JP6650134B1 - Reactive adhesive, laminated film, and package - Google Patents

Abstract

A reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) is prepared by batch charging polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid. A reactive adhesive containing a polyester polyol (A1) as a reaction product, a laminated film obtained by laminating the reactive adhesive layer between a first plastic film and a second plastic film, and polyethylene terephthalate And a polyhydric alcohol and a polybasic acid are collectively charged and reacted to produce a polyester polyol (A1).

Description

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

2. Description of the Related Art Conventionally, a laminate formed by laminating various plastic films or laminating (laminating) a plastic film with a metal-deposited film or a metal foil has been used for various purposes, such as packaging materials for foods, pharmaceuticals, daily necessities, and barriers. Materials used for materials such as materials, roofing materials, solar panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automobile parts, signboards, stickers, etc. Used for applications.
In these laminates, various plastic films, metal-deposited films or metal foils are appropriately combined according to the characteristics required for each application, and an adhesive is selected according to the characteristics required. For example, in the case of foods and daily necessities, functions such as strength, resistance to cracking, retort resistance, heat resistance, and content resistance are used to protect the contents from various distributions, storage such as refrigeration, and treatment such as heat sterilization. Is required. Alternatively, in outdoor industrial applications, weather resistance and hydrolysis resistance are required to maintain adhesiveness for a long time even in an open-air environment.
Furthermore, these laminates rarely circulate in the form of a sheet. For example, the laminate may be heat-sealed at the end, or may be formed by thermoforming. It may be done.

As an adhesive used for such a laminate, a reactive adhesive (also referred to as a two-component adhesive) for reacting a hydroxyl group with an isocyanate has been conventionally known.
For example, in food applications, in an adhesive containing a diol compound (A) having two hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups, the number average of the diol compound (A) A polyisocyanate (B) having a molecular weight (Mn) in the range of 400 to 3000, wherein the polyisocyanate (B) is a trivalent or higher valent polyisocyanate compound (b1), and a diisocyanate compound (b2) obtained by adding an isocyanate compound to a polyester diol. Adhesives which are mixtures of are known. (For example, see Patent Document 1)
Adhesive for laminated film of battery packaging material, containing polyurethane polyester polyol having a number average molecular weight of 5,000 or more and less than 14,000, and the total content of urethane bonds and isocyanate groups is specified. It is known that a laminating adhesive falling within the range is excellent in moldability and wet heat resistance (for example, see Patent Document 2).

  These reactive adhesives are required to have properties according to various uses, and in recent years, from the viewpoint of productivity, a laminated film that does not cause poor appearance even at a coating speed of, for example, 200 m / min or more. Is required. However, under such high-speed coating (also referred to as high-speed processing) conditions, not only a solventless reactive adhesive which does not use an organic solvent, but also a dry laminate type reactive adhesive whose viscosity can be adjusted using an organic solvent. Even in such a case, there was a problem that a citrus skin-like appearance defect was likely to occur depending on the base material.

JP 2014-101422A JP-A-2006-196580 JP-A-2002-3815 JP 2010-248345 A

  The problem to be solved by the present invention is that it can be applied as an adhesive for a laminate obtained by appropriately combining various kinds of plastic films, metal-deposited films or metal foils, and has high adhesiveness and lamination even under high-speed coating conditions. An object of the present invention is to provide a reactive adhesive capable of obtaining a laminated film having an excellent appearance later.

  The present inventors provide a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) comprises polyethylene terephthalate, a polyhydric alcohol, and a polybasic. It has been found that a reactive adhesive containing a polyester polyol (A1), which is a reaction product obtained by batch charging with an acid, solves the above problem.

  An adhesive using a polyester polyol made of polyethylene terephthalate as a raw material is known (for example, see Patent Documents 3 and 4). For example, Patent Literature 3 discloses that a reaction between a polyester polyol obtained by decomposing polyethylene terephthalate by a reaction with a low-molecular-weight polyol and then subjecting the decomposed product to a polybasic acid and a polyisocyanate curing agent is performed. An adhesive is disclosed. However, Patent Literature 3 evaluates a laminated film prepared by applying an adhesive at a film speed of 50 m / min, but does not discuss a form prepared under a high-speed coating condition of a coating speed of 200 m / min or more. There is no description or suggestion. Patent Document 4 discloses that a polyol compound obtained by depolymerizing a polyester (a) with a polyol (b) having two or more hydroxyl groups in one molecule is used as a raw material of an adhesive. However, as for the evaluation of the adhesive, the evaluation is also made on a laminated film obtained by applying the film to the film with a thickness of 30 μm using an applicator and then laminating the film. There is no description or suggestion about the form. That is, a reactive adhesive having high adhesiveness and an excellent appearance after laminating is now available even under high-speed coating conditions of a coating speed of 200 m / min or more using a polyester polyol made of polyethylene terephthalate as a raw material. What is not known is the fact.

  The present inventors have recognized that polyester polyols obtained by the methods disclosed in Patent Literatures 3 and 4 cause poor appearance at the time of high-speed coating properties, while polyethylene terephthalate and polyhydric alcohols If the polyester polyol (A1), which is a reaction product obtained by batch charging with a polybasic acid, is used as a component of the reactive adhesive, poor appearance during high-speed coating is unlikely to occur, and a high level after lamination. The inventors have found that a laminated film having adhesive properties, particularly heat resistance and content resistance, can be obtained, and have reached the present invention.

  That is, the present invention relates to a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) comprises polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid. To provide a reactive adhesive containing a polyester polyol (A1) which is a reaction product obtained by batch charging with the above.

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

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

  The present invention also provides a method for producing a polyester polyol (A1), in which polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid are charged and reacted at once.

The present invention also provides a method for producing a polyester polyol (A1) in which polyethylene terephthalate, a polyhydric alcohol and a polybasic acid are charged and reacted at once, and a polyester polyurethane polyol (A2) in which a polyisocyanate is reacted.

  The reactive adhesive of the present invention can be applied as an adhesive for a laminate obtained by appropriately combining various kinds of plastic films, metal-deposited films or metal foils, and has high adhesiveness and high lamination even under high-speed coating conditions. A laminated film having an excellent appearance can be obtained. Furthermore, since it is excellent in heat resistance and content resistance, it can be suitably used particularly as a food packaging bag.

  The present invention relates to a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) comprises polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid. Characterized by containing a polyester polyol (A1) which is a reaction product obtained by batch charging of the above.

(Polyol composition (A))
The polyester polyol (A1) contained in the polyol composition (A) is a reaction product obtained by batch charging of polyethylene terephthalate, polyhydric alcohol, and polybasic acid.

(Polyester polyol (A1))
Polyethylene terephthalate (hereinafter sometimes referred to as PET) used in the present invention can be obtained by polycondensation of terephthalic acid or dimethyl terephthalate with ethylene glycol, and further, if necessary, isophthalic acid, phthalic anhydride, adipic acid, Those modified with substances such as cyclohexanedicarboxylic acid, 1,3-butanediol, and cyclohexanedimethanol can also be used. Furthermore, commercially available unused PET bottles, PET films, and other remnants from the production of PET products may be pulverized, or recycled PET recovered from waste and washed, and the like. Among them, it is preferable to use recycled PET. These can be obtained from the market in washed and pelletized form.

  The intrinsic viscosity (IV) of PET is preferably from 0.50 to 0.80 dL / g. Within this range, the polycondensation reaction between PET and other raw materials can be performed at 250 ° C. or lower. In addition, this range is also preferable from the viewpoint of 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 a known polyhydric alcohol 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, Aliphatic diols such as 2,4-trimethyl-1,3-pentanediol; 1,3-bis (2-hydroxypropyl) cyclopentane, 1,3-bis (2-hydroxybutyl) cyclopentane, 1,4- Alicyclic 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- Bisphenols such as hydroxyphenyl) methane (hereinafter abbreviated as “bisphenol F”) and bis (4-hydroxyphenyl) sulfone (hereinafter abbreviated as “bisphenol S”) can be added to 1,2-propylene oxide and 1,2-butylene. Alkylene oxide adduct of bisphenol obtained by adding an alkylene oxide having a secondary hydroxyl group such as oxide; ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,3 -Butanediol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol and the like Aliphatic polyols; ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol;

Modification 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 polyols; lactone-based polyester polyols obtained by polycondensation reaction of the aliphatic polyols with various lactones such as ε-caprolactone; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenol A, bisphenol F and the like And ethylene oxide adduct of bisphenol obtained by adding ethylene oxide to bisphenol.

  These may be used alone or in combination of two or more. 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 and orthophthalic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexahydroacid 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- Aliphatic unsaturated dicarboxylic acids such as dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, fumaric acid, mesaconic acid, itaconic acid, and glutaconic acid; 1,2,5-hexanetricarboxylic acid, 1,2,2 Aliphatic tricarboxylic acids such as 4-cyclohexanetricarboxylic acid; trimellitic acid, 1,2,5-ben Ntorikarubon acid, 2,5,7 aromatic tricarboxylic acids such as naphthalene tricarboxylic acid, such as dimer acid. These may be used alone or in combination of two or more. Among them, dimer acid is preferred.

The production method in which PET, a polyhydric alcohol, and a polybasic acid are collectively charged and reacted can be arbitrarily produced by a known polycondensation reaction method. Specifically, PET, a polyhydric alcohol, and a polybasic acid are used. The acid is charged into the production apparatus, and the temperature is raised to 180 ° C. or higher while stirring under a nitrogen atmosphere. May be implemented. When the PET, the polyhydric alcohol, and the polybasic acid described in the present application are used, the dehydration under reduced pressure can be applied at a reaction temperature of 230 ° C. or less, and the reaction time can be reduced 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 production apparatus used at this time, for example, a batch-type production apparatus such as a reaction vessel equipped with a nitrogen inlet, a thermometer, a stirrer, a rectification tower, and the like can be suitably used, and a deaeration port is provided. Extruders, continuous reactors, kneaders and the like can also be used. Further, if necessary, an esterification catalyst (a tin compound, a titanium compound, a zirconium compound, or the like) 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 transesterified reaction product with a polybasic acid are bonded to the polyol because the ethylene terephthalate unit is decomposed separately. Even when used as an agent, the appearance, adhesive strength, heat resistance, and content resistance during high-speed coating, which are the objects of the present application, cannot be achieved.

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

  Further, the PET has a ratio of 5 to 50% by mass relative to the total amount of the polyhydric alcohol and the polybasic acid with respect to 100% of the total amount of the polyhydric alcohol and the polybasic acid. Is more preferable, and more preferably 8 to 48% by mass.

  In the present application, as a raw material of the 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 obtain an adhesive strength to a substrate. And an adhesive excellent in heat resistance and content resistance can be obtained. Although the reason for this is not clear, this composition makes it possible to carry out the reaction at a reaction temperature of 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, resulting in a high reaction temperature. It is presumed that the molecular weight remains as it is, and this contributes to the appearance, adhesive strength, heat resistance and content resistance during high-speed coating. In the case of a trihydric alcohol (trimethylolpropane) as a polyhydric alcohol, the ethylene terephthalate unit in PET may be sufficiently decomposed, and the reaction temperature must be higher than 220 ° C. Thus, the polyhydric alcohol is preferably 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 reactivity of the adhesive. Further, from the viewpoint of high-speed coating properties, 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 are values converted into solid contents unless otherwise specified.

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

(Hydroxyl value)
6 to 10 g of polyester polyol is weighed in a 300 ml Erlenmeyer flask. The weighed amount is defined as (S). To this, 25 ml of an acetylating agent prepared in advance is added and dissolved. A condenser was attached to the mouth of the Erlenmeyer flask, and the acetylation reaction was performed at 100 ° C. for 1 hour. 10 ml of ion-exchanged water is added and cooled to room temperature. After adding 2 to 3 drops of phenolphthalein as an indicator thereto, titration is performed with a 0.5 mol / L potassium hydroxide alcohol solution. The point at which a slight red color lasting for 30 seconds is taken as the end point, and the hydroxyl value is calculated from the titer (V) at that time by the following formula. Simultaneously, a blank test is performed, and the titer at that time is defined as (B). Let the titer of the 0.5 mol / L potassium hydroxide alcohol solution be (F). Separately, measure the acid value.
Hydroxyl value = ((B−V) × F × 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 2,000 to 12,000, more preferably 3,000 to 8,000, 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.

Measurement device: Tosoh Corporation HLC-8220GPC
Column: Tosoh Corporation TSK-GUARDCOLUMN SuperHZ-L
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent Tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodisperse polystyrene sample: 0.2% by mass of resin in solid tetrahydrofuran solution filtered through a microfilter (100 μl)

(Polyester polyurethane polyol (A2))
Further, the polyester polyol (A1) is a polyester polyurethane polyol (A2) obtained by collectively reacting polyethylene terephthalate, a polyhydric alcohol and a polybasic acid, followed by further reacting with an isocyanate compound described below. Is also 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 reactivity of the adhesive. The hydroxyl value is preferably 30 or less, more preferably 25 or less, from the viewpoint of heat resistance and content resistance.

(Other polyols)
In the present invention, in addition to the polyester polyol (A1), polyester polyols, polyether polyols, polyurethane polyols, and polyethers that do not use polyethylene terephthalate as a raw material in addition to the polyester polyol (A1) within a range not to impair the effects of the present invention. A polymer polyol selected from an ester polyol, a polyester (polyurethane) polyol, a polyether (polyurethane) polyol, a polyesteramide polyol, an acrylic polyol, a polycarbonate polyol, a polyhydroxylalkane, a 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 from 1 to 50% by mass, more preferably from 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. The polyisocyanate compound used in the present invention may be any known one without any particular limitation, and may 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, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, and the NCO group of these polyisocyanates A compound in which a part of is modified with carbodiimide;

Alphanate compounds derived from these polyisocyanates; polyisocyanates having an alicyclic structure in the molecular structure such as isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), and 1,3- (isocyanatomethyl) cyclohexane; Linear aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate, and this alphanate compound; isocyanurates of these polyisocyanates; allophanates derived from these polyisocyanates; Biuret bodies derived from these polyisocyanates; adduct bodies modified with trimethylolpropane;

Examples thereof include polyisocyanates, which are reaction products of the above-described various polyisocyanate compounds with polyhydric alcohols.

In the polyisocyanate which is a reaction product of the above-described various polyisocyanate compounds and a polyhydric alcohol, the polyhydric alcohol is a polyhydric alcohol which is a raw material of the polyol composition (A), the polyester polyol (A1), Polyester polyol (A1-2), polyester polyol not using polyethylene terephthalate as a raw material, polyether polyol, polyurethane polyol, polyether ester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyester amide polyol, acrylic polyol , Polycarbonate polyol, polyhydroxyl alkane, castor oil or a polymer polyol selected from a mixture thereof can be used. . Among them, it is preferable to use a polyisocyanate which is a reaction product of the above-mentioned various polyisocyanates 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 of isocyanate group to hydroxyl group [isocyanate group / hydroxyl group] is in the range of 1.0 to 5.0, and the cohesion of the adhesive coating film is determined. It is preferable in terms of balance between force and flexibility.

  The polyisocyanate compound preferably has an average molecular weight in the range of 100 to 1,000 from the viewpoint of adhesive strength, heat resistance and content resistance.

(solvent)
The reactive adhesive used in the present invention is an adhesive that is cured by a chemical reaction between an isocyanate group and a hydroxyl group, and can be used as a solvent-type or non-solvent-type adhesive. The “solvent” of the solventless adhesive according to the present invention refers to a highly soluble organic solvent capable of dissolving the polyisocyanate compound or the polyol compound used in the present invention, and refers to a “solvent-free”. Means not containing these highly soluble organic solvents. Specific examples of highly soluble organic solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, Examples include toluene, xylol, n-hexane, cyclohexane and the like. Among them, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are known as organic solvents having particularly high solubility.
On the other hand, when there is a demand for a low viscosity or the like, the adhesive of the present invention may be appropriately diluted with the highly soluble organic solvent according to a desired viscosity before use. In that case, either one of the polyisocyanate composition (B) and 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, toluene, xylol, n-hexane, cyclohexane and the like. Is 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 used in the range of about 20 to 50% by mass.

  In the reactive adhesive used in the present invention, the mixing ratio of the polyisocyanate composition (B) and the polyol composition (A) is such that the mixing ratio of the polyisocyanate compound (B) contained in the polyisocyanate composition (B) is Adhesion strength or heat sealing is that 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. 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 properties 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 blending it as a third component at the time of coating, it can be added to an aromatic amine in a laminate package. Elution of representative harmful low molecular chemical substances into the contents can be effectively suppressed.

  Examples of the aliphatic cyclic amide compound used here include δ-valerolactam, ε-caprolactam, ω-enanthol lactam, η-caprylactam, β-propiolactam and the like. Among them, ε-caprolactam is preferable because of its excellent effect of reducing the amount of low-molecular-weight chemical substance eluted. Moreover, it is preferable to mix the aliphatic cyclic amide compound in the range of 0.1 to 5 parts by mass per 100 parts by mass of the polyol component A.

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

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 (bismuth), and Co (cobalt) are acetylacetonate salts of metals. For example, iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate and the like can be mentioned. Among them, iron acetylacetonate (Fe (acac) ₃ ) Or manganese acetylacetonate (Mn (acac) ₂ ).

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

  As the organometallic catalyst, stannas diacetate, stannas dioctoate, stannas dioleate, stannas dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, Examples include nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, bismuth neodecanoate, and the like. Among these, preferred compounds are organotin catalysts, and more preferred are stannas dioctoate and dibutyltin 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 preferred 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'-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N'-(2-hydroxy Ethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, bis ( Methylaminopropyl) 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 -Methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N, N-dimethylhexanolamine, N-methyl-N '-(2-hydroxyethyl) piper , 1- (2-hydroxyethyl) imidazole, 1- (2-hydroxypropyl) imidazole, 1- (2-hydroxyethyl) -2-methylimidazole, 1- (2-hydroxypropyl) -2-methylimidazole Is mentioned.

  Examples of the aliphatic cyclic amide compound include δ-valerolactam, ε-caprolactam, ω-enanthol lactam, η-caprylactam, β-propiolactam and the like. Among them, ε-caprolactam is more effective for accelerating curing.

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

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

  The reactive adhesive of the present invention may use a pigment, if necessary. The pigment that can be used in this case is not particularly limited. For example, extenders, white pigments, black pigments, gray pigments, and red pigments described in the 1970 Handbook of Paint Materials (edited by the Japan Paint Manufacturers Association) Examples of the pigment include organic pigments and inorganic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearlescent pigments, and further, plastic pigments. Specific examples of these colorants include various pigments, and examples of organic pigments include various insoluble azo pigments such as benzidine 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 mordant dye pigments such as quinoline lake and fast sky blue; anthraquinone Vat dyes such as thioindigo pigments and perinone pigments; various quinacridone pigments such as synchasia red B; various oxazine pigments such as oxazine violet; various condensed azos such as chromophtal Pigment; aniline black, etc. And the like.

  Examples of the inorganic pigments include various chromates such as graphite, zinc chromate, and molybdate orange; various ferrocyan compounds such as navy blue; titanium oxide, zinc white, mapico yellow, iron oxide, red iron oxide, and chrome oxide. Various metal oxides such as green and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types of calcium silicate and ultramarine blue 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 flakes coated with metal oxide Pigments, metallic pigments and pearl pigments such as micaceous iron oxide pigments; graphite, carbon black and the like.

  As the extender pigment, for example, precipitated barium sulfate, powder, precipitated calcium carbonate, calcium bicarbonate, dolomite, alumina white, silica, hydrated fine powdered silica (white carbon), ultrafine powdered anhydrous silica (Aerosil), silica sand (silica) Sand), talc, precipitated magnesium carbonate, bentonite, clay, kaolin, loess 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, inorganic oxides such as titanium oxide and zinc white as a white pigment, and carbon black as a black pigment are more preferable because of excellent durability, weather resistance and design.

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

(Adhesion promoter)
Further, the reactive adhesive used in the present invention can also be used in combination with an adhesion promoter. Examples of the adhesion promoter include a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, and an epoxy resin.

  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 and N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-gly Epoxysilanes such as sidoxypropyltriethoxysilane; vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-mel Hept trimethoxysilane and the like.

  Examples of titanate-based coupling agents include, for example, 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.

  Examples of the aluminum-based coupling agent include, for example, acetoalkoxyaluminum diisopropylate.

  Epoxy resins include generally commercially available epbis type, novolak type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, Various epoxy resins such as trivalent carboxylic acid ester type, aminoglycidyl type, resorcinol type, triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylic glycidyl Ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butylphenyl glycidyl ether, diglycidyl adipic ester, o Phthalic acid diglycidyl ester, glycidyl methacrylate, compounds such as butyl glycidyl ether.

(Other additives)
If necessary, the reactive adhesive used in the present invention may contain other additives other than those described above. Examples of additives include a leveling agent, inorganic fine particles such as colloidal silica and alumina sol, organic fine particles of polymethyl methacrylate, an antifoaming agent, an anti-sagging agent, a wetting and dispersing agent, a viscosity adjusting agent, an ultraviolet absorber, and a metal. Deactivator, peroxide decomposer, flame retardant, reinforcing agent, plasticizer, lubricant, rust inhibitor, fluorescent brightener, inorganic heat ray absorber, flame retardant, antistatic agent, dehydrating agent, Known and commonly used thermoplastic elastomers, tackifiers, phosphate 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 one of the polyisocyanate composition (B) and 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 previously blended with the polyol composition (A) is prepared, and immediately before construction, the premix is mixed with the polyisocyanate composition (B). Prepare by mixing.

(Laminated film)
The laminated film of the present invention is obtained by laminating an adhesive layer made of the reactive adhesive between a first plastic film and a second plastic film. Specifically, it is obtained by applying the reactive adhesive to a first plastic film, then laminating a second plastic film on the applied surface, and curing the adhesive layer. For example, when the reactive adhesive is a solventless type, a method of applying the first adhesive to a first plastic film by a roll coater coating method, and then bonding another substrate without a drying step may be used. When the reactive adhesive contains a solvent, a method in which the reactive adhesive is applied to a first plastic film by a roll coater coating method, passed through a drying oven at 60 ° C., and then bonded to another base material may be used. Coating conditions are, in a normal roll coater, in a state of heating to 30 ° C. to 90 ° C., the viscosity of the compounding liquid of the adhesive is preferably about 300 to 3000 mPa · s at 40 ° C., but the adhesive of the present invention is compounded. Since the viscosity after leaving in a 40 ° C. atmosphere for 30 minutes is 5000 mPa · s or less, coating can be performed without any problem. Further, the coating amount is preferably 0.5 to 5 g / m ² , and more preferably about 0.5 to 3 g / m ² .

  In addition, a gravure or flexo-printed printing ink may be used on the first plastic film. Even in this case, a good laminate appearance can be exhibited. As the above-mentioned printing ink, a solvent type, aqueous type or active energy ray curable type ink can be used.

  When the reactive adhesive used in the present invention is used, after laminating, the adhesive is cured at room temperature or under heating for 12 to 72 hours to exhibit practical physical properties.

  As the first plastic film used herein, a PET (polyethylene terephthalate) film, a nylon film, an OPP (biaxially oriented polypropylene) film, a K coat film such as polyvinylidene chloride, a base film such as various vapor deposition films, and an aluminum foil. Examples of the second plastic film include, as the other substrate, a CPP (unstretched polypropylene) film, VMCPP (aluminum-deposited unstretched polypropylene film), LLDPE (linear low-density polyethylene), LDPE (Low-density polyethylene), HDPE (high-density polyethylene), and sealant films such as VMLDPE (aluminum-deposited low-density polyethylene film) films.

  In the present invention, not only when high-speed laminating with a dry laminating machine having a drying step of an organic solvent in the adhesive, but also excellent laminating film appearance can be obtained even when high-speed laminating with a solventless laminating machine. For example, a high-speed processing of 200 m / min or more for a PET (polyethylene terephthalate) film / VMCPP (aluminum-deposited unstretched polypropylene film) film configuration and a high-speed processing of 350 m / min or more for an OPP / CPP film configuration is satisfactory. It can take on the appearance.

(Package)
The package of the present invention is formed by molding the laminated film into a bag shape. Specifically, the package is formed by heat-sealing the laminated film. In addition, when considering the use as a package, required performance (easy tearing property and hand-cutting property), rigidity and durability required for the package (for example, impact resistance and pinhole resistance, etc.), Other layers can be laminated as needed. Usually, it is used with a base material layer, a paper layer, a second sealant layer, a non-woven cloth layer and the like. As a method of laminating another layer, a known method can be used. For example, an adhesive layer may be provided between other layers and laminated by a dry lamination method, a heat lamination method, a heat sealing method, an extrusion lamination method, or the like. As the adhesive, the above-mentioned reactive adhesive may be used, or another one-pack type urethane-based adhesive, epoxy-based adhesive, aqueous dispersion of acid-modified polyolefin, or the like may be used.

  Specific laminate structures include a first plastic film layer / adhesive layer / second plastic layer, and a first plastic layer, which can be suitably used for general packaging, lid materials, refill containers, and the like. Base layer / adhesive layer / first plastic film layer / adhesive layer / second plastic layer / paper which can be suitably used for paper containers, paper cups, etc. Layer / adhesive layer / first plastic film layer / adhesive layer / second plastic, second plastic layer / paper layer / polyolefin resin layer / substrate layer / first plastic layer / adhesive layer / second plastic Layer, paper layer / first plastic film layer / adhesive layer / sealant layer, second plastic layer / adhesive layer / first plastic which can be suitably used for tube containers, etc. Such as a layer / adhesive layer / second plastic layer. These laminates may have a print layer, a top coat layer, and the like, if necessary.

  The first plastic film layer includes, for example, polyester resin films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN) and polylactic acid (PLA); polyolefin resin films such as polypropylene; polystyrene resin films; Polyamide resin film such as p-xylylene adipamide (MXD6 nylon); polycarbonate resin film; polyacrylonitrile resin film; polyimide resin film; a multilayer body of these (for example, nylon 6 / MXD6 / nylon 6, nylon 6 / Ethylene-vinyl alcohol copolymer / nylon 6) or a mixture is used. Among them, those having mechanical strength and dimensional stability are preferable. In particular, among these, films stretched arbitrarily in the biaxial direction are preferably used.

  In addition, the first plastic film layer is formed of a soft metal foil such as an aluminum foil to provide a barrier function, as well as an evaporation layer such as aluminum evaporation, silica evaporation, alumina evaporation, and silica-alumina binary evaporation; An organic barrier layer made of modified polyvinyl alcohol, ethylene vinyl alcohol copolymer, MXD nylon, or the like can be used.

  As the second plastic film layer, a conventionally known sealant resin can be used. For example, polyethylene such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and high density polyethylene (HDPE), acid-modified polyethylene, polypropylene (PP), acid-modified polypropylene, copolymerized polypropylene, ethylene-vinyl acetate Examples include copolymers, ethylene- (meth) acrylate copolymers, ethylene- (meth) acrylic acid copolymers, and polyolefin resins such as ionomers. Above all, a polyethylene resin is preferable from the viewpoint of low-temperature sealing properties, and polyethylene is particularly preferable because it is inexpensive. The thickness of the sealant layer is not particularly limited, but is preferably in the range of 10 to 60 μm, and more preferably in the range of 15 to 40 μm, in consideration of workability into a packaging material, heat sealability, and the like. Further, by providing the sealant layer with unevenness having a height difference of 5 to 20 μm, it is possible to impart slipperiness and tearability of the packaging material to the sealant layer.

  Examples of the paper layer include natural paper and synthetic paper. The first and second sealant layers can be formed of the same material as the above-described sealant layer. A printing layer may be provided on the outer surface or the inner surface side of the base material layer and the paper layer as necessary.

  The “other layer” may contain known additives and stabilizers, for example, an antistatic agent, an easy-adhesion coating agent, a plasticizer, a lubricant, an antioxidant, and the like. The “other layer” is obtained by subjecting the film surface to a corona treatment, a plasma treatment, an ozone treatment, a chemical treatment, a solvent treatment, or the like as a pre-treatment in order to improve adhesion when laminated with another material. You may.

  Examples of the package of the present invention include a three-sided seal bag, a four-sided seal bag, a gusset packaging bag, a pillow packaging bag, a bottomed container of a Gebel top type, a tetra-classic, a Bruch type, a tube container, a paper cup, a lid material, and the like. There are various. Further, the package of the present invention may be provided with an easy-opening process or a re-sealing means as appropriate.

  The laminate obtained in this way can be used in various applications, for example, packaging materials for foods, pharmaceuticals, household goods, barrier materials, roof materials, solar panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting. Protective materials, automotive materials, signboards, stickers, etc., outdoor industrial applications, decorative sheets used for simultaneous injection molding decoration methods, washing liquid detergents, kitchen liquid detergents, bath liquid detergents, bath liquid soaps, liquid shampoos It can be suitably used as a packaging material for liquid conditioners and the like.

  Hereinafter, the contents and effects of the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the examples, “parts” means “parts by weight”.

(Synthesis example 1)
Synthesis of PET-containing polyester polyol (A1-1) 27.2 g of ethylene glycol and neopentyl glycol 205 were placed in a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a rectification tower. 1.0 g, 178.7 g of adipic acid, 164.0 g of isophthalic acid, 64.0 g of regenerated PET pellets, and 0.11 g of dibutyltin oxide as a polymerization catalyst. The temperature was gradually raised to 230 ° C. while performing a dehydration reaction under a nitrogen stream at normal pressure, and after reacting at 230 ° C. for 2 hours, it was confirmed that the contents became transparent. When it is confirmed that the top temperature of the mixture has become 80 ° C. or lower, the rectification column is removed and switched to a glass condenser, and a line is connected from a nitrogen gas introduction pipe to a vacuum pump to carry out a condensation reaction under a reduced pressure of 50 Torr for 5 hours. When a 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 PET-containing polyester polyol (A1-1). The weight fraction of PET pellets, the weight fraction of 1,6-hexanediol, the weight fraction of dimer acid, and the acid value of the obtained PET-containing polyester polyol (A1-1) in terms of solids and solids in preparing the raw materials. Tables 1 and 2 show the hydroxyl value, solid content, and number average molecular weight of the polymer.

(Synthesis Example 2), (Synthesis Example 6), (Synthesis Example 7)
Synthesis of PET-containing polyester polyols (A1-2), (A1-6), and (A1-7) Except for using the raw materials shown in Tables 1 and 2, it was produced in the same manner as the PET-containing polyester polyol (A1-1). Tables 1 and 2 show properties and the like.

(Synthesis example 3)
Synthesis of PET-Containing Polyester Polyol (A1-3) In a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a rectification tower, 20.0 g of ethylene glycol and 150 g of neopentyl glycol were placed. .1 g, 92.0 g of 1,6-hexanediol, 92.0 g of dimer acid, 174.7 g of adipic acid, 160.5 g of isophthalic acid, 76.5 g of PET pellets, and 0.14 g of dibutyltin oxide as a polymerization catalyst. The temperature was gradually raised under a normal pressure nitrogen stream, and the temperature was raised to 220 ° C. while performing a dehydration reaction. After reacting at 220 ° C. for 2 hours, it was confirmed that the contents became transparent. After confirming that the temperature of the top of the column became 80 ° C. or lower, the rectification column was removed and switched to a glass condenser, and a line was connected from the nitrogen gas introducing pipe to a vacuum pump to carry out a condensation reaction under reduced pressure of 50 Torr for 4 hours. When a 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 PET-containing polyester polyol (A1-3). The weight fraction of PET pellets, the weight fraction of 1,6-hexanediol, the weight fraction of dimer acid, and the acid value and solid value of the obtained PET-containing polyester polyol (A1-3) at the time of charging the raw materials. Tables 1 and 2 show the hydroxyl value, solid content, and number average molecular weight of the polymer.

(Synthesis Example 4), (Synthesis Example 5), (Synthesis Example 8), (Synthesis Example 10)
Synthesis of PET-containing polyester polyol (A1-4), (A1-5), (A1-8), (A1-10) PET-containing polyester polyol (A1-3) except that the raw materials shown in Tables 1 and 2 were used. It was manufactured in the same manner as described above. Tables 1 and 2 show properties and the like.

(Synthesis example 9)
Synthesis of PET-Containing Polyester Polyol (A1-9) 14.6 g of ethylene glycol and neopentyl glycol 109 were placed in a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a rectification tower. 0.7 g, 1,6-hexanediol 21.0 g, dimer acid 21.0 g, adipic acid 90.3 g, isophthalic acid 83.0 g, PET pellets 690.0 g, and 0.14 g of dibutyltin oxide as a polymerization catalyst are charged. The temperature was gradually increased under a normal pressure nitrogen stream, and the temperature was raised to 220 ° C. while performing a dehydration reaction. After reacting at 220 ° C. for 5 hours, it was confirmed that the contents became transparent, and the rectification column When it is confirmed that the top temperature of the mixture has become 80 ° C. or lower, the rectification column is removed and switched to a glass condenser, and a line is connected from a nitrogen gas introduction pipe to a vacuum pump to carry out a condensation reaction under a reduced pressure of 50 Torr for 5 hours. When a 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 PET-containing polyester polyol (A1-9). The weight fraction of PET pellets, the weight fraction of 1,6-hexanediol, the weight fraction of dimer acid, and the acid value and solid value of the obtained PET-containing polyester polyol (A1-9) at the time of charging the raw materials. Tables 1 and 2 show the hydroxyl value, solid content, and number average molecular weight of the polymer.

(Comparative Synthesis Example 1)
Synthesis of PET-decomposed polyester polyol (A1-11) 27.2 g of ethylene glycol and neopentyl glycol were placed in a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a glass cooling tube. 205.0 g, regenerated PET pellets 372.0 g, and 0.60 g of tetraisopropyl titanate as a transesterification catalyst are charged. The temperature was raised to 190 ° C. under a nitrogen stream at normal pressure, and the decomposition reaction of PET was sufficiently performed at 190 ° C. for 7 hours, and the reaction liquid was completely transparent and uniform without any insoluble matter in the PET pellets. After confirming the above, the mixture was cooled to 130 ° C., and 157.5 g of adipic acid and 144.7 g of isophthalic acid were charged. The temperature was gradually raised to 250 ° C. while performing a dehydration reaction under a normal pressure nitrogen stream, and the reaction was performed at 250 ° C. for 2 hours. Remove the distillation tower, switch to a glass condenser, and lower the temperature to 230 ° C. When the temperature reaches 230 ° C., a line is connected from the nitrogen gas introducing pipe to a vacuum pump, and the condensation reaction is carried out for 8 hours under a reduced pressure of 50 Torr. When a 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 PET-containing polyester polyol (A1-11). Tables 1 and 2 show the weight fraction of the PET pellets at the time of charging the raw materials, the acid value in terms of solid, the hydroxyl value in terms of solid, the solid content, and the number average molecular weight of the obtained PET-decomposed polyester polyol (A1-11).

(Comparative Synthesis Example 2)
Synthesis of PET-decomposed polyester polyol (A1-12) 434.0 g of regenerated PET pellets are charged into a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube, and a glass cooling tube. It was immersed in a salt bath at 300 ° C. under a nitrogen stream at normal pressure, and when PET started to be dissolved, stirring was started, and 1.47 g of dibutyltin oxide was charged as a transesterification catalyst. Then, 300.0 g of trimethylolpropane previously dissolved at 130 ° C. was added little by little while paying attention not to solidify the PET, and then reacted for 5 hours while maintaining the internal temperature at 220 ° C. in a 240 ° C. oil bath. A polyester polyol (A1-12) was obtained. Tables 1 and 2 show the weight fraction of the PET pellets at the time of charging the raw materials, and the solid acid value, solid hydroxyl value, solid content, and number average molecular weight of the obtained PET-decomposed polyester polyol (A1-12).

(Comparative Synthesis Example 3)
Synthesis of PET-decomposed polyester polyol (A1-13) 61.6 g of neopentyl glycol, 1,6-, were placed in a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a rectification tower. 118.7 g of hexanediol, 23.0 g of trimethylolpropane, 157.8 g of adipic acid, 89.4 g of isophthalic acid, 328.2 g of regenerated PET pellets, and 0.60 g of monobutyltin oxide as a polymerization catalyst are charged. The temperature was gradually increased under a normal pressure nitrogen stream, and the temperature was raised to 230 ° C. while performing a dehydration reaction, and the reaction was carried out at 230 ° C. for 2 hours. However, since the contents did not become transparent, the temperature was raised to 240 ° C. When the top temperature of the rectification column was confirmed to be 80 ° C. or less, the rectification column was removed and switched to a glass condenser. A line was connected from the nitrogen gas introduction pipe to the vacuum pump, and the pressure was reduced under 50 Torr. For 9 hours. When a 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 PET-containing polyester polyol (A1-13). The weight fraction of PET pellets, the weight fraction of 1,6-hexanediol, the weight fraction of dimer acid, and the acid value of the obtained PET-decomposed polyester polyol (A1-13) in terms of solids and solids in preparing the raw materials. Tables 1 and 2 show the hydroxyl value, solid content, and number average molecular weight of the polymer.

  In Tables 1 and 2, the unit of the charged amount is g.

(Synthesis example 11)
Synthesis of PET-containing polyester polyurethane polyol (A2-1) PET-containing polyester polyol (A1-1) was placed in a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube, and a glass cooling tube. 500.0 g and 0.10 g of dibutyltin dilaurate are charged as a polymerization catalyst. When the temperature is raised to 60 ° C. under a normal pressure nitrogen stream, 15.0 g of isophorone diisocyanate (IPDI) is charged, the temperature is raised to 80 ° C., and the urethanization reaction is performed at 80 ° C. for 5 hours. After confirming that the viscosity reaches a predetermined value and that the residual isocyanate content is 0.05% or less, the temperature is lowered to 50 ° C., and the solid content is appropriately adjusted with ethyl acetate to obtain a PET-containing urethane-modified polyester polyol (A2-1). Obtained. Table 3 shows the acid value in terms of solid, the hydroxyl value in terms of solid, the solid content, and the number average molecular weight of the obtained PET-containing polyester polyurethane polyol (A2-1).

(Synthesis Example 12) to (Synthesis Example 20), (Comparative Synthesis Example 4) to (Comparative Synthesis Example 5)
Synthesis of PET-Containing Polyester Polyurethane Polyols (A2-2) to (A2-10) and Synthesis of PET-Decomposed Polyester Polyurethane Polyol (A2-11) (A2-12) PET-containing except for using the raw materials shown in Tables 3 and 4. It was manufactured in the same manner as the polyester polyurethane polyol (A2-1). Tables 3 and 4 show properties and the like. In Tables 3 and 4, IPDI is an abbreviation for isophorone diisocyanate.

(Examples and Comparative Examples)
Reactive adhesives for Examples and Comparative Examples were prepared by blending the polyol composition (A) and the polyisocyanate composition (B) in the ratios shown in Tables 5 to 7. The isocyanate (B) is a trifunctional polyisocyanate obtained by adding tolylene diisocyanate (TDI) to commercially available trimethylolpropane (TMP) (trade name: Dick Dry KW-75 manufactured by DIC, TDI-added product of TDI, solid content: 75) %).
Laminated films were prepared and evaluated according to the method of each evaluation item, and evaluated according to evaluation criteria. The results are shown in Tables 5 to 7.

(Evaluation)
(High-speed workability)
A dry laminator (Musashino Machinery Design Co., Ltd., dry lami test coater) was used as the laminating machine, the processing speed was 250 m / min, and the first plastic film layer was a PET film (a commercially available polyethylene terephthalate film). After applying the adhesive of Example or Comparative Example so that the coating amount was 3 g / m ² , VMCPP (a commercially available aluminum-deposited unstretched polypropylene film) was laminated as a second plastic film layer to obtain a laminated film.
Immediately after lamination, the appearance of the film (whether there was no problem such as wrinkles or bubbles due to bubbles or tunneling caused by a gap between the films) was judged visually and using a scale loupe based on the following evaluation criteria. The evaluation with the scale loupe was performed based on the number of bubbles in a 1 cm 2 scale.
Evaluation criteria
：: No bubbles, no wrinkles or tunneling ○: 1 to 4 bubbles, no wrinkles or tunneling ○-: 5 to 9 bubbles, no wrinkles or tunneling △: Bubbles Wrinkles and tunneling are partially generated in several tens to 16 ×: Wrinkles and tunneling are generated in many places with 17 or more bubbles

(Heat resistance (highlet resistance))
A dry laminator (Musashino Machine Design Co., Ltd., dry lami test coater) was used as the laminating machine, the processing speed was 250 m / min, and PET-AL (a commercially available aluminum foil was adhered as the first plastic film layer). Polyethylene terephthalate) was coated with the adhesive of Example or Comparative Example so that the coating amount was 4.3 g / m ^2, and then CPP (commercially unstretched polypropylene film) was laminated as a second plastic film layer. Thereafter, aging was performed at 40 ° C for 5 days under aging conditions to obtain a laminated film.
Using the obtained laminated film, a pouch having a size of 120 mm × 120 mm was prepared, and the pouch was filled with 70 g of a water / oil = 9/1 weight ratio as a content. After that, retort treatment was performed at 135 ° C. for 30 minutes in a high-pressure kettle, and evaluation was made by measuring peel strength.

The evaluation method was as follows. A test piece having a width of 15 mm was cut out from the pouch after the retort treatment using a Tensilon universal testing machine manufactured by Orientec Co., Ltd., and the contents were thoroughly wiped off. The tensile strength when peeled by the 180 ° peeling method was compared as the adhesive strength. The unit of the adhesive strength was N / 15 mm. If the adhesive strength is 5 N / 15 mm or more, it can be said that it is practically sufficient.
Evaluation criteria A: Adhesive strength 12 N / 15 mm or more O: Adhesive strength 7 N / 15 mm or more, less than 12 N / 15 mm O-: Adhesive strength 5 N / 15 mm or more, less than 7 N / 15 mm Δ: Adhesive strength 1 N / 15 mm or more and less than 5 N / 15 mm ×: Adhesion strength less than 1 N / 15 mm

(Content resistance)
Using a dry laminator (Dry Lami Test Coater, Musashino Machinery & Design Co., Ltd.) as a laminating machine, a processing speed of 250 m / min, Nyl (a commercially available nylon film) as a first plastic film layer, Alternatively, the adhesive of Comparative Example was applied so as to have an application amount of 4.3 g / m ^2, and then LLDPE (a commercially available linear low-density polyethylene film) was laminated as a second plastic film layer. Thereafter, aging was performed at 40 ° C for 5 days under aging conditions to obtain a laminated film.
Using the obtained laminated film, a pouch having a size of 120 mm × 120 mm was prepared, and 70 g of Super sol pH = 13 was filled in the pouch as a content. Thereafter, the treatment was carried out in a thermostat at 50 ° C. for 3 days, and evaluated by peel strength measurement.

The evaluation method was as follows: a test piece having a width of 15 mm was cut out from the pouch after the content resistance test using a Tensilon universal testing machine manufactured by Orientec Co., Ltd., and the content was thoroughly wiped off. / Min, tensile strength when peeled by 180 ° peeling method was compared as adhesive strength. The unit of the adhesive strength was N / 15 mm. If the adhesive strength is 2 N / 15 mm or more, it can be said that it is practically sufficient.
Evaluation criteria ：: Adhesive strength 7 N / 15 mm or more ：: Adhesive strength 5 N / 15 mm or more and less than 7 N / 15 mm-: Adhesive strength 2 N / 15 mm or more and less than 5 N / 15 mm △: Adhesive strength 1 N / 15 mm or more and less than 2 N / 15 mm ×: Adhesion strength less than 1 N / 15 mm

(Comparative Example 1) to (Comparative Example 5)
The adhesive composition shown in Table 8 and evaluation were performed in the same manner as in the example.

  According to the reactive adhesive of the present invention, it can be applied as an adhesive for a laminate obtained by appropriately combining various plastic films, metal-deposited films or metal foils, and even under high-speed coating conditions, high Not only can a laminated film having excellent adhesion and excellent appearance after lamination be obtained, but also a laminated film having excellent heat resistance and content resistance can be obtained.

Claims (7)

A reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) is prepared by batch charging of polyethylene terephthalate, a dihydric alcohol, and a polybasic acid. A method for producing a reactive adhesive, comprising a polyester polyol (A1) as a reaction product. The method for producing a reactive adhesive according to claim 1, wherein the proportion of polyethylene terephthalate in the raw material charged for the polyester polyol (A1) is 5 to 50% by mass. 3. The method for producing a reactive adhesive according to claim 1, wherein the polybasic acid is a dimer acid, and a ratio of the dimer acid in a raw material charged to 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). Production method. A method for producing a laminated film in which an adhesive layer is laminated between a first plastic film and a second plastic film, wherein the adhesive layer is obtained by the production method according to any one of claims 1 to 4 . A method for producing a laminated film, which is a layer of a reactive adhesive. It is a manufacturing method of the laminated film which laminate | stacks a 1st plastic film, a printing layer, an adhesive layer, and a 2nd plastic film in this order, The said adhesive layer is the manufacturing method in any one of Claims 1-4. A method for producing a laminated film, which is a layer of the reactive adhesive obtained in the above . A method for producing a package, wherein the laminated film obtained by the production method according to claim 5 or 6 is formed into a bag.