WO2019188335A1 - Reactive adhesive agent, laminate film, and packaging body - Google Patents

Abstract

Provided are: a reactive adhesive agent containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) contains a polyester polyol (A1) which is the reaction product of the batch charging of a polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid; a laminate film obtained by laminating a reactive adhesive agent layer between a first plastic film and a second plastic film; and a production method for the polyester polyol (A1), said method being characterized in that the polyethylene terephthalate, the polyhydric alcohol, and the polybasic acid are charged and reacted as a batch.

Description

Reactive adhesive, laminated film, and package

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

Conventionally, laminates made by laminating various plastic films and laminating plastic films with metal-deposited films and metal foils have been used in various applications, such as packaging materials for foods, pharmaceuticals, and household goods, and barriers. Decoration for roofing materials, roofing materials, solar panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signs, stickers, etc. Used for applications.
These laminates are appropriately combined with various plastic films, metal-deposited films or metal foils according to the required properties for each application, and an adhesive is selected according to the required properties. For example, in the case of food and daily necessities, functions such as strength, resistance to cracking, retort resistance, heat resistance, and content resistance are required to protect the contents from various distribution, storage such as refrigeration, and heat sterilization. Is required. Alternatively, in outdoor industrial applications, weather resistance and hydrolysis resistance are required to maintain long-term adhesion even in open-air environments.
Furthermore, these laminates rarely circulate in the form of sheets. For example, they may be heat-sealed in the form of bags, or may be molded by thermoforming, requiring heat sealability and moldability. Sometimes it is done.

As an adhesive used for such a laminate, a reactive adhesive (also referred to as a two-component adhesive) for reacting a hydroxyl group with an isocyanate has been conventionally known.
For example, in food applications, in an adhesive comprising a diol compound (A) having two hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups, the number average of the diol compound (A) The molecular weight (Mn) is in the range of 400 to 3000, the polyisocyanate (B) is a triisocyanate or higher polyisocyanate compound (b1), a diisocyanate compound (b2) obtained by adding an isocyanate compound to a polyester diol, Adhesives that are mixtures of these are known. (For example, see Patent Document 1)
It is an adhesive for laminate film of battery packaging materials, and contains polyurethane polyester polyol whose number average molecular weight of polyol component is 5000 or more and less than 14000, and the total content of urethane bond and isocyanate group is specified. It is known that the laminating adhesive within the range of 1 is excellent in molding processability and wet heat resistance (see, for example, Patent Document 2).

These reactive adhesives are required to have properties according to various uses, and in recent years, from the viewpoint of productivity, for example, even if the coating speed is 200 m / min. Is required. However, under such high-speed coating (also called high-speed processing) conditions, not only solventless reactive adhesives that do not use organic solvents, but also dry laminate reactive adhesives that can be adjusted for viscosity using organic solvents. Even in this case, there is a problem that a skin-like appearance defect tends to occur depending on the base material.

JP 2014-101422 A Japanese Unexamined Patent Publication No. 2016-196580 Japanese Patent Laid-Open No. 2002-3815 JP 2010-248345 A

The problem to be solved by the present invention can be applied as an adhesive for laminates in which various plastic films, metal vapor deposition films or metal foils are appropriately combined, and has high adhesiveness and lamination even under high-speed coating conditions. It is providing the reactive adhesive which can obtain the laminated | multilayer film which has the outstanding external appearance later.

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

Adhesives using polyester polyols made from polyethylene terephthalate are known (see, for example, Patent Documents 3 and 4). For example, Patent Document 3 discloses a reactivity containing a polyester polyol obtained by decomposing polyethylene terephthalate by a reaction with a low molecular polyol and then a condensation reaction of the decomposed product with a polybasic acid, and a polyisocyanate curing agent. An adhesive is disclosed. However, although Patent Document 3 has been evaluated for a laminate film prepared by applying an adhesive at a film speed of 50 m / min, there is nothing about a form prepared under high-speed coating conditions at a coating speed of 200 m / min or more. There is no description or suggestion. Patent Document 4 discloses that a polyol compound obtained by depolymerizing polyester (a) with polyol (b) having two or more hydroxyl groups in one molecule is used as a raw material for the adhesive. However, as for the evaluation of the adhesive, it has been evaluated for a laminated film which is applied to a film with a film thickness of 30 μm by an applicator and then laminated, and is prepared under a high speed coating condition of a coating speed of 200 m / min or more. There is no description or suggestion about the form. In other words, a reactive adhesive that uses polyester polyol made from polyethylene terephthalate and has high adhesion and excellent appearance after lamination even under high-speed coating conditions of 200 m / min or more is now available. The fact is not known.

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

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

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

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

Also, the present invention provides a method for producing a polyester polyol (A1), in which polyethylene terephthalate, polyhydric alcohol, and polybasic acid are charged and reacted together.

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

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

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

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

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

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

The polyhydric alcohol used by this invention is not specifically limited, A well-known polyhydric alcohol can be used.
For example, 1,2-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,3-butanediol, 2, Aliphatic diols such as 2,4-trimethyl-1,3-pentanediol; 1,3-bis (2-hydroxypropyl) cyclopentane, 1,3-bis (2-hydroxybutyl) cyclopentane, 1,4- Alicyclic diols such as bis (2-hydroxypropyl) cyclohexane and 1,4-bis (2-hydroxybutyl) cyclohexane; 1,4-bis (2-hydroxypropyl) benzene, 1,4-bis (2-hydroxy) Aromatic diols such as butyl) benzene;

2,2-bis (4-hydroxyphenyl) propane (hereinafter abbreviated as “bisphenol A”), 2,2-bis (4-hydroxyphenyl) butane (hereinafter abbreviated as “bisphenol B”), bis (4- Hydroxyphenyl) methane (hereinafter abbreviated as “bisphenol F”), bisphenol such as bis (4-hydroxyphenyl) sulfone (hereinafter abbreviated as “bisphenol S”), 1,2-propylene oxide and 1,2-butylene Alkylene oxide adduct of bisphenol obtained by adding alkylene oxide having secondary hydroxyl group such as oxide; ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 3-methyl-1,3 -Butanediol, 1,5-pentanediol, 3-methyl- 1,5-pentanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3-propanediol, 1,6-hexanediol, trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, etc. Aliphatic polyols; エ ー テ ル ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol;

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

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

The polybasic acid used by this invention is not specifically limited, A well-known polybasic acid can be used.
For example, aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, hexahydro Aliphatic dicarboxylic acids such as phthalic acid and 1,4-cyclohexanedicarboxylic acid; maleic acid, maleic anhydride, citraconic acid, dimethylmaleic acid, cyclopentene-1,2-dicarboxylic acid, 1-cyclohexene-1,2- Aliphatic unsaturated dicarboxylic acids such as dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, fumaric acid, mesaconic acid, itaconic acid, glutaconic acid; 1,2,5-hexanetricarboxylic acid, 1,2, Aliphatic tricarboxylic acids such as 4-cyclohexanetricarboxylic acid; trimellitic acid, 1,2,5-ben Ntorikarubon acid, 2,5,7 aromatic tricarboxylic acids such as naphthalene tricarboxylic acid, such as dimer acid. These may be used alone or in combination of two or more. Of these, dimer acid is preferred.

The production method in which PET, polyhydric alcohol, and polybasic acid are charged and reacted together can be arbitrarily produced by a known polycondensation reaction method. Specifically, PET, polyhydric alcohol, and polybasic are available. Acid is added to the production equipment and heated to 180 ° C or higher with stirring in a nitrogen atmosphere, and any production method such as atmospheric pressure dehydration reaction, reduced pressure and vacuum dehydration reaction, solution polycondensation method, solid phase polycondensation reaction, etc. You may carry out in. In the case of using the PET, polyhydric alcohol and polybasic acid described in the present application, the vacuum dehydration reaction can be applied at a reaction temperature of 230 ° C. or lower, and the reaction time can be set to about 5 hours. The progress of the polycondensation reaction can be confirmed by measuring the acid value, hydroxyl value, viscosity or softening point. As the production apparatus used at this time, for example, a batch production apparatus such as a reaction vessel equipped with a nitrogen inlet, a thermometer, a stirrer, a rectifying tower, etc. can be suitably used, and a deaeration port is provided. Extruders, continuous reactors, kneaders and the like can also be used. Furthermore, the esterification reaction can be promoted by using an esterification catalyst (such as a tin compound, a titanium compound, or a zirconium compound) as necessary.
The polyol obtained by the method of transesterifying PET in polyhydric alcohol and the method of polycondensation of the transesterification product and polybasic acid decomposes the ethylene terephthalate unit apart. Even if it is used as an agent, the appearance, adhesive strength, heat resistance and content resistance properties during high-speed coating, which are the purposes of the present application, cannot be achieved.

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

In the PET, the ratio of the polyester polyol (A1) charged to the total amount of the polyhydric alcohol and polybasic acid is 5 to 50% by mass with respect to 100% of the total amount of polyhydric alcohol and polybasic acid. And more preferably 8 to 48% by mass.

In the present application, as a raw material for the polyester polyol (A1), a long-chain unsaturated dibasic acid such as dimer acid, 1,6-hexanediol, and other monomers are synthesized together with PET, so that the adhesive strength to the substrate is increased. In addition, it is possible to obtain an adhesive having superior heat resistance and content resistance. The reason for this is not clear, but with this composition, it is possible to carry out the reaction at 220 ° C., and the ethylene terephthalate unit in the reaction product thus obtained is less likely to be decomposed by long-chain unsaturated groups, and the reaction temperature is high. It is presumed that the molecular weight body remains as it is, and it is presumed that this contributes to the appearance, adhesive strength, heat resistance and content resistance at high speed coating. In the case of trihydric alcohol (trimethylolpropane) as polyhydric alcohol, the ethylene terephthalate unit in PET may be sufficiently decomposed, and the reaction temperature must be higher than 220 ° C. Therefore, the polyhydric alcohol is preferably a dihydric alcohol such as 1,6-hexanediol.

(Acid value, hydroxyl value)
The polyester polyol (A1) preferably has an acid value of 5.0 or less from the viewpoint of hydrolysis resistance, and more preferably 3.0 or less from the viewpoint of the reactivity of the adhesive. Moreover, it is preferable that a hydroxyl value is 50 or less from a viewpoint of high-speed coating property, and 40 or less is more preferable.
In the present invention, the acid value and the hydroxyl value are measured by the following methods, and indicate values converted into solid contents unless otherwise specified.

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

(Hydroxyl value)
Weigh 6-10 g of polyester polyol into a 300 ml Erlenmeyer flask. Let the weighed amount be (S). To this, 25 ml of an acetylating agent prepared in advance is added and dissolved. A condenser tube is attached to the mouth of the Erlenmeyer flask, and acetylation reaction is performed 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, titration is performed with a 0.5 mol / L potassium hydroxide alcohol solution. The point showing a slight red color lasting 30 seconds is set as the end point, and the hydroxyl value is calculated by the following formula from the titration amount (V) at that time. A blank test is performed at the same time, and the titer at that time is (B). The titer of the 0.5 mol / L potassium hydroxide alcohol solution is defined as (F). Separately, the acid value is measured.
Hydroxyl value = ((B−V) × F × 28.05) / S + acid value

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

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

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

(Polyester polyurethane polyol (A2))
The polyester polyol (A1) is a polyester polyurethane polyol (A2) obtained by reacting polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid all at once, and then further reacting with an isocyanate compound described later. Also good. At this time, the isocyanate compound is preferably isophorone diisocyanate.

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

(Other polyols)
In the present invention, within the range that does not impair the effects of the present invention, in addition to the polyester polyol (A1), the polyhydric alcohol itself, a polyester polyol that does not use polyethylene terephthalate as a raw material, a polyether polyol, a polyurethane polyol, and a polyether A polymer polyol selected from ester polyols, polyester (polyurethane) polyols, polyether (polyurethane) polyols, polyester amide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyl alkanes, castor oil, or mixtures thereof may be used in combination.

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

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

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

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

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

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

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

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

(Aliphatic cyclic amide compound)
As described in detail, the reactive adhesive of the present invention comprises the polyol composition (A) and the polyisocyanate composition (B) as essential components, and further includes an aliphatic cyclic amide compound. Either the polyol composition (A) or the polyisocyanate composition (B) is mixed with one of the components, or is blended at the time of coating as a third component, whereby an aromatic amine is formed in the laminate package. Elution into the contents of the representative harmful low molecular chemical substances can be effectively suppressed.

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

(catalyst)
In the present invention, by using a catalyst, elution of harmful low molecular chemical substances typified by aromatic amines into the contents of the laminate package can be effectively suppressed.
The catalyst used in the present invention is not particularly limited as long as it is for accelerating the urethanation reaction. For example, metal catalysts, amine catalysts, diazabicycloundecene (DBU), aliphatic cyclic amide compounds A catalyst such as a titanium chelate complex can be used.

Examples of metal catalysts include metal complex systems, inorganic metal systems, and organic metal systems. Specific examples of metal complex systems include Fe (iron), Mn (manganese), Cu (copper), and Zr (zirconium). ), Th (thorium), Ti (titanium), Al (aluminum), Sn (tin), Zn (zinc), Bi (bismuth) and Co (cobalt) acetylacetonate salts of metals selected from the group For example, iron acetylacetonate, manganese acetylacetonate, copper acetylacetonate, zirconia acetylacetonate and the like can be mentioned. Of these, from the viewpoint of toxicity and catalytic activity, iron acetylacetonate (Fe (acac) ₃ ) Or manganese acetylacetonate (Mn (acac) ₂ ).

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

Examples of organometallic catalysts include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octylate, Examples thereof include nickel naphthenate, cobalt octylate, cobalt naphthenate, bismuth octylate, bismuth naphthenate, and bismuth neodecanoate. Of these, preferred compounds are organotin catalysts, and more preferred are stannous dioctate and dibutyltin dilaurate.

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

Other tertiary amine catalysts include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N ″, N "-Pentamethyldiethylenetriamine, N, N, N ', N", N "-pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N', N", N "-pentamethyldipropylenetriamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N ′-(2-hydroxy Ethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, bis Dimethylaminopropyl) amine, bis (dimethylaminopropyl) isopropanolamine, 3-quinuclidinol, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro -S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, N-methyl-N '-(2-dimethylaminoethyl) piperazine, N, N'-dimethylpiperazine, dimethylcyclohexylamine, N -Methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N, N-dimethylhexanolamine, N-methyl-N '-(2-hydroxyethyl) pipette Gin, 1- (2-hydroxyethyl) imidazole, 1- (2-hydroxypropyl) imidazole, 1- (2-hydroxyethyl) -2-methylimidazole, 1- (2-hydroxypropyl) -2-methylimidazole, etc. Is mentioned.

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

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

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

The reactive adhesive of the present invention may be used in combination with a pigment, if necessary. In this case, usable pigments are not particularly limited. For example, extender pigments, white pigments, black pigments, gray pigments, red pigments described in the Paint Material Handbook 1970 edition (edited by the Japan Paint Industry Association) Examples thereof include organic pigments and inorganic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearl pigments, and plastic pigments. Specific examples of these colorants include various types, and examples of organic pigments include various insoluble azo pigments such as Bench Gin Yellow, Hansa Yellow, Raked 4R, etc .; Soluble properties such as Raked C, Carmine 6B, Bordeaux 10 and the like. Azo pigments; various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and fast sky blue; anthraquinone Various vat dyes such as pigments, thioindigo pigments and perinone pigments; various quinacridone pigments such as Cincacia Red B; various dioxazine pigments such as dioxazine violet; various condensed azos such as chromoftal Pigment; aniline black, etc. And the like.

Examples of inorganic pigments include various chromates such as chrome lead, zinc chromate, and molybdate orange; various ferrocyan compounds such as bitumen; titanium oxide, zinc white, mapico yellow, iron oxide, bengara, chrome oxide Various metal oxides such as green and zirconium oxides; various sulfides or selenides such as cadmium yellow, cadmium red and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types such as calcium silicate and ultramarine blue Silicates; various carbonates such as calcium carbonate and magnesium carbonate; various phosphates such as cobalt violet and manganese purple; various metal powders such as aluminum powder, gold powder, silver powder, copper powder, bronze powder and brass powder Pigments; flake pigments of these metals, mica flake pigments; mica flakes coated with metal oxides Click pigments, micaceous iron oxide pigments such as metallic pigment and pearl pigment; graphite, carbon black and the like.

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

Furthermore, examples of the plastic pigment include “Grandall PP-1000” and “PP-2000S” manufactured by DIC Corporation.

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

The mass ratio of the pigment used in the present invention is 1 to 400 parts by mass, particularly 10 to 300 parts by mass with respect to a total of 100 parts by mass of the isocyanate component B and the polyol component A. More preferable.

(Adhesion promoter)
Moreover, an adhesion promoter can also be used together with the reactive adhesive used in the present invention. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, and epoxy resins.

Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) -γ. Amino silanes such as aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycyl Epoxy silanes such as Sidoxypropyltriethoxysilane; Vinylsilanes such as Vinyltris (β-methoxyethoxy) silane, Vinyltriethoxysilane, Vinyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane; Hexamethyldisilazane, γ-Me Mercaptopropyl trimethoxysilane and the like.

Examples of titanate coupling agents include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, tetrastearoxy Titanium etc. can be mentioned.

Also, examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.

As epoxy resins, there are generally commercially available Epbis type, novolak type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, many Various epoxy resins such as carboxylic acid ester type, aminoglycidyl type, resorcin type, triglycidyl tris (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylic glycidyl Ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, pt-butylphenyl glycidyl ether, adipic acid diglycidyl ester, - phthalic acid diglycidyl ester, glycidyl methacrylate, compounds such as butyl glycidyl ether.

(Other additives)
If necessary, the reactive adhesive used in the present invention may contain other additives other than those described above. Examples of additives include leveling agents, inorganic fine particles such as colloidal silica and alumina sol, polymethyl methacrylate organic fine particles, antifoaming agents, anti-sagging agents, wetting and dispersing agents, viscosity modifiers, ultraviolet absorbers, metals Deactivator, peroxide decomposer, flame retardant, reinforcing agent, plasticizer, lubricant, rust preventive, fluorescent brightener, inorganic heat absorber, flame retardant, antistatic agent, dehydrating agent, Known and commonly used thermoplastic elastomers, tackifiers, phosphoric acid compounds, melamine resins, or reactive elastomers can be used. The content of these additives can be appropriately adjusted and used within a range that does not impair the function of the reactive adhesive used in the present invention.

These adhesion promoters and additives may be mixed with one component of the polyisocyanate composition (B) or the polyol composition (A), or may be used as a third component by blending at the time of application. it can. Usually, the premix which mix | blended components other than polyisocyanate composition (B) with the polyol composition (A) beforehand is prepared, and this premix and polyisocyanate composition (B) are just before construction. Prepare by mixing.

(Laminated film)
The laminated film of the present invention is formed by laminating an adhesive layer made of the reactive adhesive between a first plastic film and a second plastic film. Specifically, the reactive adhesive is applied to a first plastic film, then a second plastic film is laminated on the coated surface, and the adhesive layer is cured. For example, when the reactive adhesive is a solventless type, there is a method in which the first adhesive film is applied by a roll coater coating method, and then another substrate is bonded without passing through a drying step. In the case where the reactive adhesive contains a solvent, there is a method in which the first plastic film is applied by a roll coater coating method, passed through a drying oven at 60 ° C., and then another substrate is bonded. The coating conditions are preferably about 300 to 3000 mPa · s at 40 ° C. with a normal roll coater heated to 30 ° C. to 90 ° C., but the adhesive of the present invention is blended. Since the viscosity after leaving for 30 minutes in a 40 ° C. atmosphere is 5000 mPa · s or less, coating can be performed without any problem. The coating amount is preferably 0.5 to 5 g / m ² , more preferably about 0.5 to 3 g / m ² .

Also, a gravure or flexographic print of printing ink may be used on the first plastic film, and even in this case, a good laminate appearance can be exhibited. As the above-mentioned printing ink, a solvent type, aqueous type or active energy ray curable ink can be used.

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

The first plastic film used here is a PET (polyethylene terephthalate) film, a nylon film, an OPP (biaxially oriented polypropylene) film, a K-coated film such as polyvinylidene chloride, a base film such as various deposited films, and an aluminum foil. Examples of the second plastic film include CPP (unstretched polypropylene) film, VMCP (aluminum vapor-deposited unstretched polypropylene film), LLDPE (linear low density polyethylene), and LDPE. Examples thereof include sealant films such as (low density polyethylene), HDPE (high density polyethylene), and VMLDPE (aluminum vapor-deposited low density polyethylene film) films.

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

(Packaging body)
The package of the present invention is formed by forming the laminated film into a bag shape. Specifically, the package is formed by heat-sealing the laminated film. In addition, when considering the use as a package, required performance (easy tearability and hand cutability), rigidity and durability required for the package (for example, impact resistance, pinhole resistance, etc.) Other layers can be laminated as required. Usually, it is used with a base material layer, a paper layer, a second sealant layer, a non-work cloth layer and the like. As a method of laminating other layers, a known method can be used. For example, an adhesive layer may be provided between other layers and laminated by a dry laminate method, a heat laminate method, a heat seal method, an extrusion laminate method, or the like. As the adhesive, the reactive adhesive may be used, or other one-component type urethane adhesive, epoxy adhesive, aqueous dispersion of acid-modified polyolefin, or the like may be used.

As a specific laminate structure, the first plastic film layer / adhesive layer / second plastic layer, first plastic layer, which can be suitably used for general packaging bodies, lid materials, refill containers, etc. A second plastic layer / paper that can be suitably used for a base layer / adhesive layer / first plastic film layer / adhesive layer / second plastic layer, paper container, paper cup, etc. Layer / adhesive layer / first plastic film layer / adhesive layer / second plastic, second plastic layer / paper layer / polyolefin resin layer / substrate layer / first plastic layer / adhesive layer / second plastic Layer, paper layer / first plastic film layer / adhesive layer / sealant layer, second plastic layer / adhesive layer / first plastic that can be suitably used for tube containers, etc. Click layer / adhesive layer / etc. second plastic layer. These laminates may have a print layer, a top coat layer, or the like as necessary.

The first plastic film layer includes, for example, a polyester resin film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polylactic acid (PLA); a polyolefin resin film such as polypropylene; a polystyrene resin film; a nylon 6, a poly- Polyamide resin film such as p-xylylene adipamide (MXD6 nylon); Polycarbonate resin film; Polyacrylonitrile resin film; Polyimide resin film; Multilayers thereof (for example, nylon 6 / MXD6 / nylon 6, nylon 6 / An ethylene-vinyl alcohol copolymer / nylon 6) or a mixture is used. Among them, those having mechanical strength and dimensional stability are preferable. Of these, a film arbitrarily stretched in the biaxial direction is preferably used.

Further, the first plastic film layer is made of a soft metal foil such as an aluminum foil to provide a barrier function, as well as a vapor deposition layer such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, and silica alumina binary vapor deposition; vinylidene chloride resin An organic barrier layer made of modified polyvinyl alcohol, ethylene vinyl alcohol copolymer, MXD nylon or the like can be used. *

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

Examples of paper layers include natural paper and synthetic paper. The first and second sealant layers can be formed of the same material as the above-described sealant layer. You may provide a printing layer in the outer surface or inner surface side of a base material layer and a paper layer as needed. *

The “other layer” may contain a known additive or stabilizer, for example, an antistatic agent, an easy adhesion coating agent, a plasticizer, a lubricant, an antioxidant, or the like. In addition, “other layers” are those in which the surface of the film has been subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc. as a pretreatment in order to improve adhesion when laminated with other materials. May be. *

As an aspect of the package of the present invention, a three-sided seal bag, a four-sided seal bag, a gusset packaging bag, a pillow packaging bag, a gobeltop-type bottomed container, a tetra classic, a backpack type, a tube container, a paper cup, a lid material, etc. There are various types. In addition, an easy-opening treatment or resealability means may be provided as appropriate in the package of the present invention.

The laminate obtained in this way can be used in various applications, such as packaging materials for foods and pharmaceuticals, daily necessities, barrier materials, roofing materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting. Protective materials, automotive parts, signboards, stickers, etc. for outdoor industrial use, decorative sheets used for simultaneous injection molding methods, liquid detergent for washing, liquid detergent for kitchen, liquid detergent for bath, liquid soap for bath, liquid shampoo It can be suitably used as a packaging material such as a liquid conditioner.

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

(Synthesis Example 1)
Synthesis of PET-containing polyester polyol (A1-1) In a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a rectifying tower, 27.2 g of ethylene glycol, neopentyl glycol 205 0.08 g, adipic acid 178.7 g, isophthalic acid 164.0 g, regenerated PET pellets 64.0 g and dibutyltin oxide 0.11 g as a polymerization catalyst are charged. Gradually raise the temperature under normal pressure nitrogen flow and raise the temperature to 230 ° C. while performing dehydration reaction. After reacting at 230 ° C. for 2 hours, confirm that the contents became transparent, and the rectification tower After confirming that the column top temperature was 80 ° C. or lower, the rectifying column was removed and switched to a glass condenser, and a line was connected from a nitrogen gas inlet tube to a vacuum pump, and a condensation reaction was performed for 5 hours under a reduced pressure of 50 Torr. When the prescribed acid value and viscosity were reached, the temperature was lowered to 130 ° C., and ethyl acetate was added and diluted using a dropping funnel to obtain a PET-containing polyester polyol (A1-1). Weight fraction of PET pellets at the time of raw material charging, weight fraction of 1,6-hexanediol, weight fraction of dimer acid and acid value of solid conversion of the obtained PET-containing polyester polyol (A1-1), solid conversion Tables 1 and 2 show the hydroxyl value, solid content, and number average molecular weight.

(Synthesis Example 2), (Synthesis Example 6), (Synthesis Example 7)
Synthesis of PET-containing polyester polyol (A1-2), (A1-6), (A1-7) The PET-containing polyester polyol (A1-1) was prepared in the same manner as in Tables 1 and 2, except that the raw materials shown in Tables 1 and 2 were used. Properties and the like are shown in Tables 1 and 2.

(Synthesis Example 3)
Synthesis of PET-containing polyester polyol (A1-3) In a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a rectifying column, 20.0 g of ethylene glycol, 150 of neopentyl glycol 150 0.1 g, 1,6-hexanediol 92.0 g, dimer acid 92.0 g, adipic acid 174.7 g, isophthalic acid 160.5 g, PET pellets 76.5 g and dibutyltin oxide 0.14 g as a polymerization catalyst are charged. Gradually raise the temperature under normal pressure nitrogen flow and raise the temperature to 220 ° C. while performing dehydration reaction. After reacting at 220 ° C. for 2 hours, confirm that the contents became transparent, and the rectification tower After confirming that the column top temperature was 80 ° C. or lower, the rectifying column was removed and switched to a glass condenser, a line was connected from the nitrogen gas inlet tube to a vacuum pump, and a condensation reaction was carried out for 4 hours under a reduced pressure of 50 Torr. When the predetermined acid value and viscosity were reached, the temperature was lowered to 130 ° C., and ethyl acetate was added and diluted using a dropping funnel to obtain a PET-containing polyester polyol (A1-3). Weight fraction of PET pellets at the time of raw material charging, weight fraction of 1,6-hexanediol, weight fraction of dimer acid and acid value of solid conversion of the obtained PET-containing polyester polyol (A1-3), solid conversion Tables 1 and 2 show the hydroxyl value, solid content, and number average molecular weight.

(Synthesis Example 4), (Synthesis Example 5), (Synthesis Example 8), (Synthesis Example 10)
Synthesis of PET-containing polyester polyol (A1-4), (A1-5), (A1-8), (A1-10) PET-containing polyester polyol (A1-3) except that the raw materials shown in Tables 1 and 2 were used Manufactured in the same manner. Properties and the like are shown in Tables 1 and 2.

(Synthesis Example 9)
Synthesis of PET-containing polyester polyol (A1-9) In a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a rectifying column, 14.6 g of ethylene glycol, neopentyl glycol 109 .7 g, 1,6-hexanediol 21.0 g, dimer acid 21.0 g, adipic acid 90.3 g, isophthalic acid 83.0 g, PET pellet 690.0 g and dibutyltin oxide 0.14 g as a polymerization catalyst are charged. Gradually raise the temperature under normal pressure nitrogen flow and raise the temperature to 220 ° C while performing dehydration reaction. After reacting at 220 ° C for 5 hours, confirm that the contents became transparent, and the rectification tower After confirming that the column top temperature was 80 ° C. or lower, the rectifying column was removed and switched to a glass condenser, and a line was connected from a nitrogen gas inlet tube to a vacuum pump, and a condensation reaction was performed for 5 hours under a reduced pressure of 50 Torr. When the prescribed acid value and viscosity were reached, the temperature was lowered to 130 ° C., and ethyl acetate was added and diluted using a dropping funnel to obtain a PET-containing polyester polyol (A1-9). Weight fraction of PET pellets at the time of raw material charging, weight fraction of 1,6-hexanediol, weight fraction of dimer acid and acid value of solid conversion of the obtained PET-containing polyester polyol (A1-9), solid conversion Tables 1 and 2 show the hydroxyl value, solid content, and number average molecular weight.

(Comparative Synthesis Example 1)
Synthesis of PET-Decomposed Polyester Polyol (A1-11) In a glass 2-liter four-necked flask equipped with a stirring blade, temperature sensor, nitrogen gas introduction tube and glass cooling tube, 27.2 g of ethylene glycol, neopentyl glycol 205.0 g, 372.0 g of recycled PET pellets and 0.60 g of tetraisopropyl titanate as a transesterification catalyst are charged. The temperature was raised to 190 ° C. under a normal pressure nitrogen stream, and the PET was sufficiently decomposed at 190 ° C. over 7 hours, and the reaction solution became completely transparent and uniform with no insoluble matter in the PET pellets. After confirming the above, it is cooled to 130 ° C., and 157.5 g of adipic acid and 144.7 g of isophthalic acid are charged. Gradually raise the temperature under normal pressure nitrogen and raise the temperature to 250 ° C. while performing a dehydration reaction, and react for 2 hours at 250 ° C. After confirming that the top temperature of the rectifying column is 80 ° C. or less, Remove the distillation column, switch to a glass condenser, and lower the temperature to 230 ° C. When the temperature reaches 230 ° C., a line is connected from the nitrogen gas inlet tube to a vacuum pump, and a condensation reaction is performed for 8 hours under a reduced pressure of 50 Torr. When the predetermined acid value and viscosity were reached, the temperature was lowered to 130 ° C., and ethyl acetate was added and diluted using a dropping funnel to obtain a PET-containing polyester polyol (A1-11). Tables 1 and 2 show the weight fraction of the PET pellets when the raw materials are charged, the solid-converted acid value, the solid-converted hydroxyl value, the solid content, and the number-average molecular weight of the obtained PET-decomposed polyester polyol (A1-11).

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

(Comparative Synthesis Example 3)
Synthesis of PET-Decomposed Polyester Polyol (A1-13) In a glass 2-liter four-necked flask equipped with a stirring blade, a temperature sensor, a nitrogen gas inlet tube and a rectifying column, 61.6 g of neopentyl glycol, 1,6- 118.7 g of hexanediol, 23.0 g of trimethylolpropane, 157.8 g of adipic acid, 89.4 g of isophthalic acid, 328.2 g of recycled PET pellets, and 0.60 g of monobutyltin oxide as a polymerization catalyst are charged. The temperature was raised gradually to 230 ° C. while performing a dehydration reaction under a normal nitrogen flow, and the reaction was carried out at 230 ° C. for 2 hours, but the contents did not become transparent. After 3 hours of reaction, confirm that the top temperature of the rectification column is 80 ° C or less, remove the rectification column, switch to a glass condenser, connect the line from the nitrogen gas inlet tube to the vacuum pump, and reduce the pressure to 50 Torr. The condensation reaction is carried out for 9 hours. When the prescribed acid value and viscosity were reached, the temperature was lowered to 130 ° C., and ethyl acetate was added and diluted using a dropping funnel to obtain a PET-containing polyester polyol (A1-13). Weight fraction of PET pellets at the time of raw material charging, weight fraction of 1,6-hexanediol, weight fraction of dimer acid and acid value of solid conversion of the obtained PET-decomposed polyester polyol (A1-13), solid conversion Tables 1 and 2 show the hydroxyl value, solid content, and number average molecular weight.

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

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

(Synthesis Example 12) to (Synthesis Example 20), (Comparative Synthesis Example 4) to (Comparative Synthesis Example 5)
Synthesis of PET-containing polyester polyurethane polyols (A2-2) to (A2-10) and synthesis of PET-decomposed polyester polyurethane polyols (A2-11) (A2-12) PET-containing except that the raw materials shown in Tables 3 and 4 were used It was produced in the same manner as the polyester polyurethane polyol (A2-1). Tables 3 and 4 show property values and the like. In Tables 3 and 4, IPDI is an abbreviation for isophorone diisocyanate.

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

(Evaluation)
(High speed processability)
A dry laminator (Musashino Machine Design Office, dry lami test coater) is used as the laminating machine, the processing speed is 250 m / min, and the first plastic film layer is a PET film (commercial polyethylene terephthalate film). After applying the adhesives of Examples or Comparative Examples so that the application amount was 3 g / m ² , VMCP (commercially available aluminum-deposited unstretched polypropylene film) was laminated as a second plastic film layer to obtain a laminated film.
The appearance of the film immediately after laminating (whether there are defects such as wrinkles, bubbles due to bubbles, tunneling caused by misalignment between films) was judged based on the following evaluation criteria using visual and scale loupes. The evaluation with a scale loupe was performed with the number of bubbles in a 1 cm 2 scale.
Evaluation criteria
◎: No bubbles, no wrinkles or tunneling ○: No bubbles, no wrinkles or tunneling ○-: No bubbles, no tunneling △: No bubbles Wrinkles and tunneling partially occur in several tens to sixteen. ×: Wrinkles and tunneling occur in many places with 17 or more bubbles.

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

The evaluation method uses a Tensilon universal testing machine manufactured by Orientec Co., Ltd., cuts out a 15 mm wide test piece from the pouch after retort treatment, wipes the contents well, and then has an atmosphere temperature of 25 ° C. and a peeling speed of 300 mm / min. The tensile strength when peeled by the 180 degree peeling method was compared as the adhesive strength. The unit of adhesive strength was N / 15 mm. If the adhesive strength is 5 N / 15 mm or more, it can be said that it is practically sufficient.
Evaluation criteria A: Adhesive strength 12 N / 15 mm or more ○: Adhesive strength 7 N / 15 mm or more, less than 12 N / 15 mm ○: Adhesive strength 5 N / 15 mm or more, less than 7 N / 15 mm Δ: Adhesive strength 1 N / 15 mm or more, less than 5 N / 15 mm X: Adhesive strength less than 1 N / 15 mm

(Content resistance)
A dry laminator (Musashino Machine Design Office, dry lami test coater) was used as the laminating machine, the processing speed was 250 m / min, and the first plastic film layer was Nyl (commercial nylon film). Or after apply | coating the adhesive agent of a comparative example so that the application quantity might be 4.3 g / m < ² >, LLDPE (commercially available linear low density polyethylene film) was laminated as a 2nd plastic film layer. Thereafter, aging was performed at 40 ° C. for 5 days to obtain a laminated film.
A pouch having a size of 120 mm × 120 mm was prepared using the obtained laminated film, and 70 g of Super sol pH = 13 was filled in the pouch as a content. Thereafter, treatment was performed for 3 days in a thermostatic bath at 50 ° C., and evaluation was performed by measuring peel strength.

The evaluation method is a Tensilon universal testing machine manufactured by Orientec Co., Ltd., a test piece having a width of 15 mm is cut out from the pouch after the content resistance test, the content is thoroughly wiped, and the atmosphere temperature is 25 ° C., and the peeling speed is 300 mm. / Min, the tensile strength when peeled by the 180 degree peeling method was compared as the adhesive strength. The unit of adhesive strength was N / 15 mm. If the adhesive strength is 2 N / 15 mm or more, it can be said that it is practically sufficient.
Evaluation criteria A: Adhesive strength 7 N / 15 mm or more B: Adhesive strength 5 N / 15 mm or more, less than 7 N / 15 mm B: Adhesive strength 2 N / 15 mm or more, less than 5 N / 15 mm Δ: Adhesive strength 1 N / 15 mm or more, less than 2 N / 15 mm X: Adhesive strength less than 1 N / 15 mm

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

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

Claims (9)

1. A reactive adhesive containing a polyol composition (A) and a polyisocyanate composition (B), wherein the polyol composition (A) is prepared by batch feeding of polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid. A reactive adhesive comprising polyester polyol (A1) which is a reaction product.
2. The reactive adhesive according to claim 1, wherein the proportion of polyethylene terephthalate in the charged raw material of the polyester polyol (A1) is 5 to 50% by mass.
3. The reactive adhesive according to claim 1 or 2, wherein the polybasic acid is a dimer acid, and a ratio of the dimer acid in the raw material of the polyester polyol (A1) is 5 to 20% by mass.
4. The reactive adhesive according to any one of claims 1 to 3, wherein the polyol composition (A) contains a polyester polyurethane polyol (A2) which is a reaction product of a polyisocyanate and the polyester polyol (A).
5. The reactive adhesive layer according to any one of claims 1 to 4, wherein the adhesive layer is a laminated film formed by laminating an adhesive layer between a first plastic film and a second plastic film. A laminated film characterized by the above.
6. 5. The reactive adhesion according to claim 1, wherein the first plastic film, the printing layer, the adhesive layer, and the second plastic film are laminated in this order, and the adhesive layer is the reactive adhesive according to any one of claims 1 to 4. A laminated film characterized by being a layer of an agent.
7. The package formed by shape | molding the laminated | multilayer film of Claim 5 or 6 in a bag shape.
8. A method for producing a polyester polyol (A1), wherein polyethylene terephthalate, polyhydric alcohol, and polybasic acid are charged and reacted together.
9. A method for producing a polyester polyurethane polyol (A2), comprising reacting a polyester polyol (A1) in which polyethylene terephthalate, a polyhydric alcohol, and a polybasic acid are charged and reacted together, and a polyisocyanate.