of protecting foods, pharmaceuticals and the like. When used as a multi-layer packaging material, its layer structure may change depending on the contents, usage environment, and usage pattern. Further, the package of the present invention may be appropriately provided with an easy-opening process or a resealing means.

The packaging material of the present invention is obtained by using the laminate of the present invention, laminating the surfaces of the sealant films of the laminate facing each other, and then heat-sealing the peripheral ends thereof to form a bag. As a bag-making method, the laminate of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type. There are three-way seal type, four-way seal type, envelope-attached seal type, gassho-attached seal type, fold-attached seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-seal methods. Be done. The packaging material of the present invention can take various forms depending on the contents, the environment of use, and the form of use. Free-standing packaging materials (standing pouches), etc. are also possible. As a heat sealing method, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

After filling the packaging material of the present invention with the contents from the opening, the opening is heat-sealed to manufacture a product using the packaging material of the present invention. As the contents to be filled, for example, foods include rice confectionery, bean confectionery, nuts, biscuits and cookies, wafer confectionery, marshmallows, pies, half-baked cakes, candy, snack confectionery and other confectionery, bread, snack noodles, instant noodles. , Dried noodles, pasta, sterile packaged rice, elephants, rice cakes, packaged rice cakes, staples such as cereal foods, pickles, boiled beans, natto, miso, frozen tofu, tofu, licked mushrooms, konjac, processed wild vegetables, jams, peanut cream, Processed agricultural products such as salads, frozen vegetables and processed potatoes, processed livestock products such as hams, bacon, sausages, processed chicken products and confectionery, fish meat hams and sausages, marine products, kamaboko, paste, boiled vegetables, Processed marine products such as sardines, salted spicy, smoked salmon, spicy cod roe, peaches, oranges, pineapples, apples, pears, cherries and other fruits, corn, asparagus, mushrooms, onions, carrots, radishes, potatoes and other vegetables , Hamburgers, meatballs, fried fishery products, frozen side dishes such as gyoza and croquettes, cooked foods such as chilled side dishes, butter, margarine, cheese, cream, instant creamy powder, dairy products such as baby-prepared powdered milk, liquids Examples include foods such as seasonings, retort curry, and pet food.

Non-food items include tobacco, disposable body warmers, medicines such as infusion packs, liquid detergents for washing, liquid detergents for kitchens, liquid detergents for baths, liquid soaps for baths, liquid shampoos, liquid conditioners, cosmetics such as lotions and emulsions, and vacuum. It can also be used as various packaging materials such as heat insulating materials and batteries.

The contents and effects of the present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the example, "part" means "part by weight".

Synthesis Examples 1 to 11, Synthesis Examples H1 to H4 Method for producing polyol composition (A) (Synthesis Example 1)
Method for Synthesizing Polyester Polyester (a1-1) 18.6 g of ethylene glycol, 24.3 g of diethylene glycol, in a 2-liter glass four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas introduction tube and a rectification tower. PET pellet B containing 83.3 g of neopentyl glycol, 105.3 g of 1,6 hexanediol, 124.0 g of adipic acid, 126.4 g of isophthalic acid, 63.2 g of terephthalic acid, 96.5 g of dimer acid, and 100 ppm of metal element. 73.1 g and 0.2 g of dibutyltin oxide were charged as a polymerization catalyst. The temperature was gradually raised under a normal pressure nitrogen stream to 260 ° C. while performing a dehydration reaction, and after reacting at 260 ° C. for 2 hours, it was confirmed that the contents became transparent and rectification was performed. After confirming that the temperature at the top of the column was 80 ° C or lower, remove the rectification column, switch to a glass condenser, connect a line from the nitrogen gas introduction tube to the vacuum pump, and perform a condensation reaction under a reduced pressure of 50 Torr for 5 hours. It was. When the predetermined acid value and viscosity were reached, the temperature was lowered to 130 ° C., and ethyl acetate was added and diluted using a dropping funnel to obtain a polyester polyol (a1-1). Weight fraction of PET pellets at the time of raw material preparation, solid equivalent acid value of polyester polyol (a1-1), solid equivalent hydroxyl value, content of metal elements derived from PET pellets in polyester polyol (a1-1) ( ppm) is shown in Table 1.

(Synthesis Example 2) to (Synthesis Example 8), (Synthesis Examples H1 to H3)
Polyester polyols (a1-2) to (a1-8) and (a1-H1) to (a1-H3) were obtained by synthesizing in the same manner as in (Synthesis Example 1) except that the raw materials shown in the table were used. Weight fraction of PET pellets at the time of raw material preparation and solid equivalent acid value of polyester polyols (a1-2) to (a1-8), (a1-H1) to (a1-H3), solid equivalent hydroxyl value, polyester The contents (ppm) of metal elements derived from PET pellets in the polyols (a1-2) to (a1-8) and (a1-H1) to (a1-H3) are shown in Tables 1 to 3, respectively.

(Synthesis Example 9)
Method for synthesizing polyester polyurethane polyol (a2-1) 300.0 g of polyester polyol (a1-2) in a 2-liter glass four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas introduction tube and a glass cooling tube. And 0.1 g of dibutyltin dilaurate was charged as a polymerization catalyst. When the temperature was raised to 60 ° C. under a normal pressure nitrogen stream, 8.1 g of isophorone diisocyanate and 0.7 g of tolylene diisocyanate were charged, and the temperature was raised to 80 ° C. to carry out a urethanization reaction at 80 ° C. for 5 hours. After confirming that the predetermined viscosity was reached and the residual isocyanate content was 0.05% or less, the temperature was lowered to 50 ° C. and the solid content was appropriately adjusted with ethyl acetate to obtain a polyester urethane polyol (a2-1). The acid value of the obtained polyester polyurethane polyol (a2-1) in terms of solids, the hydroxyl value in terms of solids, and the content (ppm) of metal elements derived from PET pellets in the polyester polyurethane polyol (a2-1) are shown in Tables 1 to 1. It is shown in Table 3.

(Synthesis Example 10), (Synthesis Example 11), (Synthesis Example H4)
Polyester polyurethane polyols (a2-2), (a2-3), and (a2-H1) were obtained by synthesizing in the same manner as in (Synthesis Example 9) except that the raw materials shown in the table were used. The acid value of the obtained polyester polyurethane polyols (a2-2), (a2-3), and (a2-H1) in terms of solids, the hydroxyl value in terms of solids, the polyester polyurethane polyol (a2-2), (a2-3) , (A2-H1) show the content (ppm) of the metal element derived from PET pellets in Tables 1 to 3.

In Tables 1 to 3, the unit of the charged amount is g. In addition, the blank is not mixed.

The terms in Tables 1 and 2 are as follows.
PET pellet A: (metal element content 200 ppm)
PET pellet B: (metal element content 100 ppm)
PET pellet C: (metal element content 50 ppm)

(Examples and comparative examples)
The reactive adhesives for Examples and Comparative Examples were prepared by blending the polyol composition (A) and the polyisocyanate composition (B) shown in Tables 4 and 5 in a ratio. The polyisocyanate composition (B) is a trifunctional polyisocyanate (DIC DIC Dry KW-75, solid content 75%) obtained by adding tolylene diisocyanate to trimethylolpropane, and a biuret of hexamethylene diisocyanate. (Manufactured by DIC Graphics, 90% solid content) was used. The evaluation was carried out according to the criteria shown below. The results are shown in Tables 4 and 5, respectively. Blanks indicate unmixed or unevaluated.

(Evaluation)
(Storage stability of polyol composition (A))
The polyol composition (A) obtained in Examples and Comparative Examples was diluted with ethyl acetate to a solid content of 60%, collected in a glass bottle, sealed, and then stored in a dryer at 50 ° C. for 2 weeks. The resin viscosity before and after storage was measured with a Gardner viscometer, converted into mpas units, and then the thickening rate was evaluated.
Evaluation ⊚: The thickening rate was less than 20%.
Evaluation ◯: The thickening rate was 20% or more and less than 40%.
Evaluation ×: The thickening rate was 40% or more.

(How to make a laminate for retort resistance test) Composition including aluminum foil)
After blending the adhesive according to the formulation in the table, apply the adhesive to a PET film with a thickness of 12 μm so that the solid content is about 3.5 g / m ² , dry the solvent, and then use a laminator to apply the adhesive. The adhesive-coated surface and a nylon film having a thickness of 15 μm were laminated and adhered to each other. Next, the nylon surface of this laminate is coated so that the amount of adhesive applied is about 3.5 g / m ² solid content, the solvent is dried, and then the adhesive coated surface of this laminate and the thickness of 9 μm are used with a laminator. It was laminated by laminating it with the aluminum foil of. Further, an adhesive is applied to the surface of the aluminum foil opposite to the adhesive-coated surface so that the solid content is about 3.5 g / m ² , the solvent is dried, and then the adhesive of the laminate is applied with a laminator. A surface and a heat-resistant non-stretched polypropylene film (heat-resistant CPP) having a thickness of 70 um were bonded and bonded to each other. After that, it was stored in a constant temperature bath at 40 ° C. for 3 days to obtain a laminate.

(How to make a laminate for boil resistance test)
After blending the adhesive according to the formulation in the table, the solid content is 3.0 g / an adhesive is applied such that the m ² approximately, with a laminator, and the coated surface of the adhesive was laminated to combined adhesive lamination and linear low density polyethylene film having a thickness of 60 [mu] m (LLDPE). After that, it was stored in a constant temperature bath at 40 ° C. for 3 days to obtain a laminate.

(Method of preparing a laminate for retort resistance test)
After blending the adhesive according to the formulation in the table, the coating amount is 3.0 g / solid content on the vapor-deposited layer of a PET film having a thickness of 12 um, a nylon (Ny) film having a thickness of 15 um, or a transparent vapor-deposited film having a thickness of 15 μm. m ² about the adhesive is applied so as to laminator, it is laminated by combined adhesive lamination and heat unstretched polypropylene film coated surface and the film thickness 70um of the adhesive (heat CPP). After that, it was stored in a constant temperature bath at 40 ° C. for 3 days to obtain a laminate.

(Measuring method of laminate strength)
The laminate was cut to a width of 15 mm, and the adhesive strength (T-type peeling) was measured at a peeling speed of 300 mm / min using a tensile tester. (Unit: N / 15mm)

(Lamination strength and appearance after boiling)
The laminate for the boil resistance test was cut out at 120 mm × 220 mm, bent so that the LLDPE was on the inside, and heat-sealed at 1 atm at 180 ° C. for 1 second to prepare a pouch. 1/1/1 sauce (meat sauce: vegetable oil: vinegar = 1: 1: 1) was added as the contents.
The filled pouch was boiled at 98 ° C. for 60 minutes, the contents were removed, and the strength by T-type peeling between PET / LLDPE, Ny / LLDPE and transparent vapor-deposited PET / LLDPE was measured. In addition, the appearance of each pouch after removal was observed, and the following evaluation was performed based on the presence or absence of derami.
Evaluation ○: No deflation Evaluation △: 5 points or less for deflation points Evaluation ×: 6 points or more for deflation points

(Laminate strength and appearance after retort treatment)
The laminate for the retort resistance test was cut out at 120 mm × 220 mm, bent so that the heat-resistant CPP was on the inside, and heat-sealed at 1 atm at 180 ° C. for 1 second to prepare a pouch. 1/1/1 sauce (meat sauce: vegetable oil: vinegar = 1: 1: 1) was added as the contents.
The filled pouch was retorted at 125 ° C. for 30 minutes (steam type) to remove the contents, and between PET / CPP, Ny / CPP, transparent vapor-deposited PET / CPP, and aluminum foil / CPP. The strength due to T-type peeling was measured. In addition, the appearance of each pouch after removal was observed, and the following evaluation was performed based on the presence or absence of derami.
Evaluation ○: No deflation Evaluation △: 5 points or less for deflation points Evaluation ×: 6 points or more for deflation points

In Table 4-6, the abbreviations are as follows.
(A): Polyester polyol (A)
(B): Polyisocyanate composition (B)
KW-75: Trifunctional polyisocyanate obtained by adding tolylene diisocyanate to trimethylolpropane Solid content 75%
KR-90: Hexamethylene diisocyanate biuret Lami strength: Laminate strength PET: Polyethylene terephthalate LLDPE: Linear low density polyethylene laminated film Ny: Nylon PET-AL: Polyethylene terephthalate and aluminum laminated film CPP: Unstretched polypropylene film /: Indicates that it is an adhesive layer

As a result, the polyol composition (A) used in (Example 1) to (Example 11) had little thickening with time, and sufficient adhesive strength was obtained even when used as an adhesive. .. On the other hand, in the polyol compositions used in (Comparative Example 1) to (Comparative Example 4), thickening occurred with time.

Claims (7)

1. A reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) is prepared by collectively charging polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid. It contains a polyester polyol (A1) which is a reaction product and / or a polyester polyurethane polyol (A2) which is a reaction product of a polyester polyol (A1) and an isocyanate compound, and the content of a metal element derived from the polyethylene terephthalate is high. A reactive adhesive characterized by less than 50 ppm.
2. The reactive adhesive according to claim 1, wherein the ratio of polyethylene terephthalate to the charged raw material of the polyester polyol (A1) is 5 to 50% by mass.
3. The reactive adhesive according to claim 1 or 2, wherein the polybasic acid is a dimer acid, and the ratio of the dimer acid to the charged raw material of the polyester polyol (A1) is 5 to 20% by mass.
4. The reactive adhesive according to any one of claims 1 to 3, wherein the polyol composition (A) contains a polyester polyurethane polyol (A2) which is a reaction product of a polyisocyanate and the polyester polyol (A).
5. A laminate obtained by laminating a plurality of films or papers with an adhesive, wherein the adhesive is the reactive adhesive according to any one of claims 1 to 4.
6. A laminate obtained by laminating a film or paper provided with a plurality of printing layers with an adhesive, wherein the adhesive is the reactive adhesive according to any one of claims 1 to 4. Laminated body.
7. A package obtained by molding the laminate according to claim 5 or 6 into a bag shape.