TW202031849A - Reactive adhesive agent, laminate, and package body - Google Patents

Abstract

A 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 by collective charging of 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, the polyol composition (A) also containing microparticles (C) that have an average particle diameter of at least 1*10<SP>-3</SP> mm and less than 0.5 mm; and the microparticles (C) are contained in the polyol composition (A) in an amount of at least 1 * 10<SP>-6</SP> mass% and less than 0.1 mass% with respect to the total resin solids content of the polyol composition (A).

Description

Reactive adhesives, laminates and packaging

The present invention relates to a reactive adhesive, a laminate and a package formed by using the reactive adhesive.

In the past, various plastic films were laminated to each other, and the laminated system of plastic film and metal vapor deposition film, metal foil laminated (laminated) was used in various applications, such as packaging materials and barrier materials for food, medicine, and daily necessities. , Roofing materials, solar cell panel materials, battery packaging materials, window materials, outdoor floor materials, lighting protection materials, automotive components, signs, labels and other outdoor industrial uses, and decorative uses such as injection molding and decoration methods. These laminates can be appropriately combined with various plastic films, metal vapor-deposited films or metal foils according to the required characteristics in various applications, and an adhesive corresponding to the required characteristics can be selected. For example, as long as it is food and daily necessities, functions such as strength, resistance to breakage, sterilization resistance, heat resistance, and content resistance are required in order to protect the contents from various distribution, storage such as refrigeration, heat sterilization, and the like. Or in outdoor industrial applications, weather resistance and hydrolysis resistance are required to maintain adhesion for a long time even in the open air environment. Furthermore, these laminates are rarely circulated in the form of sheets. For example, they may be made into a bag shape with the end heat-sealed, or they may be molded by thermoforming, or they may require heat-sealability and moldability. .

As an adhesive used for such a laminate, a reactive adhesive (also referred to as a two-component adhesive) that reacts a hydroxyl group with an isocyanate is known. For example, in food applications, an adhesive is known, which is an adhesive containing a diol compound (A) having two hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups. The number average molecular weight (Mn) of the diol compound (A) is in the range of 400 to 3000, and the polyisocyanate (B) is obtained by adding a polyisocyanate compound (b1) having a valence of three or more to the polyester diol. A mixture of the diisocyanate compound (b2) (for example, refer to Patent Document 1). An adhesive for laminate is known, which is an adhesive for laminate films of battery packaging materials. It contains a polyol component and a polyurethane polyester polyol with a number average molecular weight of 5000 or more and less than 14000. The sum of the content of the urethane bond and the content of the isocyanate group is within a specific range; this laminate adhesive system is excellent in molding processability and moisture and heat resistance (for example, refer to Patent Document 2).

These reactive adhesives require characteristics corresponding to various uses. For example, the adhesive before two-component mixing requires storage stability over time (this means that when stored in a warehouse, etc., it can withstand outdoor temperatures, especially even at high temperatures in summer. Tolerable); or from the viewpoint of productivity, for example, even if the coating speed is 200m/min or more, it is required to obtain a laminate without appearance defects. However, under such high-speed coating (also known as high-speed processing) conditions, it is needless to say that the solvent-free reactive adhesive does not use organic solvents, even if it is a dry laminated type reaction that can use organic solvents to adjust the viscosity Depending on the base material, the situation of the sexual adhesive is also prone to the appearance of poor orange peel. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2014-101422 A [Patent Document 2] JP 2016-196580 A [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-3815 [Patent Document 4] JP 2010-248345 A

[The problem to be solved by the invention]

The problem to be solved by the present invention is to provide a reactive adhesive, which can be suitably used as an adhesive for a laminate of various plastic films, metal vapor-deposited films, or metal foils, and has excellent storage stability over time, and even in Under high-speed coating conditions, a laminate with high adhesion and excellent appearance after lamination processing can also be obtained. [Means to solve the problem]

The inventors of the present invention found a reactive adhesive to solve the aforementioned problems, which is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), characterized in that the polyol composition (A) contains Polyethylene terephthalate, polyester polyol (A1), which is the reaction product of a one-time input of polyol and polyacid, and the total resin solid content of the aforementioned polyol composition (A) That is, the particles (C) having an average particle size of 1×10 ^-6 mass% or more and less than 0.1 mass %, and 1×10 ^-3 mm or more and less than 0.5 mm.

An adhesive using a polyester polyol using polyethylene terephthalate as a raw material is known (for example, refer to Patent Documents 3 and 4). For example, Patent Document 3 discloses a reactive adhesive that contains a polyester polyol and a polyisocyanate curing agent. The polyester polyol decomposes polyethylene terephthalate in the reaction with a low molecular polyol. Polyester polyol obtained by condensation reaction of the decomposition product and polybasic acid. However, although Patent Document 3 evaluates a laminated film produced by applying an adhesive at a film speed of 50 m/min, it does not describe or suggest a form produced under high-speed coating conditions at a coating speed of 200 m/min or more. In addition, Patent Document 4 discloses the use of a polyol compound obtained by depolymerizing polyester (a) with a polyol (b) having two or more hydroxyl groups in one molecule as a raw material for the adhesive, but it is also aimed at films The evaluation of the laminate film laminated after coating with a film thickness of 30 μm by the applicator is used as the evaluation of the adhesive, and there is no description or suggestion of the form produced under high-speed coating conditions with a coating speed of 200 m/min or more. That is, the fact is that even if polyester polyols using polyethylene terephthalate as the raw material are used, under high-speed coating conditions at a coating speed of 200 m/min or more, it has high adhesion and excellent appearance after lamination processing. Reactive adhesives have not yet come out.

The inventors of the present invention understand that polyester polyols obtained by the methods disclosed in Patent Documents 3 and 4 have poor appearance during high-speed coatability. On the other hand, they have discovered that as long as they contain poly(ethylene terephthalate) and The polyester polyol (A1), which is the reaction product of the one-time input of alcohol and polybasic acid, and the total resin solid content of the aforementioned polyol composition (A) is 1×10 ^-6 mass% or more and less than 0.1 The polyol composition (A) with the average particle size of 1×10 ^-3 mm or more and fine particles (C) less than 0.5 mm in mass% can be obtained with excellent storage stability over time and less appearance defects during high-speed coatability. , And has high adhesiveness after lamination processing, especially a laminate with heat resistance and content resistance, and has completed the present invention.

That is, the present invention provides a reactive adhesive, which is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), and is characterized in that the polyol composition (A) contains Polyester polyol (A1) and/or polyester polyol (A1) of the reaction product of the reaction product of ethylene terephthalate, polyol and polybasic acid and/or the reaction product of polyester polyol (A1) and isocyanate compound Urethane polyol (A2), and fine particles (C) with an average particle size of 1×10 ^-3 mm or more and less than 0.5 mm, relative to the total resin solid content of the polyol composition (A), containing 1 ×10 ^-6 mass% or more and less than 0.1 mass% of the aforementioned fine particles (C).

In addition, the present invention provides a laminated body in which an adhesive layer is laminated between a first plastic film and a second plastic film, wherein the adhesive layer is a layer of the reactive adhesive described above.

In addition, the present invention provides a laminate in which a first plastic film, a printing layer, an adhesive layer, and a second plastic film are laminated in this order, wherein the adhesive layer is the reactive adhesive described above The layer of agent.

In addition, the present invention provides a package formed by molding the aforementioned laminate into a bag shape.

In addition, the present invention provides a method for producing a polyester polyol (A1), which includes a step of adding polyethylene terephthalate, a polyol, and a polybasic acid at once and reacting them, followed by filtering with a filter.

In addition, the present invention provides a method for producing polyester polyurethane polyol (A2), which has a poly(ethylene terephthalate), a polyol, and a polyacid that are reacted at one time. After the ester polyol (A1) reacts with the polyisocyanate, it is a step of filtering with a filter. [Effects of Invention]

The reactive adhesive of the present invention can be suitably used as an adhesive for a laminate of various plastic films, metal vapor-deposited films, or metal foils. It has excellent storage stability over time, and can be used even under high-speed coating conditions. A laminate with high adhesion and excellent appearance after lamination processing. Furthermore, since it is excellent in heat resistance and content resistance, it can be particularly ideally used as a food packaging bag.

[Form to implement the invention]

The present invention is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), and is characterized in that the aforementioned polyol composition (A) contains polyethylene terephthalate, polyol Polyester polyol (A1) and/or polyester polyol (A1) and isocyanate compound reaction product of a one-time input of polyacid , And particles (C) with an average particle size of 1×10 ^-3 mm or more and less than 0.5 mm, relative to the total resin solid content of the polyol composition (A), containing 1×10 ^-6 mass% or more and less than 0.1 mass % Of the aforementioned particles (C).

(Polyol composition (A)) The polyester polyol (A1) contained in the aforementioned polyol composition (A) is a reaction product of polyethylene terephthalate, a polyol and a polybasic acid by throwing in at once.

(Polyester polyol (A1)) The polyethylene terephthalate (hereinafter sometimes referred to as PET) used in the present invention is obtained by polycondensation of terephthalic acid or dimethyl terephthalate and ethylene glycol, or Further, according to needs, those modified with substances such as isophthalic acid, phthalic anhydride, adipic acid, cyclohexane dicarboxylic acid, 1,3-butanediol, and cyclohexane dimethanol are used. Furthermore, it can be used: pulverizing defective products in the manufacture of unused PET bottles, PET films, and other PET products on the market, recycled PET recovered and washed from waste, etc. Among them, it is better to use recycled PET. These can be cleaned and granulated from the market.

The intrinsic viscosity (IV) of PET is preferably 0.50-0.80dL/g. With this range, the polycondensation reaction of PET and other raw materials can be carried out below 250°C. Moreover, this range is also preferable from the viewpoint that the reactive adhesive containing the PET-containing polyester polyol exhibits adhesive strength, durability, and heat resistance.

As the polyol used in the present invention, well-known polyols can be used without particular limitation. Examples include: 1,2-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,3- Aliphatic diols such as butanediol, 2,2,4-trimethyl-1,3-pentanediol; 1,3-bis(2-hydroxypropyl)cyclopentane, 1,3-bis(2 -Hydroxybutyl)cyclopentane, 1,4-bis(2-hydroxypropyl)cyclohexane, 1,4-bis(2-hydroxybutyl)cyclohexane and other alicyclic diols; 1,4 -Bis(2-hydroxypropyl)benzene, 1,4-bis(2-hydroxybutyl)benzene and other aromatic diols;

In 2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as “bisphenol A”), 2,2-bis(4-hydroxyphenyl)butane (hereinafter referred to as “bisphenol B”), Bis(4-hydroxyphenyl)methane (hereinafter referred to as "bisphenol F"), bis(4-hydroxyphenyl) sulfite (hereinafter referred to as "bisphenol S") and other bisphenol addition 1,2-epoxy Alkylene oxide adducts of bisphenols derived from alkylene oxides with secondary hydroxyl groups such as propane and 1,2-butylene oxide; ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4- Butylene glycol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-butyl-2- Aliphatic polyols such as ethyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and neopentylerythritol; polyoxyethylene two Ether glycols such as alcohol and polyoxypropylene glycol;

With the aforementioned aliphatic polyols and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, and phenyl glycidyl ether Modified polyether polyols obtained by ring-opening polymerization of various compounds containing cyclic ether bonds such as allyl glycidyl ether; by combining the aforementioned aliphatic polyols and various lactones such as ε-caprolactone Lactone polyester polyol obtained by polycondensation reaction; Bisphenol A, Bisphenol F, Bisphenol S, etc.; Bisphenol A, Bisphenol F and other bisphenols added with ethylene oxide Ethylene oxide adducts, etc.

These may be used individually, respectively, and may use 2 or more types together. 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, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, trimethylol Aliphatic polyhydric alcohols such as propane, glycerin, hexanetriol and neopentylerythritol are preferred, and 1,6-hexanediol is preferred.

As the polybasic acid used in the present invention, well-known polybasic acids can be used without particular limitation. Examples include: phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, phthalic acid and other aromatic dicarboxylic acids; malonic acid, succinic acid, glutaric acid, adipic acid Aliphatic dicarboxylic acids such as acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexahydrophthalic acid, 1,4-cyclohexanedicarboxylic acid; maleic acid, maleic anhydride, citrus Conic acid, dimethyl maleic acid, cyclopentene-1,2-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, fumaric acid , Mesaconic acid, itaconic acid, glutenedioic acid and other aliphatic unsaturated dicarboxylic acids; 1,2,5-hexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid and other aliphatic tricarboxylic acids ; Aromatic tricarboxylic acids such as trimellitic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and dimer acids. These may be used individually, respectively, and may use 2 or more types together. Among them, dimer acid is preferred.

The manufacturing method of reacting PET, polyol and polybasic acid at once can be arbitrarily manufactured by the known polycondensation reaction method. Specifically, PET, polyol and polybasic acid can be put into the manufacturing device under nitrogen atmosphere The temperature is raised to 180°C or higher while stirring, and it is implemented by any production method such as normal pressure dehydration reaction, reduced pressure and vacuum dehydration reaction, solution polycondensation method, and solid phase polycondensation reaction. When using the PET, polyhydric alcohol and polybasic acid described in this case, the reduced pressure dehydration reaction can be applied at a reaction temperature below 230°C, and the reaction time can be set to about 5 hours. The progress of the polycondensation reaction can be confirmed by measuring acid value, hydroxyl value, viscosity, or softening point. As the manufacturing device used at this time, for example, in addition to a batch-type manufacturing device equipped with a reaction vessel such as a nitrogen inlet, a thermometer, a stirring device, a rectification tower, etc., an extrusion device with a degassing port can also be used. Machine, continuous reaction device, kneader, etc. It is also possible to further use an esterification catalyst (tin compound, titanium compound, zirconium compound, etc.) as needed to promote the esterification reaction. In addition, the method of transesterifying PET in a polyol, and the method of polycondensing the transesterified reactant with a polybasic acid will decompose the ethylene terephthalate unit in a scattered manner. The polyol is used in adhesives, but it cannot achieve the appearance, adhesive strength, heat resistance and content resistance of high-speed coating for the purpose of the project.

(Better combination of raw materials) Among the aforementioned polyester polyols (A1), 1,6-hexanediol is used as the polyol and the dimer acid is used as the polyacid. At this time, the weight fraction of 1,6-hexanediol is preferably 5-20% by mass in terms of the ratio of the aforementioned polyester polyol (A1) input raw materials, and 6-18% by mass Better. In addition, the weight fraction of the dimer acid is preferably 5-20% by mass, and more preferably 6-18% by mass in terms of the ratio of the aforementioned polyester polyol (A1) to the input raw materials.

In addition, the aforementioned PET is based on the input raw material (that is, the ratio of the total amount of polyol and polybasic acid) of the aforementioned polyester polyol (A1) as 5 to 100% relative to the total amount of polyol and polybasic acid. It is preferably 50% by mass, more preferably 8 to 48% by mass.

In this case, as the raw material of polyester polyol (A1), by synthesizing long-chain unsaturated dibasic acid such as dimer acid, 1,6-hexanediol and other monomers together with PET, Adhesive that has better adhesion strength, heat resistance and content resistance to the substrate. The reason for this has not been determined, but it is assumed that as long as it has this composition, it becomes possible to proceed at a reaction temperature of 220°C, whereby the ethylene terephthalate unit in the resulting reaction product becomes difficult to be caused by long-chain unsaturated groups. It decomposes and remains in the state of a high-molecular-weight body, and it is estimated that it contributes to the appearance, adhesive strength, heat resistance, and content resistance during high-speed coating. In addition, as a polyol, in the case of triol (trimethylolpropane), the ethylene terephthalate unit in PET may be fully decomposed, and it will not proceed if the reaction temperature is not higher than 220°C. The polyol is preferably a diol such as 1,6-hexanediol.

(Acid value, hydroxyl value) From the viewpoint of hydrolysis resistance, the acid value of the polyester polyol (A1) is preferably 5.0 or less, and from the viewpoint of the reactivity of the adhesive, 3.0 or less is more preferable. In addition, from the viewpoint of high-speed coatability, the hydroxyl valence is preferably 50 or less, and more preferably 40 or less. In addition, in the present invention, the acid value and the hydroxyl value are measured by the following methods, and unless otherwise specified, they represent values converted to solid content.

(Acid value) Weigh 5-10g of polyester polyol in a 100ml Erlenmeyer flask. Set the weighing amount to (S). It was dissolved in 30 ml of tetrahydrofuran. After adding 2 to 3 drops of phenolphthalein as an indicator, it is titrated with a 0.1 mol/L potassium hydroxide alcohol solution. The time point at which the reddish color lasted for 30 seconds was regarded as the end point, and the acid value was calculated from the titer (V) at that time by the following formula. In addition, the strength value of the 0.1 mol/L potassium hydroxide alcohol solution is set as (F).

Acid value=(V×F×5.61)/S

(Hydroxyl value) Weigh 6-10g of polyester polyol in a 300ml Erlenmeyer flask. Set the weighing amount to (S). 25ml of pre-made acetylating agent was added to it to dissolve it. A cooling tube was installed at the mouth of the Erlenmeyer flask, and the acetylation reaction was carried out at 100°C for 1 hour. Add 10 ml of ion exchange water and cool to room temperature. After adding 2 to 3 drops of phenolphthalein as an indicator, it is titrated with a 0.5mol/L potassium hydroxide alcohol solution. The titration amount (V) at that time was taken as the end point when the reddish color appeared for 30 seconds to calculate the hydroxyl value using the following formula. In addition, a blank test was carried out at the same time and the titration amount at this time was set as (B). Set the strength value of 0.5 mol/L potassium hydroxide alcohol solution as (F). Separately determine the acid value in advance.

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 from the viewpoint of an appropriate resin viscosity at the time of coating, it is usually preferably adjusted to the range of 2000 to 12000, and more preferably 3000 to 8000.

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

Measuring device: HLC-8220GPC manufactured by TOSOH Co., Ltd. Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by TOSOH Co., Ltd. ＋TOSOH Co., Ltd. TSK-GEL SuperHZM-M×4 Detector: RI (differential refractometer) Data processing: Multi Station GPC-8020modelII manufactured by TOSOH Co., Ltd. Measurement conditions: column temperature 　40℃ Solvent 　 tetrahydrofuran Flow rate　0.35ml/min Standard: Monodisperse Polystyrene Sample: 0.2% by mass of tetrahydrofuran solution in terms of resin solid content is filtered with a microfilter (100μl)

(Polyester polyurethane polyol (A2)) The polyester polyol (A2) contained in the polyol composition (A) is a polyester polyol (A2) obtained by further reacting the polyester polyol (A1) with an isocyanate compound ( A2). The polyisocyanate compound used in the present invention can be used without particular limitation, and known ones can be used alone or in combination of a plurality of them. For example, toluene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, etc. have aromatics in the molecular structure Structured polyisocyanates, compounds in which part of the isocyanate groups (sometimes called NCO groups) of these polyisocyanates are modified with carbodiimide;

Alphanate compounds derived from these polyisocyanates; isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl) cyclohexane, etc. in the molecular structure Polyisocyanate with alicyclic structure; straight-chain aliphatic polyisocyanate such as 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, etc., and the Alphanate compound; Isocyanurate bodies of these polyisocyanates; allophanate bodies derived from these polyisocyanates; biuret bodies derived from these polyisocyanates; trimethylolpropane modified adducts;

The polyisocyanate etc. which are the reaction products of the aforementioned various polyisocyanate compounds and polyols.

From the viewpoint of reaction stability, among them, diisocyanate is preferred, and isophorone diisocyanate is the most preferred.

From the viewpoint of hydrolysis resistance, the aforementioned polyester polyurethane polyol (A2) preferably has an acid value of 5.0 or less, and from the viewpoint of the reactivity of the adhesive, it is 3.0 or less Better. In addition, from the viewpoint of heat resistance and content resistance, the hydroxyl valence is preferably 30 or less, and more preferably 25 or less.

(Fine particles (C)) The particles (C) contained in the aforementioned polyol composition (A) are particles (C) having an average particle size of 1×10 ^-3 mm or more and less than 0.5 mm. In the present invention, the average particle diameter is the average particle diameter measured by the following method.

[Average particle size of particles] Dilute the polyol composition in which the fine particles are dispersed with an appropriate solvent, and use the diluted solution to measure the average particle size on a volume basis by the laser scattering method (laser diffraction particle size distribution analyzer SALD-2300 (Shimadzu Corporation) ). When adding particles, the refractive index inherent to the particles is used. When the fine particles of polyethylene terephthalate are contained in advance, the refractive index is measured as 1.4.

When the average particle diameter of the aforementioned fine particles (C) is larger than "less than 0.5 mm", the storage stability may deteriorate over time. Among them, it is more preferable that the average particle size is 1×10 ^-3 mm or more and less than 0.4 mm, and the best is 1×10 ^-3 mm or more and less than 0.3 mm.

The aforementioned fine particles (C) may be fine particles having any one of an organic compound and an inorganic compound as a main component, and an organic compound is particularly preferred. Among them, organic polymer compounds are preferred. Examples include: polyester resin particles, polyurethane resin particles, polyethylene, polybutene, polypropylene, and other polyolefin resin particles, including styrene Polymer particles with polyolefins, particles containing their hydrogenated products, cellulose, cellulose resin particles, silicone particles, melamine resin particles, acrylic resin particles (e.g. polymethyl methacrylate resin particles) Etc.), acrylic-styrene-based copolymer particles, polycarbonate-based particles, polystyrene-based particles, benzoguanidine-based resin particles, etc. These resins can also become composite resins. In addition, these can be crosslinked or non-crosslinked, and are not particularly limited. Examples of other organic compounds include organic pigments. Examples of the inorganic compound include inorganic fillers such as silica, alumina, mica, talc, thin aluminum flakes, and glass flakes, and layered inorganic compounds. The fine particles having organic compounds and inorganic compounds as main components may be used alone or in combination of two or more kinds.

The fine particles (C) preferably contain 1×10 ^-3 mass% or more and less than 0.1 mass% with respect to the total resin solid content of the polyol composition (A). It is possible to obtain a reactive adhesive that has excellent storage stability over time and can obtain a laminate having high adhesiveness and excellent appearance after lamination processing even under high-speed coating conditions. Among them, the content is preferably 1×10 ^-6 mass% or more and less than 0.08 mass%, and more preferably 1×10 ^-3 mass% or more and less than 0.05 mass%.

The fine particles (C) may be added in the desired amount after synthesizing the polyester polyol (A1) as the main component of the polyol composition (A), or may be added in advance during the reaction of the polyester polyol (A1). When a commercially available product is used to add fine particles, it is possible to remove fine particles other than the average particle size corresponding to the aforementioned fine particles (C) by filtration or the like. In the present invention, polyethylene terephthalate is used as the raw material of the aforementioned polyester polyol (A1), and fine particles preliminarily contained in the polyethylene terephthalate can also be used. In particular, when using a product that crushes defective products in the manufacture of unused PET bottles, PET films, and other PET products on the market, or recycled PET recovered and washed from waste, it contains particles equivalent to the aforementioned particles (C) Many particles of average particle size can also be used. When the fine particles contained in the polyethylene terephthalate are used, the fine particles other than the average particle diameter corresponding to the aforementioned fine particles (C) can be removed by filtration or the like. In addition, the content can be set to the desired content by measuring the amount of fine particles contained in the polyethylene terephthalate in advance, and using the desired amount of polyethylene terephthalate as a raw material. When the content of the fine particles contained in the polyethylene terephthalate is unknown, the turbidity of the solution of the polyol composition diluted with an appropriate solvent is measured from the turbidity unit "NTU (Nephelometric Turbidity Unit)" The degree is converted to mass, and the content can also be calculated.

Examples of specific methods such as filtration include: removal of particulates by filtration using a filter or filter paper. Also, it can also be used: sedimentation by centrifugal separation, cooling precipitation, etc. Among them, the step of filtering with a filter is the easiest and preferred. Specifically, by throwing in polyethylene terephthalate, polyol and polybasic acid at one time and reacting, filtering with a filter, it is possible to obtain The polyester polyol (A1), which is the reaction product of the one-time input of alcohol and polybasic acid, and the total resin solid content of the aforementioned polyol composition (A) is 1×10 ^-6 mass% or more and less than 0.1 The aforementioned polyol composition (A) having an average particle diameter of 1×10 ^-3 mm or more and less than 0.5 mm (C).

As the material of the filter used here, for example, polypropylene, polyester, polyethylene, polypropylene, rayon, nylon, fluororesin, cellulose and other fibers, glass fibers, and impregnation of these Phenolic resin, epoxy resin, etc. Also, these can be used together. The filter mesh is preferably 5 μm, which is commonly used, and is not particularly limited. Specifically, the Cuno Filter Cartridge made by Nihon Pall (model: 5RPN19.5, material: polyester fiber impregnated with phenol resin), Cuno Filter Cartridge made by Nihon Pall (model: XFRPN19.5, material: impregnated with phenol resin) The polyester fiber) and so on. The filtration can be repeated by circulating filtration, etc., until the particles reach the target average particle size and content.

(Other polyols) In the present invention, in addition to the aforementioned polyester polyol (A1), in addition to the aforementioned polyester polyol (A1), the aforementioned polyol itself, selected from poly(ethylene terephthalate) which does not use polyethylene terephthalate as a raw material, can be used together in the present invention. Ester polyol, polyether polyol, polyurethane polyol, polyether ester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, Polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyalkane, castor oil or polymer polyol of a mixture of these, etc.

When other polyols are used in combination, the ratio of the aforementioned polyester polyol (A1) in the polyol composition (A) is preferably 1-50% by mass, and more preferably 1-40% 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 can be used without particular limitation, and known ones can be used alone or in combination of a plurality of them. For example, toluene diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, etc. have aromatics in the molecular structure Structured polyisocyanates, compounds in which part of the isocyanate groups (sometimes called NCO groups) of these polyisocyanates are modified with carbodiimide;

Alphanate compounds derived from these polyisocyanates; isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl) cyclohexane, etc. in the molecular structure Polyisocyanate with alicyclic structure; straight-chain aliphatic polyisocyanate such as 1,6-hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate, etc., and the Alphanate compound; Isocyanurate bodies of these polyisocyanates; allophanate bodies derived from these polyisocyanates; biuret bodies derived from these polyisocyanates; trimethylolpropane modified adducts;

The polyisocyanate etc. which are the reaction products of the aforementioned various polyisocyanate compounds and polyols.

Among the aforementioned polyisocyanates of the reaction products of various polyisocyanate compounds and polyols, polyols can be used: polyols of the raw materials of the polyol composition (A), the polyester polyol (A1), and the polyester Polyol (A1-2), selected from polyester polyols, polyether polyols, polyurethane polyols, polyether ester polyols, polyesters that do not use polyethylene terephthalate as raw materials (Polyurethane) polyol, polyether (polyurethane) polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyalkane, castor oil or the like The mixture of polymer polyols, etc. From the viewpoint of adhesive strength, heat resistance, and content resistance, among them, it is preferable to use a polyisocyanate that is a reaction product of the aforementioned various polyisocyanates and the aforementioned polyester polyol (A1). From the viewpoint of the balance between the cohesive force and flexibility of the adhesive coating film, the reaction ratio of the polyisocyanate compound and the polyol is based on the equivalent ratio of isocyanate groups to hydroxyl groups [isocyanate group/hydroxy group] in the range of 1.0 to 5.0 For better.

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

(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-based or solvent-free adhesive. In addition, the “solvent” of the solvent-free adhesive referred to in the present invention refers to an organic solvent with high solubility that can dissolve the polyisocyanate compound and polyol compound used in the present invention, and “solvent-free” refers to not containing These highly soluble organic solvents. Specifically, organic solvents with high solubility include toluene, xylene, dichloromethane, tetrahydrofuran, methanol, ethanol, isopropanol, methyl acetate, ethyl acetate, n-butyl acetate, Acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, cyclohexane, etc. Among them, toluene, xylene, dichloromethane, tetrahydrofuran, methyl acetate, and ethyl acetate are known as particularly highly soluble organic solvents. On the other hand, when the adhesive of the present invention is required to have low viscosity, etc., it can be suitably diluted with the aforementioned highly soluble organic solvent according to the desired viscosity. In this case, either the polyisocyanate composition (B) or the polyol composition (A) can be diluted and both can be diluted. As the organic solvent used in such a case, for example, methanol, ethanol, isopropanol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, Toluol, xylol, n-hexane, cyclohexane, etc. From the viewpoint of solubility, among these, ethyl acetate and methyl ethyl ketone (MEK) are preferred, and ethyl acetate is particularly preferred. The amount of organic solvent used depends on the desired viscosity, and it is often used in the range of about 20-50% 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 based on the excellent adhesive strength and heat resistance during heat sealing. The equivalent ratio [isocyanate group/hydroxyl] of the isocyanate group in the polyisocyanate compound contained in the polyisocyanate composition (B) to the hydroxyl group in the polyol compound contained in the polyol composition (A) is The range of 0.6-5.0 is preferable, and the range of 1.0-3.5 is especially preferable from a viewpoint that these performances become remarkable.

(Aliphatic cyclic amide compound) The reactive adhesive of the present invention, as described in detail, has the aforementioned polyol composition (A) and the aforementioned polyisocyanate composition (B) as essential components, and by further mixing an aliphatic cyclic amide compound in the aforementioned The polyol composition (A) and any component of the aforementioned polyisocyanate composition (B), or blending as the third component during coating, can effectively suppress the harmful low-pressure components represented by aromatic amines in the laminated package. The molecular chemicals dissolve into the contents.

The aliphatic cyclic amide compounds used here include, for example, δ-valerolactam, ε-caprolactam, ω-heptanolactam, η-caprolactam, β-propiolactin (β-propiolactam) and so on. From the viewpoint of the excellent effect of reducing the dissolution amount of low-molecular-weight chemical substances, ε-caprolactam is preferred among these. In addition, the blending amount of the aliphatic cyclic amine compound is preferably 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, it is possible to effectively inhibit the elution of harmful low-molecular chemical substances represented by aromatic amines into the contents of the laminated package. The catalyst used in the present invention is not particularly limited as long as it is used to promote the urethane reaction. For example, metal-based catalysts, amine-based catalysts, diazebicycloundecene (DBU), and fatty acids can be used. Cyclic amide compounds, titanium chelate complexes and other catalysts.

Examples of metal-based catalysts include metal complexes, inorganic metal, and organic metal. The metal complexes are specifically selected from those containing Fe (iron), Mn (manganese), and Cu( Copper), Zr (zirconium), Th (thorium), Ti (titanium), Al (aluminum), Sn (tin), Zn (zinc), Bi (bismuth) and Co (cobalt) Acetone, for example, iron acetone acetonate, manganese acetone acetonate, copper acetone acetonate, zirconium dioxide acetone acetonate, etc., from the viewpoint of toxicity and catalyst activity, among these Iron acetone acetonate (Fe(acac) ₃ ) or manganese acetone acetonate (Mn(acac) ₂ ) is preferred.

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

Examples of organometallic catalysts include: stannous acetate, stannous octoate, stannous oleate, stannous laurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride Butyl tin, dioctyl tin dilaurate, nickel octoate, nickel naphthenate, cobalt octoate, cobalt naphthenate, bismuth octoate, bismuth naphthenate, bismuth neodecanoate, etc. Among these, the preferred compound is an organotin catalyst, more preferably stannous octoate and dibutyl tin dilaurate.

啶、2-甲基

啶等。從觸媒活性優異且工業上可取得的觀點來看，此等之中又以三伸乙二胺、2-甲基三伸乙二胺為較佳。The tertiary amine catalyst is not particularly limited as long as it is a compound having the above-mentioned structure. For example, triethylenediamine, 2-methyltriethylenediamine,

Pyridine, 2-methyl

Pyridine etc. From the viewpoint of excellent catalyst activity and industrial availability, among these, triethylenediamine and 2-methyltriethylenediamine are preferred.

Examples of other tertiary amine catalysts include: N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N ,N',N”,N”-pentamethylethylenetriamine, N,N,N',N”,N”-pentamethyl-(3-aminopropyl)ethylenediamine, N ,N,N',N”,N”-pentamethyldipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylamino Ethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyethyl)ethylenediamine , N,N-Dimethyl-N'-(2-hydroxyethyl)propane diamine, bis(dimethylaminopropyl)amine, bis(dimethylaminopropyl)isopropanolamine, 3-quinuclidinol, N,N,N',N'-tetramethylguanidine, 1,3,5-ginseng(N,N-dimethylaminopropyl)hexahydro-S -Three 𠯤, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl) piper𠯤, N,N'-di Methyl piperidine, dimethylcyclohexylamine, N-methylpyridine, N-ethylpyridine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methyl Imidazole, 1-dimethylaminopropyl imidazole, N,N-dimethylhexanolamine, N-methyl-N'-(2-hydroxyethyl)piperidine, 1-(2-hydroxyethyl) Yl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2-methylimidazole, etc.

Examples of the aliphatic cyclic amide compound include: δ-valerolactam, ε-caprolactam, ω-heptanolactam, η-caprolactam, β-propiolactam (β-propiolactam) Wait. Among these, ε-caprolactam is more effective in promoting hardening.

Titanium chelate complexes are compounds that increase the catalytic activity by ultraviolet radiation. From the standpoint of excellent hardening promotion effect, titanium chelate complexes with aliphatic or aromatic diketones as ligands are preferred good. Furthermore, in the present invention, from the viewpoint of becoming a more significant effect of the present invention, as the ligand, in addition to an aromatic or aliphatic diketone, an alcohol having 2 to 10 carbon atoms is preferred. In the present invention, the aforementioned catalyst may be used alone or in combination.

The mass ratio of the aforementioned catalyst is based on 100 parts of the mixture of polyisocyanate composition (B) and polyol composition (A), preferably in the range of 0.001 to 80 parts, and more preferably in the range of 0.01 to 70 parts. good.

紫(Dioxazine Violet)等各種二㗁𠯤系顏料；Cromophtal等各種縮合偶氮顏料；苯胺黑等。The reactive adhesive of the present invention can be combined with pigments as needed. The pigments that can be used at this time are not particularly limited, and examples include extender pigments, white pigments, black pigments, gray pigments, red pigments, brown pigments, which are described in the 1970 edition of the Paint Material Handbook (edited by the Japan Paint Industry Association). Organic pigments and inorganic pigments such as green pigments, blue pigments, metallic powder pigments, luminescent pigments, pearl pigments, and plastic pigments can be mentioned. Various specific examples of these colorants have been disclosed. Examples of organic pigments include various insoluble azo pigments such as Benzidine Yellow, Hansa Yellow, and Raked 4R; Raked C, Magenta 6B (Carmine 6B), Bordeaux 10 (Bordeaux 10) and other soluble azo pigments; Phthalocyanine Blue (Phthalocyanine Blue), Phthalocyanine Green (Phthalocyanine Green) and other (copper) phthalocyanine pigments; Rose Red Lake (Rhodamine) Various chlorine-based dyeing lakes such as Methyl Violet Lake and Methyl Violet Lake; various mordant dye-based pigments such as Quinoline Lake and Fast Sky Blue; anthraquinone-based pigments, thioindigo Various vat dye-based pigments such as series pigments and percyclic ketone pigments; various quinacridone pigments such as Cinquasia Red B; two

Dioxazine Violet and other dioxazine pigments; Cromophtal and other condensed azo pigments; aniline black, etc.

Examples of inorganic pigments include: various chromates such as chrome yellow, zinc chromate, molybdenum orange, etc.; various ferrocyanides such as Prussian blue; titanium oxide, zinc bloom, Mapico Yellow, iron oxide, Bengala, chromium oxide Various metal oxides such as green and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and cinnabar; various sulfates such as barium sulfate and lead sulfate; various silicates such as calcium silicate and ultramarine blue; calcium carbonate, carbonic acid Various carbonates such as magnesium; various phosphates such as cobalt violet and manganese violet; various metal powder pigments such as aluminum powder, gold powder, silver powder, copper powder, bronze powder, and brass powder; flake pigments, mica, flakes of these metals Pigments; Metallic pigments such as mica, flake pigments, mica-like iron oxide pigments, and pearlescent pigments in the form of coating metal oxides; graphite, carbon black, etc.

Extender pigments include, for example, precipitating barium sulfate, Paris White, precipitating calcium carbonate, bicarbonate, cold water stone, alumina white, silica, hydrous micropowder silica (white Carbon), ultrafine powdered anhydrous silica (Aerosil), silica sand (silica sand), talc, settling magnesium carbonate, bentonite, clay, kaolin, loess, etc.

Furthermore, as the plastic pigment, for example, "Grandoll PP-1000" and "PP-2000S" manufactured by DIC (Stock) can be cited.

As the pigment used in the present invention, due to its excellent durability, weather resistance and design, it is more preferable to use inorganic oxides such as titanium oxide and zinc bloom as white pigments, and carbon black as black pigments.

The mass ratio of the pigment used in the present invention is set to 1 to 400 parts by mass relative to the total of 100 parts by mass of isocyanate component B and polyol component A, among which it is set to 10 to 300 parts by mass due to adhesiveness and resistance. Excellent and better adhesion, etc.

(Following accelerator) In addition, the reactive adhesive used in the present invention may also use an adhesive accelerator in combination. Examples of accelerators 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, and N-β(aminoethyl)-γ-aminopropyltrimethoxy Amino silane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc.; β- (3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl triethoxy silane, etc.; Vinyl ginseng (β-methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane, γ-methacryloxy propyl trimethoxy silane and other vinyl silanes; six Methyl disilazane, γ-mercaptopropyl trimethoxysilane, etc.

As the titanate coupling agent, for example, titanium tetraisopropoxide, titanium tetra-n-butoxide, butyl titanate dimer, tetrastearyl titanate, titanium acetone acetonate, titanium lactate, tetra Octanediol titanate, titanium lactate, titanium tetrastearyl oxide, etc.

In addition, as an aluminum coupling agent, for example, Acetoalkoxy Aluminium Diisopropylate and the like can be cited.

Examples of epoxy resins include: generally commercially available Epi-Bis type, novolac type, β-methylepichlorohydrin type, cyclic ethylene oxide type, glycidyl ether type, and epoxypropyl Ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polyvalent carboxylic acid ester type, aminoglycidyl type, resorcinol type and other epoxy resins, tri-epoxy Propyl ginseng (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, p-tertiary butyl phenyl glycidyl ether, diglycidyl adipate, o-benzene Diglycidyl dicarboxylate, glycidyl methacrylate, butyl glycidyl ether and other compounds.

(Other additives) The reactive adhesive used in the present invention may contain other additives other than the foregoing, if necessary. As additives, for example: leveling agent, colloidal silica, alumina sol and other inorganic particles, polymethyl methacrylate-based organic particles, defoaming agent, anti-sagging agent, wetting and dispersing agent, viscosity Regulators, UV absorbers, metal deactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent brighteners, inorganic hot line absorbers, flame retardants Agent, antistatic agent, dehydrating agent, well-known and customary thermoplastic elastomer, tackifier, phosphoric acid compound, melamine resin, or reactive elastomer. 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 any component of the polyisocyanate composition (B) or the polyol composition (A), or may be blended during coating and used as the third component. Usually, it is prepared by premixing the polyol composition (A) with components other than the polyisocyanate composition (B) in advance, and mixing the premix and the polyisocyanate composition (B) just before construction .

(Layered body) The laminated system of the present invention is obtained, for example, by using the adhesive of the present invention on a plurality of films or papers, and bonding them by a dry lamination method or a non-solvent lamination method. In particular, the adhesive obtained by using the adhesive of the present invention for a plurality of films is called a laminated film. There are no special restrictions on the film used, and the film suitable for the application can be selected appropriately. For example, as food packaging, it can include: polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film, HDPE : High-density polyethylene film), polypropylene film (CPP: non-stretched polypropylene film, OPP: biaxially stretched polypropylene film) and other polyolefin films, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer film and other plastic films ( Also known as polymer film).

The film may be one subjected to extension treatment. As a stretching treatment method, the resin is usually melt-extruded by an extrusion film method or the like to form a sheet, and then simultaneously biaxial stretching or successive biaxial stretching is performed. In addition, in the case of successive biaxial stretching, the longitudinal stretching process is usually performed first, and then the lateral stretching is performed second. Specifically, a combination of longitudinal extension using the speed difference between rolls and lateral extension using a tenter is often used.

Or it can also be used in combination: films laminated with vapor deposition layers of metals such as aluminum, silicon dioxide, aluminum oxide and other metal oxides, and gas barrier layers containing polyvinyl alcohol, ethylene and vinyl alcohol copolymers, polyvinylidene chloride, etc.性膜。 The film. By using such a film, a laminate having barrier properties against water vapor, oxygen, alcohols, inert gases, volatile organic compounds (fragrance), etc. can be produced.

In order to form an adhesive layer free from defects such as insufficient film and cissing, various surface treatments such as flame treatment and corona discharge treatment can be applied to the surface of the film as needed.

Or the laminate of the present invention can be obtained by applying the adhesive of the present invention as an adhesive auxiliary agent (anchor coating agent) to a film by a laminator, and after curing reaction, the laminate is laminated by an extruder Layer of molten polymer material (extrusion lamination method). As the film, the same films as those used in the above-mentioned dry lamination method and non-solvent lamination method can be used. As the molten polymer material, polyolefin resins such as low-density polyethylene resins, linear low-density polyethylene resins, and ethylene-vinyl acetate copolymer resins are preferred.

As a more specific structure of the laminate, one can include: (1) Base film 1 / Adhesive layer 1 / Sealing film (2) Base film 1 / Adhesive layer 1 / Metal evaporation unstretched film (3) Base film 1 / Adhesive layer 1 / Metal vapor deposition stretched film (4) Transparent vapor deposition stretched film/adhesive layer1/sealing film (5) Base film 1 / Adhesive layer 1 / Base film 2 / Adhesive layer 2 / Sealing film (6) Base film 1 / Adhesive layer 1 / Metal vapor deposition stretched film / Adhesive layer 2 / Sealing film (7) Base film 1 / Adhesive layer 1 / Transparent vapor deposition stretched film / Adhesive layer 2 / Sealing film (8) Base film 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Sealing film (9) Base film 1 / Adhesive layer 1 / Base film 2 / Adhesive layer 2 / Metal layer / Adhesive layer 3 / Sealing film (10) Base film 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Base film 2 / Adhesive layer 3 / Sealing film Etc., but not limited to this.

As the base film 1 used in the constitution (1), an OPP film, a PET film, a nylon film, etc. can be cited. In addition, as the base film 1, it is possible to use a coating applied for the purpose of improving gas barrier properties and ink acceptance when a printing layer described later is provided. Examples of commercially available products of the coated base film 1 include K-OPP film and K-PET film. Adhesive layer 1 is a cured coating film of the adhesive of the present invention. As a sealing film, CPP film, LLDPE film, etc. are mentioned. A printing layer can be provided on the surface of the substrate film 1 on the adhesive layer 1 side (when the substrate film 1 is used as the substrate film 1, the surface of the adhesive layer 1 side of the coating layer). The printing layer can be formed by various printing inks such as gravure printing ink, flexographic printing ink, lithographic printing ink, stencil printing ink, inkjet printing ink, etc., using the usual printing methods used in printing to polymer films.

Examples of the base film 1 used in the constitutions (2) and (3) include OPP film, PET film, and the like. Adhesive layer 1 is a cured coating film of the adhesive of the present invention. As a metal vapor-deposited unstretched film, you can use: a VM-CPP film with aluminum and other metal vapor deposited on the CPP film; as a metal vapor-deposited stretched film, you can use: a VM-OPP film with aluminum and other metal vapor deposited on the OPP film . A printing layer can be provided on the surface of the base film 1 on the adhesive layer 1 side similarly to the configuration (1).

Examples of the transparent vapor-deposition stretched film used in the configuration (4) include films obtained by vapor-depositing silicon dioxide and aluminum oxide on OPP films, PET films, nylon films, and the like. For the purpose of protecting the inorganic vapor deposition layer of silicon dioxide and aluminum oxide, it can be used as a thin film coated on the vapor deposition layer. Adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealing film are the same as those of the configuration (1). A printing layer can be provided on the surface of the adhesive layer 1 side of the transparent vapor-deposited stretched film (when a coating is applied to the inorganic vapor-deposition layer, it is the surface of the adhesive layer 1 side of the coating layer). The method of forming the printing layer is the same as that of composition (1).

As the base film 1 used in the configuration (5), a PET film or the like can be cited. As the base film 2, a nylon film etc. are mentioned. 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 sealing film are the same as those of the configuration (1). A printing layer can be provided on the surface of the base film 1 on the adhesive layer 1 side similarly to the configuration (1).

As the base film 1 of the constitution (6), the same as the constitutions (2) and (3) can be mentioned. Examples of metal vapor-deposition stretched films include VM-OPP films and VM-PET films in which metal vapor deposition such as aluminum is applied to OPP films and PET films. 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 sealing film are the same as those of the configuration (1). A printing layer can be provided on the surface of the base film 1 on the adhesive layer 1 side similarly to the configuration (1).

As the base film 1 constituting (7), a PET film or the like can be cited. As a transparent vapor-deposition stretched film, the same thing as the structure (4) is mentioned. At least one of the adhesive layers 1 and 2 is the hardened coating film of the adhesive of the present invention. Examples of the sealing film are the same as those of the configuration (1). A printing layer can be provided on the surface of the base film 1 on the adhesive layer 1 side similarly to the configuration (1).

As the base film 1 constituting (8), a PET film or the like can be cited. As a metal layer, aluminum foil etc. are mentioned. At least one of the adhesive layers 1 and 2 is the hardened coating film of the adhesive of the present invention. Examples of the sealing film are the same as those of the configuration (1). A printing layer can be provided on the surface of the base film 1 on the adhesive layer 1 side similarly to the configuration (1).

As the base film 1 constituting (9) and (10), a PET film or the like can be cited. As the base film 2, a nylon film etc. are mentioned. As a metal layer, aluminum foil etc. are mentioned. At least one of the following layers 1, 2, and 3 is the hardened coating film of the adhesive of the present invention. Examples of the sealing film are the same as those of the configuration (1). A printing layer can be provided on the surface of the base film 1 on the adhesive layer 1 side similarly to 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, then the metal vapor-deposited layer, the transparent vapor-deposited layer, and the adhesive layer of the metal layer are the hardened coating film of the adhesive of the present invention Better.

When the adhesive of the present invention is a solvent type, a roll such as a gravure printing roll is used to apply the adhesive of the present invention to a film material that becomes a base material, and after the organic solvent is volatilized by heating in an oven, etc., the adhesive is bonded to other substrates. Material to obtain the laminate of the present invention. It is preferable to carry out a continual hardening treatment after lamination. The curing temperature is preferably from room temperature to 80°C, and the curing time is preferably from 12 to 240 hours.

When the adhesive of the present invention is a solvent-free type, use a roll such as a gravure printing roll to apply the adhesive of the present invention that has been heated to about 40°C to 100°C in advance on the film material that becomes the base material, and then immediately bond the other base material Thus, the laminate of the present invention is obtained. It is preferable to carry out a continual hardening treatment after lamination. The preferred curing temperature is from room temperature to 70°C, and the preferred curing time is from 6 to 240 hours.

When using the adhesive of the present invention as an adhesive adjuvant, use a roll such as a gravure printing roll to apply the adhesive adjuvant of the present invention to the film material that becomes the base material, and after heating by an oven or the like to volatilize the organic solvent, use The extruder laminates the molten polymer material to obtain the laminate of the present invention.

The coating amount of the adhesive is adjusted appropriately. In the case of a solvent-based adhesive, the amount of 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 as an example. In the case of a solvent-free adhesive, the coating amount of the adhesive is 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 as an example.

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

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

As paper, a well-known paper base material can be used without particular limitation. Specifically, it is manufactured using a well-known papermaking machine using natural fibers for papermaking, such as wood pulp, and its papermaking conditions are not specifically defined. Examples of natural fibers for papermaking include wood pulps such as conifer pulp and hardwood pulp, non-wood pulps such as manila hemp pulp, jean hemp pulp, and flax pulp, and pulps chemically modified to these pulps. As the type of pulp, it can be used: chemical pulp, grand pulp, chemical pulp, heat by kraft digestion method, acid, neutral, alkaline sulfite digestion method, sodium carbonate digestion method, etc. Mechanical pulp and so on.

In addition, it can also be used: all kinds of road forest paper, coated paper, liner paper, impregnated paper, corrugated paper, cardboard, etc. on the market. In addition, a printing layer can be provided on the outer surface or inner surface of the paper layer as needed.

The "other layer" may contain well-known additives and stabilizers, such as antistatic agents, easy-to-bond coating agents, plasticizers, slip agents, antioxidants, etc. In addition, in order to improve the adhesion with other materials when laminated, the "other layer" can be a pre-treatment such as corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc., on the surface of the film.

As mentioned above, in order to maximize the effect of the present invention, which can obtain a laminate with high adhesion and excellent appearance after lamination processing even under high-speed coating conditions, the adhesive of the present invention is initially applied to the plastic Film, after that, the adhesive surface is bonded to another plastic film or a porous substrate other than the plastic film, such as transparent vapor-deposition film, paper, wood, leather, etc., to obtain a laminate.

The laminate of the present invention can be ideally used in various applications, for example, can be ideally used as packaging materials, covering materials, paper straws, napkins, paper spoons, paper plates, paper cups and other paper tableware for food, medicine, and daily necessities, Barrier materials, roofing materials, solar cell panel materials, battery packaging materials, window materials, outdoor floor materials, lighting protection materials, automotive parts, signs, labels and other outdoor industrial uses, and decorative sheets used in injection molding and decoration methods, etc. , Liquid lotion for washing, liquid lotion for kitchen, liquid lotion for bath, liquid soap for bath, liquid shampoo, liquid conditioner and other packaging materials.

>Packaging materials> The laminate of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, pharmaceuticals, and the like. When used as a multilayer packaging material, the layer composition can be changed according to the content, use environment, and use form. In addition, the package of the present invention may be appropriately provided with easy-opening processing and resealing means.

The packaging material of the present invention is obtained by using the laminate of the present invention, aligning and overlapping the sealing films of the laminate, and then heat-sealing the peripheral ends to form a bag. Examples of bag making methods include: bending the laminate of the present invention, or aligning and superimposing the inner layer (surface of the sealing film) to face each other, and using, for example, side seal type and double seal type , Three-side sealing type, four-side sealing type, envelope type sealing type, palm sealing type, sealing type with folding edge, flat bottom sealing type, square bottom sealing type, clamping edge folding palm type, other heat sealing types, etc.的方法。 The method. The packaging material of the present invention can take various forms according to the content, use environment, and use form. Self-supporting packaging materials (self-supporting bags) are also possible. As a method of heat sealing, well-known methods such as rod sealing, rotating roller sealing, belt sealing, instant sealing, high frequency sealing, ultrasonic sealing, etc. can be used.

After the packaging material of the present invention is filled with content from its opening, the opening is heat-sealed to produce a product using the packaging material of the present invention. As the filling content, for example, in terms of food, it can include: rice snacks, bean snacks, nuts, biscuit, cookie, wafer snacks, marshmallows, pies, half-cooked cakes, candy , Snacks and other snacks, bread, snack noodles, instant noodles, dried noodles, pasta, aseptic packaged rice, Japanese risotto, porridge, bagged rice cakes, grains and other staple foods, pickles, boiled beans, natto, miso , Frozen tofu, tofu, mushrooms, konjac, processed mountain vegetables, jams, peanut butter, salads, frozen vegetables, processed potato products and other processed agricultural products, ham, bacon, sausages, processed chicken products, corned beef, etc. Processed livestock products, fish ham, sausages, refined aquatic products, fish plate, seaweed, Tsukudani, bonito flakes, seafood pickles (Shiokara), smoked salmon, spicy mentaiko and other processed aquatic products, peaches, oranges, pineapples, Fruits such as apples, pears, cherries, corn, asparagus, mushrooms, onions, carrots, white radishes, potatoes and other vegetables, frozen as represented by hamburger steak, meatballs, aquatic fried food, fried dumplings, croquette, etc. Prepared foods such as cooked food and refrigerated cooked food, dairy products such as cheese, margarine, cheese, butter, instant creamer, formula milk powder for childcare, liquid seasonings, instant curry, pet food and other foods.

In addition, in terms of non-food products, it can also be used as medicines such as cigarettes, warm packs, infusion bags, liquid detergents for washing, liquid detergents for kitchens, liquid detergents for baths, liquid soaps for baths, liquid shampoos, Various packaging materials such as liquid hair cream, lotion, lotion and other cosmetics, vacuum insulation materials, batteries, etc. [Example]

The following examples illustrate the content and effects of the present invention in more detail, but the present invention is not limited to the following examples.

Synthesis examples 1-16: Method for producing polyol composition (A) (Synthesis example 1) The method for synthesizing polyester polyol (a1-1) is equipped with stirring blades, temperature sensors, nitrogen inlet pipes and distillation towers In a 2-liter four-necked flask made of glass, put 35.2g of ethylene glycol, 83.3g of neopentyl glycol, 105.3g of 1,6-hexanediol, 124.0g of adipic acid, and 126.4g of isophthalic acid. Formic acid, 63.2g terephthalic acid, 96.5g dimer acid, 73.1g containing 1×10 ^-6 mass% or more and less than 1 mass% with an average particle diameter of 1×10 ^-3 mm～0.5mm Fine PET particles A and 0.2g of dibutyl tin oxide as a polymerization catalyst. Under normal pressure nitrogen flow, the temperature was increased to 250°C while the dehydration reaction was carried out. After reacting at 250°C for 2 hours, it was confirmed that the contents became transparent and the top temperature of the distillation tower was confirmed to be 80°C. Next, the rectifying tower was disassembled and switched to a glass condenser, the line was connected from the nitrogen inlet pipe to the vacuum pump, and the condensation reaction was performed for 5 hours under a reduced pressure of 50 Torr. Once it reaches a predetermined acid value and viscosity, the temperature is lowered to 130°C, and ethyl acetate is poured in and diluted using a dropping funnel to obtain polyester polyol (a1-1). Table 1 shows the weight fraction of PET pellets when the raw materials are fed, the acid value in solid conversion of the polyester polyol (a1-1), and the hydroxyl value in solid conversion.

(Synthesis example 2)～(Synthesis example 7) Except for using the raw materials shown in Table 1, it was synthesized in the same manner as (Synthesis Example 1) to obtain polyester polyols (a1-2) to (a1-7). Table 1 shows the weight fraction of the PET pellets when the raw materials are fed, the acid value of polyester polyols (a1-2) to (a1-7) in solid conversion, and the hydroxyl value in solid conversion, respectively.

(Synthesis example 8) Synthetic method of polyester polyol (a1-8) Put 35.2g of ethylene glycol, 83.3g of neopentyl glycol, and 105.3g of 1,6-into a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen introduction tube, and a distillation tower. Hexanediol, 124.0g of adipic acid, 126.4g of isophthalic acid, 63.2g of terephthalic acid, 96.5g of dimer acid, 73.1g of PET particles B without particles and 0.2g of Dibutyl tin oxide as a polymerization catalyst. Under normal pressure nitrogen flow, the temperature was increased to 250°C while the dehydration reaction was carried out. After reacting at 250°C for 2 hours, it was confirmed that the contents became transparent and the top temperature of the distillation tower was confirmed to be 80°C. Next, the rectifying tower was disassembled and switched to a glass condenser, the line was connected from the nitrogen inlet pipe to the vacuum pump, and the condensation reaction was performed for 5 hours under a reduced pressure of 50 Torr. Once it reaches the specified acid value and viscosity, the temperature is reduced to 130°C, and ethyl acetate is added and diluted using a dropping funnel. After that, 0.03 g of polyethylene powder (FLO-BEADS CL-2080 manufactured by Sumitomo Seiki Co., Ltd.) was added and stirred until uniform, to obtain a polyester polyol (a1-8). Table 1 shows the weight fraction of the PET pellets when the raw materials are fed, the acid value in solid conversion of the polyester polyol (a1-8), and the hydroxyl value in solid conversion.

(Synthesis Example 9) Synthetic method of polyester polyol (a1-9) Using the raw materials shown in Table 1, it was synthesized in the same manner as (Synthesis Example 8). The styrene polymer (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was finely pulverized and then charged in the same manner as in (Synthesis Example 8) to obtain polyester polyol (a1-9). Table 1 shows the weight fraction of the PET pellets when the raw materials are fed, the acid value in solid conversion of the polyester polyol (a1-9), and the hydroxyl value in solid conversion.

(Synthesis example 10) Synthetic method of polyester polyol (a1-10) Except for using the raw materials shown in Table 1, it was synthesized in the same manner as (Synthesis Example 8) to obtain polyester polyol (a1-10). The weight fraction of PET pellets and the acid value of polyester polyol (a1-10) converted into solids and the hydroxyl value of solids converted respectively when the raw material (cellulose powder (manufactured by Fujifilm Wako Pure Chemical Co., Ltd.)) is added Shown in Table 1.

(Synthesis Example 11) Synthetic method of polyester polyurethane polyol (a2-1) Put 300.0 g of polyester polyol (a1-1) and 0.1 g of polyester polyol (a1-1) into a two-liter four-necked glass flask equipped with a stirring blade, a temperature sensor, a nitrogen introduction tube, and a glass cooling tube. Dibutyl tin dilaurate. Once the temperature was raised to 60°C under normal pressure nitrogen flow, 9.0 g of isophorone diisocyanate was put in, the temperature was raised to 80°C, and the urethane reaction was performed at 80°C for 5 hours. After confirming that the predetermined viscosity and residual isocyanate content are 0.05% or less, the temperature is lowered to 50°C, and the solid content is appropriately adjusted with ethyl acetate to obtain polyester urethane polyol (a2-1). Table 3 shows the acid value in solid conversion and the hydroxyl value in solid conversion of the obtained polyester polyurethane polyol (a2-1).

(Synthesis example 12)～(Synthesis example 16) Except for using the raw materials shown in Table 2, it was synthesized in the same manner as (Synthesis Example 11) to obtain polyester polyurethane polyols (a2-2) to (a2-6). Table 2 shows the acid value in solid conversion and the hydroxyl value in solid conversion of the obtained polyester polyurethane polyols (a2-2) to (a2-6), respectively.

In Tables 1 and 2, the unit of input is g. Also, the blank field is not blended.

[Table 1] Table 1 Synthesis example 1 Synthesis Example 2 Synthesis Example 3 Synthesis Example 4 Synthesis Example 5 Synthesis Example 6 Synthesis Example 7 Synthesis Example 8 Synthesis Example 9 Synthesis Example 10 Polyester polyol (a1) a1-1 a1-2 a1-3 a1-4 a1-5 a1-6 a1-7 a1-8 a1-9 a1-10 PET particles A 73.1 146.3 292.5 16 31.9 98.8 249.5 PET particles B 146.3 146.3 146.3 Ethylene glycol 35.2 13.1 7.6 2.4 13.1 13.1 13.1 Diethylene glycol 318.3 235.1 Neopentyl glycol 83.3 83.3 23.8 17.4 17.4 83.3 83.3 83.3 1,6-hexanediol 105.3 105.3 105.3 11.9 11.9 105.3 105.3 105.3 Adipic acid 124 124 124 18.3 18.3 143.3 143 124 124 124 Isophthalic acid 126.4 126.4 27.6 27.6 176 176 126.4 126.4 126.4 Terephthalic acid 63.2 13.8 130.3 Dimer acid 96.5 96.5 96.5 96.5 96.5 96.5 Polymerization catalyst 0.2 0.2 0.2 0.002 0.002 0.2 0.2 0.2 0.2 0.2 Polyethylene powder 0.03 Styrene polymer 0.03 Cellulose powder 0.03 Total input 707.2 695.1 642.3 112.6 109.5 866.8 804.1 695.1 695.1 695.1 PET score (%) 10 twenty one 46 14 29 11 31 twenty one twenty one twenty one Trait value Acid value (mgKOH/g) 1.7 1.4 0.8 1.7 1.3 1.7 1.3 1.7 1.7 1.7 Hydroxyl value (mgKOH/g) 19 19 20 19 18 27 28 19 19 19

[Table 2] Table 2 Synthesis Example 11 Synthesis Example 12 Synthesis Example 13 Synthesis Example 14 Synthesis Example 15 Synthesis Example 16 Polyester urethane polyol (a2) a2-1 a2-2 a2-3 a2-4 a2-5 a2-6 a1-1 300 a1-2 300 a1-3 300 a1-8 300 a1-9 300 a1-10 300 Urethane catalyst 0.1 0.1 0.1 0.1 0.1 0.1 IPDI 9 9 9 9 9 9 Total input 309 309 309 309 309 309 Trait value Acid value (mgKOH/g) 1.7 1.4 0.8 1.7 1.7 1.7 Hydroxyl value (mgKOH/g) 3.6 3.6 3.6 3.6 3.6 3.6

(Examples and Comparative Examples) The polyol composition (A) obtained in the Examples and Comparative Examples was adjusted to have the particle size and content shown in Tables 3 and 4 by appropriately diluting with ethyl acetate and then applying filtration or the like. The content of the fine particles shown in Tables 3 and 4 is based on the use of a turbidity meter (Lavibond TB300IR manufactured by Tintometer Group) for a solution in which polyester polyol (A) is diluted with ethyl acetate to a solid content of 60%. The turbidity unit "NTU (Nephelometric Turbidity Unit)" measures the turbidity and converts it into mass% based on the calculation formula of 1NTU=1mg/L=1ppm, and is obtained by solid content conversion. In addition, the reactive adhesives used in the examples and comparative examples were prepared by blending the polyol composition (A) and the polyisocyanate composition (B) shown in Tables 3 and 4. In addition, the polyisocyanate composition (B) is a tri-functional polyisocyanate (DICDRY KW-75 manufactured by DIC Corporation, solid content 75%) used for trimethylolpropane addition to toluene diisocyanate, and hexamethylene diisocyanate The biuret body (made by DIC Graphics, solid content 90%). The evaluation was carried out based on the criteria shown below. The results are shown in Tables 3 and 4, respectively.

(Evaluation) (Storage stability of polyol composition (A)) The polyol composition (A) obtained in the Examples and Comparative Examples was diluted with ethyl acetate to set the solid content to 60%, and collected into a transparent glass bottle so that no bubbles appeared. After sealing, it was dried at 40°C Keep in the machine for 1 month. The appearance after storage was observed, and the following evaluation was performed based on the degree of precipitation of fine particles. Evaluation ◎: No precipitation is seen at all. Evaluation ○: Shendian is slightly seen, but the appearance of the resin solution does not change. Evaluation △: Precipitation is clearly seen, and the appearance of the resin solution changes. Evaluation ×: Most of the particles are precipitated, and the appearance of the resin solution changes greatly.

(Appearance of the laminate) Dry Laminator (Musashino Machinery Design Co., Ltd., Dry Lami Test Coater) is used as the laminator, with a processing speed of 250m/min, on the Ny film as the first plastic film layer. After coating the adhesives of the examples or comparative examples with a coating amount of 3 to 3.5g/m ² , laminate VMPET as the second plastic film layer (commercially available aluminum vapor-deposited non-extended polymer Ethylene terephthalate film) to obtain a laminate. Visually confirm the appearance of the film immediately after lamination (whether there are defects such as wrinkles, floating due to bubbles, tunneling due to deviation between the films).

Evaluation criteria ◎ ：The number of bubbles is 0 and there are no wrinkles or tunnels at all ○: The number of bubbles is 1 to 4 and there are no wrinkles or tunnels at all ○- ：The number of bubbles is 5-9 and there are no wrinkles or tunnels at all △: The number of bubbles is 10-16 and wrinkles and tunnels occur locally ×: There are more than 17 bubbles and wrinkles and tunnels in many places

In Tables 3 and 4, the unit of blending amount is g, and the blank column means no blending.

[table 3] table 3 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Polyester polyol (A) Polyester (a1-1) 300 Polyester (a1-2) 300 Polyester (a1-3) 300 Polyester (a1-4) Polyester (a1-5) Polyester (a1-6) Polyester (a1-7) Polyester urethane (a2-1) 300 300 Polyester urethane (a2-2) 300 300 Polyester urethane (a2-3) 300 300 Polyester urethane (a2-4) Polyester urethane (a2-5) Polyester urethane (a2-6) Average diameter of particles (μm) 30 300 450 10 10 15 200 150 450 Particle content (ppm) 20 120 950 0.05 0.1 10 150 450 950 Polyisocyanate composition (B) KW-75: TMP plus finished product of TDI 250 250 250 50 50 50 50 50 50 KR-90: Biuret of HDI Evaluation results Storage stability of polyester polyol (A) ◎ ○ ○ ◎ ◎ ◎ ○ ○ ○ The appearance of the laminate ◎ ○ ○- ◎ ◎ ◎ ○ ○ ○-

[Table 4] Table 4 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Polyester polyol (A) Polyester (a1-1) Polyester (a1-2) Polyester (a1-3) Polyester (a1-4) 300 Polyester (a1-5) 300 300 Polyester (a1-6) 300 Polyester (a1-7) 300 Polyester urethane (a2-1) Polyester urethane (a2-2) Polyester urethane (a2-3) Polyester urethane (a2-4) 300 Polyester urethane (a2-5) 300 Polyester urethane (a2-6) 300 Average diameter of particles (μm) 15 90 300 60 300 20 100 100 Particle content (ppm) 300 600 900 350 700 40 40 40 Polyisocyanate composition (B) KW-75: TMP plus finished product of TDI 60 60 50 50 50 KR-90: Biuret of HDI 32 32 32 Evaluation results Storage stability of polyester polyol (A) ◎ ◎ ○ ◎ ○ ◎ ○ ○ The appearance of the laminate ○ ○- ○- ○ ○- ◎ ◎ ◎

[table 5] table 5 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Polyol composition (A) Polyester (a1-1) Polyester (a1-2) 300 Polyester (a1-3) Polyester (a1-4) 300 Polyester (a1-5) 300 Polyester (a1-6) Polyester (a1-7) 300 Polyester urethane (a2-1) Polyester urethane (a2-2) 300 300 Polyester urethane (a2-3) 300 Average diameter of particles (μm) 50 100 600 500 50 300 80 Particle content (ppm) 1200 1100 1200 1300 1200 1500 1200 Polyisocyanate composition (B) KW-75: TMP plus finished product of TDI 250 50 50 50 60 KR-90: Biuret of HDI 32 32 Evaluation results Storage stability of polyester polyol (A) ◎ ○ △ △ ◎ 〇 ◎ The appearance of the laminate △ △ △ × △ × △

The polyol composition (A) used in (Example 1) to (Example 17) has little precipitation over time, and when used as an adhesive, a laminate having an excellent appearance after lamination processing can be obtained. On the other hand, (Comparative Example 1) to (Comparative Example 7) caused precipitation over time or poor appearance after lamination processing.

(Example of laminated body) (Method of making laminated body for sterilization resistance test: a composition including aluminum foil) After mixing the adhesive according to the ratio in the table, apply it so that the amount of the adhesive becomes about 3.5 g/m ^{2 of} solid content After drying the solvent on a PET film with a film thickness of 12 μm, the adhesive-coated surface of the film and a nylon film with a film thickness of 15 μm are laminated and laminated by a laminator. Next, apply the adhesive to the nylon surface of the laminate so that the solid content of the laminate is about 3.5g/m ^2. After drying the solvent, use a laminator to make the adhesive coating surface of the laminate and the film thickness 9μm The aluminum foil is pasted and then laminated. Furthermore, the adhesive is applied to the side opposite to the adhesive coating surface of the aluminum foil so that the solid content is about 3.5g/m ² , the solvent is dried, and then the adhesive of the laminate is applied with a laminator The surface and the heat-resistant non-stretched polypropylene film (heat-resistant CPP) with a film thickness of 70um are laminated and then laminated. After that, it was stored in a constant temperature bath at 40°C for 3 days to obtain a laminate.

(Method of making laminate for boiling resistance test) After blending the adhesive according to the ratio in the table, apply the adhesive to a PET film with a film thickness of 12μm or a film thickness of 15μm so that the coating amount becomes about 3.0g/m ^{2 of} solid content After drying the solvent, use a laminator to make the coating surface of the adhesive and the linear low-density polyethylene film with a film thickness of 60 μm ( LLDPE) is laminated and then layered. After that, it was stored in a constant temperature bath at 40°C for 3 days to obtain a laminate.

(Method of making laminate for sterilization resistance test) After blending the adhesive according to the ratio in the table, apply the adhesive to a PET film with a film thickness of 12um or a film thickness of 15um so that the coating amount becomes about 3.0g/m ^{2 of} solid content After the solvent is dried, the coating surface of the adhesive and the heat-resistant non-stretch polypropylene film (heat-resistant) of 70um thickness CPP) paste and then layer. After that, it was stored in a constant temperature bath at 40°C for 3 days to obtain a laminate.

(Measurement method of normal laminate strength) Immediately after manufacturing the laminate, the laminate was cut out with a width of 15 mm, and the adhesive strength (T-peel) (unit: N/15 mm) was measured at a peeling speed of 300 mm/min using a tensile tester.

(Laminated strength and appearance after boiling treatment) The laminate for the boiling resistance test was cut out to 120 mm×220 mm, bent so that LLDPE was inside, and heat-sealed at 1 atm, 180° C., for 1 second to make a pouch. 1/1/1 sauce (meat sauce: vegetable oil: edible vinegar=1:1:1) was added as the content. The filled bag is boiled at 98℃-60 minutes to remove the contents, and the strength caused by T-peeling between PET/LLDPE, Ny/LLDPE and transparent vapor-deposited PET/LLDPE is measured. In addition, the appearance of each bag after being taken out was observed, and the following evaluation was performed based on the presence or absence of delamination. Evaluation ○: No delamination Evaluation △: The delamination is less than 5 points Evaluation ×: The delamination point is more than 6 points

(Laminated strength and appearance after sterilization) The laminate for the sterilization resistance test was cut out to 120 mm×220 mm, bent so that the heat-resistant CPP was inside, and heat-sealed at 1 atm, 180° C., for 1 second to make a bag. 1/1/1 sauce (meat sauce: vegetable oil: edible vinegar=1:1:1) was added as the content. The filled bag is sterilized at 125°C for 30 minutes (steam type) to remove the contents and measure the T-type peeling between PET/CPP, Ny/CPP, transparent vapor-deposited PET/CPP, and aluminum foil/CPP. The strength. In addition, the appearance of each bag after being taken out was observed, and the following evaluation was performed based on the presence or absence of delamination. Evaluation ○: No delamination Evaluation △: The delamination is less than 5 points Evaluation ×: The delamination point is more than 6 points

[Table 6] Table 6 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Normal stack strength PET/LLDPE 3.2 F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut Ny/LLDPE F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut PET/CPP 3.4 F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut Ny/CPP 10.2 9.8 10.4 12.2 F-cut F-cut F-cut F-cut F-cut Transparent vapor deposition PET/LLDPE F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut Transparent vapor deposition PET/CPP F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut PET-Nyl-AL/CPP (4-layer structure between AL/CPP) 9.2 9.2 9.4 9.3 9.1 9.4 Boiling tolerance test PET/LLDPE Lami intensity 3.5 3.6 3.9 F-cut F-cut F-cut F-cut F-cut F-cut Exterior ○ ○ ○ ○ ○ ○ ○ ○ ○ Ny/LLDPE Lami intensity F-cut F-cut F-cut 6.2 6.3 6.3 6.2 6.1 6.3 Exterior ○ ○ ○ ○ ○ ○ ○ ○ ○ Transparent vapor deposition PET/LLDPE Lami intensity 2.7 2.6 2.7 F-cut F-cut F-cut F-cut F-cut F-cut Exterior ○ ○ ○ ○ ○ ○ ○ ○ ○ Sterilization resistance test PET/CPP Lami intensity 3.1 3 3.4 F-cut F-cut F-cut F-cut F-cut F-cut Exterior ○ ○ ○ ○ ○ ○ ○ ○ ○ Ny/CPP Lami intensity 8.7 8.6 8.8 12.1 11.9 11.8 12.1 12 11.7 Exterior ○ ○ ○ ○ ○ ○ ○ ○ ○ Transparent vapor deposition PET/CPP Lami intensity 3.2 3.3 3.2 F-cut F-cut F-cut F-cut F-cut F-cut Exterior ○ ○ ○ ○ ○ ○ ○ ○ ○ PET-Nyl-AL/CPP Lami intensity 8.8 9 8.9 9.2 9.2 9.1 Exterior ○ ○ ○ ○ ○ ○

[Table 7] Table 7 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Normal stack strength PET/LLDPE 3.1 3.2 3.1 F-cut F-cut F-cut F-cut F-cut Ny/LLDPE F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut PET/CPP 3.3 3.7 3.5 F-cut F-cut F-cut F-cut F-cut Ny/CPP 9.2 8.9 8.8 15.1 15.2 F-cut F-cut F-cut Transparent vapor deposition PET/LLDPE 3.2 3 3.1 F-cut F-cut F-cut F-cut F-cut Transparent vapor deposition PET/CPP F-cut F-cut F-cut F-cut F-cut F-cut F-cut F-cut PET-Nyl-AL/CPP (4-layer structure between AL/CPP) 9.1 9.2 9 Boiling tolerance test PET/LLDPE Lami intensity 3.1 3 3 2.2 2.2 F-cut F-cut F-cut Exterior ○ ○ ○ ○ ○ ○ ○ ○ Ny/LLDPE Lami intensity F-cut F-cut F-cut F-cut F-cut 6.3 6.2 6.1 Exterior ○ ○ ○ ○ ○ ○ ○ ○ Transparent vapor deposition PET/LLDPE Lami intensity 2.5 2.4 2.4 2.5 2.4 F-cut F-cut F-cut Exterior ○ ○ ○ ○ ○ ○ ○ ○ Sterilization resistance test PET/CPP Lami intensity 3.1 3 3.1 1.8 2 F-cut F-cut F-cut Exterior ○ ○ ○ ○ ○ ○ ○ ○ Ny/CPP Lami intensity 7.9 8 8.1 11.2 11.1 11.9 11.7 11.8 Exterior ○ ○ ○ ○ ○ ○ ○ ○ Transparent vapor deposition PET/CPP Lami intensity 2.9 3 2.9 2.9 3 F-cut F-cut F-cut Exterior ○ ○ ○ ○ ○ ○ ○ ○ PET-Nyl-AL/CPP Lami intensity 8.8 8.9 8.9 Exterior ○ ○ ○

In Tables 2 to 7, the abbreviations are as follows. KW-75: Tri-functional polyisocyanate with toluene diisocyanate added to trimethylolpropane, solid content 75% KR-90: Biuret of hexamethylene diisocyanate Lami strength: laminated strength PET: Polyethylene terephthalate LLDPE: Laminated body of linear low density polyethylene Ny: Nylon PET-AL: laminated body of polyethylene terephthalate and aluminum CPP: Non-stretched polypropylene film /: indicates the adhesive layer Delami layer: delamination F-cut: Film cutting (indicating sufficient bonding strength)

As a result, the polyol composition (A) used in (Example 1) to (Example 17) can also obtain sufficient adhesive strength when used as an adhesive.

no.

no.

no.

Claims (8)

A reactive adhesive, which is a reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), characterized in that the polyol composition (A) contains poly(ethylene terephthalate) Polyester polyol (A1) which is the reaction product of diester, polyol and polyacid at one time and/or polyester polyurethane which is the reaction product of polyester polyol (A1) and isocyanate compound Polyol (A2) and fine particles (C) with an average particle size of 1×10 ^-3 mm or more and less than 0.5 mm, relative to the total resin solid content of the polyol composition (A), containing 1×10 ^-6 mass % Or more and less than 0.1% by mass of the particles (C). The reactive adhesive of claim 1, wherein the ratio of polyethylene terephthalate in the input raw material of the polyester polyol (A1) is 5-50% by mass. The reactive adhesive of claim 1 or 2, wherein the polybasic acid is a dimer acid, and the ratio of the dimer acid in the input raw material of the polyester polyol (A1) is 5-20% by mass . A laminate, which is a laminate in which a plurality of films or papers are bonded with an adhesive, and is characterized in that the adhesive is a reactive adhesive according to any one of claims 1 to 3. A laminated body is a laminated body in which a film or paper provided with a plurality of printing layers is laminated with an adhesive, characterized in that the adhesive is a reactive adhesive as claimed in any one of claims 1 to 4. A packaging body formed by forming a laminated body as claimed in claim 4 or 5 into a bag shape. A manufacturing method of polyester polyol (A1), which is characterized in that it has the step of putting polyethylene terephthalate, polyol and polyacid in one time and reacting them, and then filtering with a filter. A manufacturing method of polyester polyurethane polyol (A2), which is characterized in that it has a polyester polyol in which polyethylene terephthalate, polyol and polyacid are charged in one time and reacted (A1) The step of filtering with a filter after reacting with polyisocyanate.