TW202128932A - Reactive adhesive agent, laminate, and package - Google Patents

Abstract

A reactive adhesive agent comprising a polyol ingredient A and an isocyanate ingredient B, wherein the polyol ingredient A includes a polyol (A1) satisfying (1) and (2); a laminate obtained by laminating a plurality of films or paper sheets using the reactive adhesive agent; and a package. (1) To have a hydrocarbon group having a branched structure. (2) To have been formed from starting reactive materials comprising a polyol (X1) containing an ether bond but containing no ester bond, a bi- or higher-functional isocyanate (Y), and a polyol (X2) containing an ester bond.

Description

Reactive adhesive, laminate and packaging

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

Previously, various plastic films were laminated to each other, or laminates formed by laminating plastic films and paper, metal vapor-deposited films, or metal foils were used for various purposes, such as packaging materials for food, medicine, and daily necessities. , Or decoration used in outdoor industrial applications such as wall protection materials, roofing materials, solar panel materials, battery packaging materials, window materials, outdoor floor materials, lighting protection materials, automotive components, signboards, stickers, etc., injection molding and decoration methods, etc. Uses, etc. These laminated systems are manufactured by appropriately combining various plastic films, metal vapor-deposited films, or metal foils according to the required characteristics of various applications, and then perform printing on these films, and select adhesives according to various required characteristics. For example, if the use is food or daily necessities, in order to protect the contents from the effects of refrigerated storage or heat sterilization during circulation, the so-called "strength, resistance to cracking, sterilization resistance, heat resistance, and content resistance" are required Function. Furthermore, these laminates are not circulated in a sheet form. For example, when used for food packaging, the sides are generally heat-sealed and circulated in a bag form, so heat-sealability is also a required characteristic.

Regarding the adhesive used in this type of laminate, a reactive adhesive (also known as 2-component curing agent) that reacts the hydroxyl groups of polyether polyols or polyester polyols with the isocyanate groups of polyisocyanates has been known from the past. Type adhesive). For example, in Patent Document 1, it is described that an adhesive composition containing the following first component and a second component is excellent in heat-seal strength, wherein the first component contains a polyether polyol, a polyether polyurethane One or more polyols among ester polyols, polyester polyols, and polyester polyurethane polyols, and the second component contains polyisocyanate; and Patent Document 2 describes that it contains polyester polyamine The adhesive composition of carbamate and polyisocyanate is excellent in heat sealing strength, and the polyester polyurethane has a structure in which the chain of polyester polyol is extended by isophorone diisocyanate. However, the reactive adhesives including the combination of a polyol having an ester structure and an ether structure and a polyisocyanate have not been reviewed so far. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2001-164229 [Patent Document 2] JP 2011-102387

[The problem to be solved by the invention]

The problem to be solved by the present invention is to provide a reactive adhesive that has both an ester structure and an ether structure, and has excellent laminate appearance and heat seal strength. [Means to solve the problem]

Polyester polyols or polyether polyols are widely used as components of reactive adhesives, but there are some differences in the physical properties obtained. For example, a reactive adhesive with a polyester structure as the main component has excellent adhesive properties and heat resistance, but the appearance of the laminate is slightly poor, so it is mostly used for applications requiring heat resistance such as food sterilization. On the other hand, a reactive adhesive having a polyether structure as a main component has an excellent appearance of the laminate, but is slightly inferior in adhesive properties and heat resistance, so it is often used as a consumable that does not require heat resistance.

The inventors of the present invention focused on the results of the examination of polyols with these characteristics, and found that they contain hydrocarbon groups with branched structures, and polyols (X1) with ether bonds but no ester bonds, and isocyanates with two or more functions (X1) Y) and a polyol having an ester bond (X2) as a reaction raw material can solve the above-mentioned problems.

That is, the present invention provides a reactive adhesive, which is a reactive adhesive containing a polyol component A and an isocyanate component B, wherein the polyol component A contains a polyol (A1), and the polyol (A1) has a component A hydrocarbon group with a branch structure, and a polyol (X1) with an ether bond but no ester bond, a bifunctional or higher isocyanate (Y), and a polyol with an ester bond (X2) as the reaction raw materials.

Furthermore, the present invention provides a laminate which is a laminate obtained by bonding a plurality of films or papers through an adhesive, wherein the adhesive is the reactive adhesive described herein.

In addition, the present invention provides a laminate which is a laminate in which films or papers provided with a plurality of printing layers are bonded by an adhesive, and the adhesive is the reactive adhesive described above.

In addition, the present invention provides a package in which the aforementioned laminate is formed into a bag shape. [Effects of Invention]

Since the reactive adhesive of the present invention has excellent heat-seal strength, the resulting laminate film does not peel off at the interface of the adhesive after the heat-sealing treatment, and the appearance is also excellent.

[Form to implement the invention]

(Definition of term solvent) The reactive adhesive of the present invention, as described above, is a reactive two-component laminate adhesive. In the present invention, an adhesive hardened by a chemical reaction between an isocyanate group and a hydroxyl group is used. In the present invention, a solvent may be used or no solvent may be used. Furthermore, the term "solvent" in the present invention means the volatile organic solvent used in the present invention that can dissolve polyisocyanate or polyol and has high solubility. "Solvent type" means including these highly soluble Organic solvents, "solvent-free" means that they do not contain such highly soluble organic solvents. Organic solvents with high solubility, specifically, toluene, xylene, dichloromethane, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl 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 organic solvents with extremely high solubility.

The reactive adhesive of the present invention can be used after being diluted with a suitable organic solvent with high solubility according to the desired viscosity when low viscosity is required. In this case, either the polyol component A or the isocyanate component B may be diluted, or both may be diluted. As for the organic solvents used in this case, examples include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluene, Xylene, n-hexane, cyclohexane, etc. Among these, from the viewpoint of solubility, ethyl acetate or methyl ethyl ketone (MEK) is preferred, and ethyl acetate is particularly preferred. Although the organic solvent should be used according to the desired viscosity, it is usually adjusted and diluted to a solid content of about 20-60% by mass. In addition, in order to lower the viscosity of the adhesive of the present invention, a solvent that does not have a hydroxyl group but has a boiling point of 200° C. or higher with a carbonyl group, such as triacetin and propylene carbonate, can also be used. The usage amount of these high boiling point organic solvents is usually in the range of about 0.1-10% by mass according to the required viscosity and the physical properties of the coating film.

(Polyol component A) The polyol component A used in the reactive adhesive of the present invention is characterized by containing a polyol (A1) satisfying (1) and (2). The polyol (A1) is a polyurethane polyol. (1) Possess a hydrocarbon group with a branched structure. (2) A polyol (X1) having an ether bond but no ester bond, an isocyanate (Y) having more than two functions, and a polyol (X2) having an ester bond are used as reaction materials.

(Polyol component A branch structure) The aforementioned (1) "containing a branched structure-containing hydrocarbon group", specifically, in the reaction raw material of the aforementioned polyol component A, in terms of polyol or polycarboxylic acid, a compound having a branched structure is used, specifically In other words, polyols with branched structures or polycarboxylic acids with branched structures or anhydrides thereof are preferred. Specifically, by using a trifunctional or higher alcohol, or a trifunctional or higher polycarboxylic acid or its anhydride, the hydrocarbon group of the main skeleton of the polyhydric alcohol can have a branched structure. For the alcohols with three or more functions used in the present invention (in addition, the functional group of the alcohol represents the hydroxyl group, and the element system such as di-valent, tri-valent, multi-element, etc. represents the number of hydroxyl groups), glycerol, trihydric Trifunctional or tetrafunctional aliphatic alcohols such as methyl propane and neopentyl erythritol. In addition, for polycarboxylic acids with more than three functions or their anhydrides (in addition, the functional group in the carboxylic acid represents a carboxyl group, and the number of carboxyl groups such as di-, tri-, and multi-element) includes Aliphatic tribasic acids such as 1,2,5-hexanetricarboxylic acid and 1,2,4-cyclohexanetricarboxylic acid; trimellitic acid, trimellitic anhydride, 1,2,5-benzenetricarboxylic acid, Aromatic tribasic acids such as 2,5,7-naphthalene tricarboxylic acid and their anhydrides.

Since the aforementioned polyol (A1) has the aforementioned branched structure, the heat-sealing resistance, which is the effect of the present invention, can be improved. In the present invention, with regard to the polyol or polycarboxylic acid which is the raw material for the reaction of the branched structure in the polyol component A, the ratio of the trifunctional or higher alcohol, or the trifunctional or higher polycarboxylic acid or its anhydride is based on 0.1 to 2.0 mol% is preferred.

(Polyol component A is a polyol (X1) with ether bond but no ester bond) As the raw material for the reaction of the polyol (A1) in the present invention, the polyol (X1) (hereinafter sometimes referred to as "polyol (X1)") having an ether bond but no ester bond is used, as long as it is not It has an ester bond, and it is not specifically limited, A well-known ether type polyol can be used. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexane can be cited Glycol, Neopentyl Glycol, Methyl Pentylene Glycol, Dimethyl Butylene Glycol, Butyl Ethyl Propylene Glycol, Diethylene Glycol, Triethylene Glycol, Tetraethylene Glycol, Dipropylene Glycol, Tripropylene Glycol, Dihydroxy Bifunctional alcohols (diols) such as ethoxybenzene, 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol; trifunctional or tetrafunctional such as glycerol, trimethylolpropane, and neopentylerythritol Aliphatic alcohols; Bisphenols such as Bisphenol A, Bisphenol F, Hydrogenated Bisphenol A, Hydrogenated Bisphenol F;

The aforementioned diols, trifunctional or tetrafunctional aliphatic alcohols, etc., are combined with ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and ethylene oxide in the presence of a polymerization initiator. A polyether polyol obtained by addition polymerization of alkylene oxides such as alkane; the polyether polyol is further polymerized by the aforementioned aromatic or aliphatic polyisocyanate polyether urethane polyol. Among them, a mixture of a bifunctional alcohol and a trifunctional or higher alcohol is preferred, and a mixture of a bifunctional alcohol and a trifunctional or tetrafunctional aliphatic alcohol is more preferred.

(Polyol component A polyol with ester bond (X2)) The polyol (X2) having an ester bond used as the reaction material of the polyol (A1) in the present invention (hereinafter sometimes referred to as "polyol (X2)"), as long as it has an ester bond, is not particularly limited and can be used Well-known ester-based polyols. For example, polyols obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, etc. Esters, polyester polyols (1) which are the reaction products of the aforementioned diols, glycerol, trimethylolpropane, neopentyl erythritol and other polyols; the aforementioned diols, dimer diols, or the aforementioned bisphenols, etc. Polyester polyol (2) obtained by reacting the aforementioned dihydric alcohol with polycarboxylic acid or polycarboxylic acid anhydride; polyester polyol obtained by reacting the aforementioned trifunctional or tetrafunctional aliphatic alcohol with polycarboxylic acid or polycarboxylic acid anhydride Alcohol (3); polyester polyol (4) obtained by reacting the aforementioned divalent polyol, the aforementioned trifunctional or tetrafunctional aliphatic alcohol with a polycarboxylic acid or a polycarboxylic acid anhydride (4); is dimethylolpropionic acid , Castor oil fatty acid and other hydroxy acid polymer polyester polyol (5);

A polyester polyether polyol obtained by reacting the aforementioned polyester polyols (1) to (5) and the aforementioned polyether polyol with an aromatic or aliphatic polyisocyanate; the aforementioned polyester polyols (1) to (5) ) Polyester polyurethane polyol obtained by high molecular weight of aromatic or aliphatic polyisocyanate; castor oil, dehydrated castor oil, hardened castor oil which is a hydrogenated product of castor oil, 5 of castor oil ～50 moles of castor oil-based polyols such as alkylene oxide adducts, etc.

Among them, polyester polyols are preferred. Furthermore, the reaction product of a polyhydric alcohol and a polybasic carboxylic acid or a polybasic carboxylic acid anhydride is preferable, wherein at least one of the polyhydric alcohol, the polybasic carboxylic acid, or the polybasic carboxylic anhydride is a compound having 3 or more hydroxyl groups or carboxyl groups . Specifically, the polyester polyol (3) obtained by reacting the aforementioned trifunctional or tetrafunctional aliphatic alcohol with polycarboxylic acid or polycarboxylic acid anhydride; Functional aliphatic alcohol, polyester polyol (4) obtained by reacting with polycarboxylic acid or polycarboxylic acid anhydride, etc. In addition, the weight average molecular weight (Mw) of the polyol used is preferably 1,000 to 30,000.

Among them, polycarboxylic acids, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, maleic anhydride, fumaric acid, 1,3-cyclopentadicarboxylic acid , 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid and other aliphatic dicarboxylic acids; terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, naphthoic acid, diphthalic acid, 1,2-bis(phenoxy)ethane-p-,p-'-dicarboxylic acid; and these aliphatic or aromatic Anhydride or ester-forming derivatives of dicarboxylic acids; polybasic acids such as p-hydroxybenzoic acid, p-(2-hydroxyethoxy)benzoic acid and ester-forming derivatives of these dihydroxycarboxylic acids, dimer acids . Among them, if it is an aliphatic dicarboxylic acid, when it is diluted with an organic solvent and used as a solvent-based adhesive, the residual solvent after coating can be further reduced, which is preferred. Among them, adipic acid is preferred.

As for the polyol (X2), more preferably, it is a polyester polyol which is a reaction product of a bifunctional polyol and an aliphatic dicarboxylic acid, or a bifunctional polyol and a trifunctional polyol and an aliphatic dicarboxylic acid Polyester polyol which is the reaction product of acid, or polyester polyol which is the reaction product of trifunctional polyol and aliphatic dicarboxylic acid.

(Polyol component A isocyanate with more than two functions (Y)) The bifunctional or higher isocyanate (Y) used as the reaction raw material of the polyol (A1) in the present invention (Furthermore, the functional group in the isocyanate represents an isocyanate group, a bi-valent, tri-valent, multi-component, etc., It represents the number of isocyanate groups) (Hereinafter, it may be referred to as "isocyanate (Y)"), and it is not particularly limited, and well-known bifunctional or higher isocyanates can be used. For example, toluene diisocyanate, diphenylmethane diisocyanate, polymerized diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylene diisocyanate and other molecular structures have aromatic Structure of polyisocyanate, a compound in which part of the NCO group of these polyisocyanates is modified with carbodiimide; isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 1,3 -(Isocyanatomethyl) cyclohexane and other polyisocyanates with alicyclic structure in the molecular structure; 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate , Straight-chain aliphatic polyisocyanates such as trimethylhexamethylene diisocyanate, and compounds in which part of the NCO groups of these polyisocyanates are modified by carbodiimide;

The isocyanurate bodies of the aforementioned various polyisocyanates; allophanate bodies derived from the aforementioned various polyisocyanates; the biuret bodies derived from the aforementioned various polyisocyanates; the aforementioned various polyisocyanates are The adduct body modified by trimethylolpropane; the polyisocyanate, etc., which are the reaction products of the aforementioned various polyisocyanates and polyol components. Among them, toluene diisocyanate is preferred.

(Polyol component A and other reaction materials) The polyol (A1) in the present invention contains a hydrocarbon group with the aforementioned branched structure, and is a polyol (X1) having an ether bond but no ester bond, the aforementioned bifunctional or higher isocyanate (Y), and the aforementioned ester-containing polyol (X1) The bond polyol (X2) is not particularly limited except as the reaction raw material. As for other reaction raw materials, the reaction raw materials used in the well-known polyurethane resin can be made within a range that does not impair the effect of the present invention. reaction. For example, in terms of chain extenders, ethylene diamine, propylene diamine, hexamethylene diamine, triethylene tetramine, diethylene triamine, isophorone diamine , Dicyclohexylmethyl-4,4´-diamine, dimer diamine, etc. Other aspects include 2-hydroxyethyl ethylene diamine, 2-hydroxyethyl ethylene diamine, di-2-hydroxyethyl ethylene diamine, di-2-hydroxyethyl ethylene diamine, 2 -Hydroxypropyl ethylene diamine, di-2-hydroxypropyl ethylene diamine and other diamines with hydroxyl groups in the molecule; neopentyl glycol, butyl ethyl propylene glycol, ethylene glycol, diethylene glycol, Dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol, 1- or 2-methyl-1,3-butanediol, 1- or 2-methyl-1, 4-pentanediol, 2,4-diethyl-1,5-pentanediol, tripropylene glycol, diethylene glycol, 1,2-propanediol, 1,3-butanediol, 1-, 2- or Diols such as 3-methyl-1,5-pentanediol and 2-methyl-1,3-propanediol; bisphenol A's ethylene oxide, propylene oxide, ethylene oxide and other epoxy Alkane adducts, and other diols, etc. Among these, isophorone diamine is particularly preferred.

In addition, for chain extenders other than the foregoing, methyldiethanolamine, methyldiisopropanolamine, phenyldiisopropanolamine, 4-methylphenyldiisopropanolamine, 4-methyl Diols having a tertiary amine structure such as phenyldiethanolamine, and mixtures of two or more of these.

In addition, the chain elongation stopper includes monoalcohols (methanol, propanol, butanol, 2-ethylhexanol, etc.), monoamines [mono- or dialkylamines with 2 to 8 carbon atoms (butyl Amine, dibutylamine, etc.), C2-6 mono- or dialkanolamine (monoethanolamine, diethanolamine, propanolamine, isopropanolamine, etc.)] and the like.

(Polyol component A structural formula) The polyol (A1) in the present invention may be a structural formula represented by the general formula (1).

(1)

(1)

In the general formula (1), X ₁ represents the bond but not having an ether of a polyol having an ester bond (X1) a reactive residue, U represents a urethane bond, Y ₁ represents more than 2 of the multifunctional isocyanate ( The reaction residue of Y), X ₂ represents the reaction residue of the aforementioned polyol (X2) having an ester bond, Z represents the reaction residue of the aforementioned polyol (X1) or the aforementioned polyol (X2), the aforementioned X ₁ or the aforementioned Either or both of X ₂ have a hydrocarbon group with a branched structure. n represents a repeating structure, and is a value calculated from the molecular weight described later.

(Production method of polyol component A polyol (A1)) The manufacturing method of polyol (A1) is not specifically limited, It can manufacture according to a well-known method. For example, by a one-stage method of reacting the aforementioned polyol (X1) as the reaction raw material with the aforementioned isocyanate (Y) and the aforementioned polyol (X2) at a time at a ratio of excess hydroxyl groups; making the aforementioned polyol as the reaction raw material (X1), the aforementioned isocyanate (Y), and the aforementioned polyol (X2) are reacted at the excess isocyanate group ratio to obtain a prepolymer with terminal isocyanate groups, and then the obtained prepolymer is combined with a chain extender in a suitable solvent And (or) the two-stage method of reacting the terminal chain-blocking agent; or the one-stage method of reacting polypropylene glycol and the combined polyol, diisocyanate compound, chain extender and (or) the terminal chain-blocking agent in the above-mentioned appropriate solvent at a time ; To be manufactured.

In addition, the polyol (A1) represented by the aforementioned general formula (1), specifically, the aforementioned polyol (X1), the aforementioned isocyanate (Y), and the aforementioned polyol (X2), which are the reaction raw materials, have alternate connections Structure. The polyol of this structure can be obtained by, for example, the following manufacturing method. (Example 1) When the aforementioned polyol (X1) and the aforementioned polyol (X2) which are the reaction raw materials are compatible with each other, they can be obtained by one-stage polymerization. "Compatible" means that when the aforementioned polyol (X1) and the aforementioned polyol (X2) are mixed at a mass ratio of 1:1, turbidity does not occur. The turbidity can be quantified visually or by a method such as a hazemeter.

With regard to the combination of the aforementioned polyol (X1) and the aforementioned polyol (X2), for example, ・Polypropylene glycol (equivalent to polyol (X1)) and a combination of polyester polyol (equivalent to polyol (X2)), where the polyester polyol is the condensation of diethylene glycol and ethylene glycol and adipic acid Things, or ・Polypropylene glycol (equivalent to polyol (X1)) and a combination of polyester polyol (equivalent to polyol (X2)), where the polyester polyol is diethylene glycol, ethylene glycol and trimethylolpropane Condensate with adipic acid, or ・Polypropylene glycol (equivalent to polyol (X1)) and a combination of polyester polyol (equivalent to polyol (X2)), where the polyester polyol is diethylene glycol, ethylene glycol, adipic acid and partial Condensate of trimellitic anhydride, or ・A combination of polypropylene glycol (equivalent to polyol (X1)) and polyester polyol (equivalent to polyol (X2)), where the polyester polyol is a condensate of diethylene glycol and adipic acid.

The aforementioned polyol (A1) is preferably 10% to 100% by mass relative to the total mass of the polyol component A, more preferably 50% to 100% by mass, and more preferably 80% to 100% by mass Is the best. On the other hand, the compound represented by the aforementioned general formula (1) generally produces a reaction product having a molecular weight distribution in a polymer reaction, so the content is at least 10% by mass or more relative to the total mass of the polyol component A That's it.

The hydroxyl value of the aforementioned polyol (A1) is preferably in the range of 1-100 mgKOH/g, and more preferably in the range of 5-50 mgKOH/g.

The weight average molecular weight (Mw) of the aforementioned polyol (A1) is preferably in the range of 500 to 50,000, more preferably in the range of 1,000 to 30,000. In addition, the molecular weight distribution (Mw/Mn) is preferably in the range of 2-10.

Furthermore, in the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) 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 Co., Ltd. ＋TSK-GEL SuperHZM-M×4 manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: Multi-station GPC-8020modelII manufactured by Tosoh Co., Ltd. Measurement conditions: column temperature 40°C Solvent Tetrahydrofuran Flow rate 0.35ml/min Standard: Monodisperse Polystyrene Sample: A 0.2% by mass tetrahydrofuran solution converted to resin solid content, filtered through a microfilter (100μl)

(Polyol component A and other components) In this case, as mentioned above, the polyol (A1) must be contained, but other polyols may be used in combination within a range that does not impair the effect of the present invention. For example, a simple polyester polyol, a polyether polyol, or a polyol such as a polyurethane polyol can be used in combination.

(Isocyanate component B) The isocyanate component 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 is not particularly limited, and known ones can be used, and they can be used alone, or a plurality of them can be mixed and used.

For example, toluene diisocyanate, diphenylmethane diisocyanate, polymerized diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylene diisocyanate and other molecular structures have aromatic Structure of polyisocyanate; isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 1,3-(isocyanatomethyl) cyclohexane and other molecular structures with alicyclic structure Polyisocyanate; 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate and other linear aliphatic polyisocyanates;

Compounds in which part of the NCO groups of the aforementioned various polyisocyanates are modified with carbodiimide; isocyanurate bodies of the aforementioned various polyisocyanates; allophanate bodies derived from the aforementioned various polyisocyanates; derived from the aforementioned various Biuret of polyisocyanate; addition product modified by trimethylolpropane of the aforementioned various polyisocyanates; polyisocyanate, etc., which are the reaction products of the aforementioned various polyisocyanates and polyol components.

It may also be a polyisocyanate which is a reaction product of the aforementioned various polyisocyanate compounds and polyols. In this case, the polyol can be selected from polyols, polyester polyols, polyether polyols, polyurethane polyols, polyether ester polyols, Polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyalkane, castor oil or Polymer polyols of their mixtures, etc. Among them, it is preferable to use polyisocyanates which are reaction products of the aforementioned various polyisocyanates and the aforementioned polyether polyols from the viewpoints of adhesive strength, heat resistance, and resistance to contents. The reaction ratio of the polyisocyanate compound and the polyol, the equivalent ratio of the isocyanate group to the hydroxyl group [isocyanate group/hydroxyl group] is in the range of 1.0 to 5.0. From the viewpoint of the balance between the cohesive force and flexibility of the adhesive coating film, For better.

In addition, the aforementioned isocyanate may be mixed and used in various ways. Among them are the polyisocyanates which are the reaction products of the aforementioned various polyisocyanates and the aforementioned polyether polyols, and the compounds in which part of the NCO groups of the aforementioned various polyisocyanates are modified with carbodiimide; the isocyanuric acid of the aforementioned various polyisocyanates Ester body; Allophanate body derived from the aforementioned various polyisocyanates; Biuret body derived from the aforementioned various polyisocyanates; Addition bodies modified from the aforementioned various polyisocyanates with trimethylolpropane; are the aforementioned various A mixture of polyisocyanate, etc., which is a reaction product of a polyisocyanate and a polyol component, is preferred. Among them, a mixture of polyisocyanates, which are the reaction products of the aforementioned various polyisocyanates and the aforementioned polyether polyols, and the addition objects modified by the aforementioned various polyisocyanates with trimethylolpropane, is preferred, and the molecular structure is A mixture of polyisocyanate, which is a reaction product of polyisocyanate having an alicyclic structure and polyether polyol, and an adduct of polyisocyanate having an aromatic structure modified with trimethylolpropane is more preferable.

Among them, although the aforementioned isocyanate component B functions as a curing agent for the aforementioned polyol component A, when the epoxy compound and the hydroxyl-containing polycarbonate resin are used together as described later, and the resin contains a hydroxyl group, It can also react with the hydroxyl group to harden.

In the aforementioned isocyanate component B, the polyisocyanate compound is preferably 10% to 100% by mass relative to the total mass of the isocyanate component B, more preferably 50% to 100% by mass, and more preferably 80% to 100% by mass. Quality% is the best.

(Reactive adhesive ratio) The reactive adhesive of the present invention is preferably blended so that the molar ratio of the isocyanate group to the hydroxyl group in the reactive adhesive becomes 1.1 or more. If it is within this range, the heat sealing resistance can be further improved. Among them, the molar ratio is preferably 1.3 or more, and 1.5 or more is the most preferable. On the other hand, the upper limit is not particularly limited, but from the viewpoint of poor hardening, 3.0 or less is preferable. In the present invention, blending is preferred when the isocyanate group becomes excessive. It is inferred that the isocyanate group that has not reacted with the hydroxyl group contained in the polyol component A will react with moisture to form a urea bond, thereby imparting better heat sealing resistance.

(additive) The reactive adhesive of the present invention is a reactive adhesive having the aforementioned polyol component A and the aforementioned isocyanate component B as described above, but other various additives used in the reactive adhesive can also be used. By using, for example, a catalyst, the hardening reaction can be promoted. The catalyst used in the present invention is not particularly limited as long as it is used to promote the carbamate reaction. For example, metal-based catalysts, amine-based catalysts, and diazabicycloundecene (DBU) can be used. , Aliphatic cyclic amide compounds, titanium chelate complexes and other catalysts.

For metal-based catalysts, metal complexes, inorganic metal, and organometallic systems can be cited. For metal complexes, specifically, it can be selected from the group consisting of Fe (iron) and Mn (manganese). ), Cu (copper), Zr (zirconium), Th (thallium), Ti (titanium), Al (aluminum) and Co (cobalt) group of metal acetylpyruvate, for example, acetylacetone Iron, manganese acetylpyruvate, copper acetylpyruvate, zirconium acetylpyruvate, etc. Among these, from the viewpoint of toxicity and catalyst activity, iron acetylpyruvate (Fe(acac) ₃ ) or manganese acetylpyruvate (Mn(acac) ₂ ) is preferred.

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

For organometallic catalysts, stannous diacetate, stannous dicaprylate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin diacetate, Laurate, dibutyltin dichloride, dioctyltin dilaurate, nickel octoate, nickel naphthenate, cobalt octoate, cobalt naphthenate, bismuth octoate, bismuth naphthenate, etc. Among the preferred compounds, they are organotin catalysts, more preferably stannous dioctanoate and dibutyltin dilaurate.

啶(quinuclidine)、2-甲基

啶等。此等之中，從觸媒活性優良，工業可取得而言，以三伸乙基二胺、2-甲基三伸乙基二胺為較佳。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,

Quinuclidine, 2-methyl

Pyridine and so on. Among these, in terms of excellent catalyst activity and industrial availability, triethylenediamine and 2-methyltriethylenediamine are preferred.

啶醇、N,N,N’,N’-四甲基胍、1,3,5-參(N,N-二甲基胺基丙基)六氫-S-三

、1,8-二氮雜雙環[5.4.0]十一烯-7、N-甲基-N’-(2-二甲基胺基乙基)哌

、N,N’-二甲基哌

、二甲基環己基胺、N-甲基

啉、N-乙基

啉、1-甲基咪唑、1,2-二甲基咪唑、1-異丁基-2-甲基咪唑、1-二甲基胺基丙基咪唑、N,N-二甲基己醇胺、N-甲基-N’-(2-羥基乙基)哌

、1-(2-羥基乙基)咪唑、1-(2-羥基丙基)咪唑、1-(2-羥基乙基)-2-甲基咪唑、1-(2-羥基丙基)-2-甲基咪唑等。For other tertiary amine catalysts, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylethylenediamine can be listed , N,N,N',N”,N”-pentamethyldiethylenetriamine, N,N,N',N”,N”-pentamethyl-(3-aminopropyl) Ethyl diamine, N,N,N',N”,N”-pentamethyldipropylene triamine, N,N,N',N'-tetramethylhexamethylene diamine, bis( 2-Dimethylaminoethyl)ether, dimethylethanolamine, dimethylisopropanolamine, dimethylaminoethoxyethanol, N,N-dimethyl-N'-(2-hydroxyl Ethyl) ethylene diamine, N,N-dimethyl-N'-(2-hydroxyethyl) propylene diamine, bis(dimethylaminopropyl)amine, bis(dimethylamino) Propyl) isopropanolamine, 3-

Pyridinol, N,N,N',N'-tetramethylguanidine, 1,3,5-ginseng (N,N-dimethylaminopropyl)hexahydro-S-tri

, 1,8-diazabicyclo[5.4.0]undecene-7, N-methyl-N'-(2-dimethylaminoethyl)piper

, N,N'-Dimethylpiper

, Dimethylcyclohexylamine, N-methyl

Morpholine, N-ethyl

Morpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N,N-dimethylhexanolamine , N-methyl-N'-(2-hydroxyethyl)piper

, 1-(2-hydroxyethyl)imidazole, 1-(2-hydroxypropyl)imidazole, 1-(2-hydroxyethyl)-2-methylimidazole, 1-(2-hydroxypropyl)-2 -Methylimidazole and so on.

The aliphatic cyclic amide compound includes, for example, δ-valerolactam, ε-caprolactam, ω-heptanolactam, η-caprolactam, β-propiolactin, and the like. Among these, ε-caprolactam is more effective in promoting hardening.

Titanium chelate complexes are compounds that can increase the catalytic activity by ultraviolet irradiation. Titanium chelate complexes that use aliphatic or aromatic diketones as ligands have excellent hardening promotion effects. , Is better. In addition, in the present invention, in addition to the aromatic or aliphatic diketone as the ligand, an alcohol having 2 to 10 carbon atoms is preferred because the effect of the present invention is more significant. In the present invention, the aforementioned catalyst may be used alone or in combination.

The mass ratio of the aforementioned catalyst is preferably in the range of 0.001 to 3 parts, preferably in the range of 0.01 to 2 when the mixture of the polyisocyanate composition (B) and the polyol composition (A) is taken as 100 parts. The range of parts is better.

紫等各種二

系顏料；Chromophthal(商品名)等各種縮合偶氮顏料；苯胺黑等。(Pigment) In addition, the reactive adhesive of the present invention may also be combined with a pigment if necessary. The pigments that can be used in this case are not particularly limited. For example, extender pigments, white pigments, black pigments, gray pigments, red pigments, and brown pigments described in the 1970 edition of the Handbook of Coating Materials (Edited by the Japan Paint Industry Association) , Green pigments, blue pigments, metal powder pigments, luminescent pigments, pearl pigments and other organic or inorganic pigments, and plastic pigments. In terms of specific examples of these colorants, various types can be revealed. For organic pigments, for example, various insoluble azo pigments such as benzidine yellow, Hansa yellow, and lake 4R can be revealed. ; Lake C, Carmin 6B, Baudeaux 10 and other soluble azo pigments; phthalocyanine blue, phthalocyanine green and other (copper) phthalocyanine pigments; rose red (rhodamine) lake, methyl purple lake and other various Alkaline dyeing with lake; quinoline lake, fast sky blue and other mordant dye-based pigments; anthraquinone-based pigments, thioindigo-based pigments, perinone-based pigments, etc. Dyestuff pigments; various quinacridone pigments such as Cinquasia Red B; two

Purple and other various two

Series pigments; various condensed azo pigments such as Chromophthal (trade name); aniline black, etc.

As for inorganic pigments, for example, various chromates such as yellow lead, zinc chromate, molybdate orange, etc.; various ferrocyan compounds such as cyanine; titanium oxide, zinc bloom, Mapico yellow, iron oxide, etc. Various metal oxides such as iron oxide red, chromium oxide green, and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red, and mercury sulfide; various sulfates such as barium sulfate and lead sulfate; various types of silicon such as calcium silicate and ultramarine Salts; various carbonates such as calcium carbonate and magnesium carbonate; 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, brass powder, etc.; scales of these metals (flake) Pigments, mica/flake pigments; metal pigments or pearl pigments such as mica/flake pigments in the form of coated metal oxides, mica-like iron oxide pigments; black lead, carbon black, etc.

As far as extender pigments are concerned, for example, precipitating barium sulfate, hu powder, precipitating calcium carbonate, bicarbonate, cold water stone, bauxite white, silica, hydrous micro-powder silica (white smoke), superfine powder anhydrous silica ( aerosil), silica sand, talc, sedimentary magnesium carbonate, bentonite, clay, kaolin, loess, etc.

Furthermore, as for plastic pigments, for example, "Grandol PP-1000" and "PP-2000S" manufactured by DIC Co., Ltd. can be cited.

As far as the pigments used in the present invention are concerned, in terms of durability, weather resistance, and design properties, inorganic oxides such as titanium oxide and zinc bloom as white pigments, and carbon black as black pigments are more preferable.

The mass ratio of the pigment used in the present invention is 1 to 400 parts by mass relative to the total of 100 parts by mass of the isocyanate component B and the polyol component A, of which it is adjusted to 10 to 300 parts by mass, due to adhesion and blocking resistance It is better if it is good.

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

As for the silane coupling agent, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)-γ-aminopropyl Trimethoxysilane, N-β(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane and other aminosilanes; β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl triethoxy silane, etc. Silane; vinyl ginseng (β-methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane, γ-methacryloxy propyl trimethoxy silane and other vinyl silanes ; Hexamethyldisilazane, γ-mercaptopropyl trimethoxysilane, etc.

As for the titanate-based coupling agent, for example, titanium tetraisopropoxide, titanium tetra-n-butoxide, butyl titanate dimer, tetrastearyl titanate, acetylpyruvate Titanium, titanium laurate, tetrazincdiol titanate, titanium laurate, titanium tetrastearate, etc.

In addition, the aluminum-based coupling agent includes, for example, aluminum acetoxy alkoxide diisopropoxide.

Regarding epoxy resins, generally commercially available EP-BIS type, phenolic resin type, β-methyl epichloro type (β-methyl epichloro type), cyclic ethylene oxide type, glycidyl ether type, Various epoxy resins such as glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, polycarboxylic acid ester type, aminoglycidyl type, resorcinol type, etc. , Or triglycidyl ginseng (2-hydroxyethyl) isocyanurate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylic glycidyl Base ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, p-tertiary butyl phenyl glycidyl ether, diglycidyl adipic acid Compounds such as esters, diglycidyl phthalate, glycidyl methacrylate, butylglycidyl ether, etc.

(Other additives) The reactive adhesive used in the present invention may contain additives other than the foregoing if necessary. As for additives, for example, leveling agents, colloidal silica or alumina sol and other inorganic particles, polymethyl methacrylate-based organic particles, defoamers, sag inhibitors, wetting and dispersing agents, and adhesives can be used. Modifiers, ultraviolet absorbers, metal inactivators, peroxide decomposers, flame retardants, reinforcing agents, plasticizers, lubricants, rust inhibitors, fluorescent brighteners, inorganic hot-line absorbers, Anti-inflammatory agents, antistatic agents, dehydrating agents, commonly used thermoplastic elastomers, tackifiers, phosphoric acid compounds, melamine resins, or reactive elastomers. 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 the components of either the polyisocyanate composition (B) or the polyol composition (A), or they may be blended and used as the third component at the time of coating. Usually, the polyol composition (A) is pre-blended with components other than the polyisocyanate composition (B) to prepare a premix, and then just before coating, the premix is mixed with the polyisocyanate composition (B). modulation.

(Layered body) The laminate of the present invention can be obtained, for example, by laminating a plurality of films or papers using the adhesive of the present invention by a dry lamination method or a solvent-free lamination method. The film used is not particularly limited, and the film can be appropriately selected according to the application. For example, for food packaging, polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, polyethylene film (LLDPE: low density polyethylene film , HDPE: high-density polyethylene film) or polypropylene film (CPP: non-stretched polypropylene film, OPP: biaxially stretched polypropylene film) such as polyolefin film, polyvinyl alcohol film, ethylene-vinyl alcohol copolymer Combined film, etc.

The film may also be subjected to stretching treatment. Regarding the stretching treatment method, generally, the resin may be melted and extruded by an extrusion film forming method, etc., and then formed into a sheet shape, followed by simultaneous biaxial stretching or successive biaxial stretching. In addition, in the case of successive two-axis stretching, generally the vertical stretching process may be performed first, and then the horizontal stretching may be performed. Specifically, a method of combining the vertical stretching using the speed difference between the rollers and the horizontal stretching using a tenter is often used.

Alternatively, it is also possible to laminate a film containing vapor deposition layers of metal such as aluminum, metal oxides such as silica or alumina, and a gas barrier layer containing polyvinyl alcohol, ethylene/vinyl alcohol copolymer, vinylidene chloride, etc. The barrier film is used together. By using such a film, a laminate having barrier properties to water vapor, oxygen, alcohol, inert gas, volatile organic compounds (fragrance), etc. can be formed.

On the surface of the film, in order to form an adhesive layer free from defects such as film breakage or non-sticking properties, various surface treatments such as flame treatment or corona discharge treatment may be performed as needed.

Alternatively, the laminate of the present invention may be on a film, using the adhesive of the present invention as an adhesive auxiliary (anchor coating agent), coated by a laminator, and after curing reaction, by extrusion It is obtained by laminating molten polymer materials (extrusion laminating method). As for the film, the same film as the above-mentioned dry lamination method and solvent-free lamination method can be used. As for 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.

In terms of a more specific structure of the laminate, you can include (1) Base film 1 / Adhesive layer 1 / Sealant 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 layer 1/sealant film (5) Base film 1 / Adhesive layer 1 / Base film 2 / Adhesive layer 2 / Sealant film (6) Base film 1 / Adhesive layer 1 / Metal vapor deposition stretched film / Adhesive layer 2 / Sealant film (7) Base film 1 / Adhesive layer 1 / Transparent vapor deposition stretched film / Adhesive layer 2 / Sealant film (8) Base film 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Sealant film (9) Base film 1 / Adhesive layer 1 / Base film 2 / Adhesive layer 2 / Metal layer / Adhesive layer 3 / Sealant film (10) Base film 1 / Adhesive layer 1 / Metal layer / Adhesive layer 2 / Base film 2 / Adhesive layer 3 / Sealant film Etc. However, it is not limited to this.

The base film 1 used in the configuration (1) includes OPP film, PET film, nylon film, and the like. In addition, the base film 1 may be coated for the purpose of gas barrier properties, or for the purpose of improving ink receptivity when a printing layer described later is provided, and the like. The commercially available products of the base film 1 to be coated include K-OPP film, K-PET film, and the like. Adhesive layer 1 is a cured coating film of the adhesive of the present invention. As for the sealant film, CPP film, LLDPE film, etc. can be cited. The surface of the base film 1 on the side of the adhesive layer 1 (for the base film 1, the surface of the adhesive layer 1 side of the coating layer when a coating agent is used for the base film 1) may be provided with a printing layer. The printing layer can be formed by various printing inks, such as gravure printing ink, flexographic printing ink, planographic printing ink, stencil printing ink, inkjet printing ink, etc., by the general printing method used in the printing of polymer films.

As for the base film 1 used to constitute (2) and (3), an OPP film, a PET film, etc. can be mentioned. Adhesive layer 1 is a cured coating film of the adhesive of the present invention. For metal vapor-deposited unstretched films, VM-CPP films that vaporize metals such as aluminum on CPP films can be used, and for metal vapor-deposited stretched films, VM-CPP films that vaporize metals such as aluminum on OPP films can be used. OPP film. In the same manner as in the configuration (1), a printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side.

Examples of the transparent vapor-deposited stretched film used in the configuration (4) include films in which silica or alumina is vapor-deposited on OPP films, PET films, nylon films, and the like. For the purpose of protecting the inorganic vapor-deposition layer of silica or alumina, a thin film coated on the vapor-deposition layer can also be used. Adhesive layer 1 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those of the configuration (1). It is also possible to provide a printing layer on the surface of the adhesive layer 1 side of the transparent vapor-deposition stretched film (in the case of applying the coating on the inorganic vapor-deposition layer, the surface of the adhesive layer 1 side of the coating layer). The method of forming the printing layer is the same as the composition (1).

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

Regarding the base film 1 of the constitution (6), the same as the constitutions (2) and (3) can be mentioned. The metal vapor-deposition stretched film includes a VM-OPP film or a VM-PET film obtained by vapor-depositing metal such as aluminum on an OPP film or a PET film. 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. The sealant film is the same as the configuration (1). As with the configuration (1), a printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side.

The base film 1 constituting (7) includes a PET film and the like. As for the transparent vapor-deposition stretched film, the same thing as the structure (4) can be mentioned. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those of the configuration (1). As with the configuration (1), a printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side.

The base film 1 constituting (8) includes a PET film and the like. As for the metal layer, aluminum foil and the like can be cited. At least one of the adhesive layers 1 and 2 is a cured coating film of the adhesive of the present invention. Examples of the sealant film are the same as those of the configuration (1). As with the configuration (1), a printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side.

Examples of the base film 1 constituting (9) and (10) include a PET film. The base film 2 includes a nylon film and the like. As for the metal layer, aluminum foil and the like can be cited. At least one of the following layers 1, 2, and 3 is a hardened coating film of the adhesive of the present invention. Examples of the sealant film are the same as those of the configuration (1). As with the configuration (1), a printing layer may be provided on the surface of the base film 1 on the adhesive layer 1 side.

When the laminate of the present invention includes at least one of a metal vapor-deposited film, a transparent vapor-deposited film, and a metal layer, the adhesive layer in contact with the metal vapor-deposited layer, the transparent vapor-deposited layer, and the metal layer is cured by the adhesive of the present invention Coating film is preferred.

When the adhesive of the present invention is solvent-based, the adhesive of the present invention is coated on the film material that becomes the substrate using a roller such as a gravure roller, and heated by an oven or the like to volatilize the organic solvent. A substrate is bonded to obtain the laminate of the present invention. It is better to perform an aging 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, the adhesive of the present invention, which has been preheated to about 40°C to 100°C, is coated with a roller such as a gravure roll on the film material that becomes the base material, and then it is immediately combined with another substrate. The materials are bonded together to obtain the laminate of the present invention. After layering, it is better to perform an aging treatment. The curing temperature is preferably from room temperature to 70°C, and the curing time is preferably from 6 to 240 hours.

When the adhesive of the present invention is used as an adhesive adjuvant, the adhesive adjuvant of the present invention is coated on a film material that becomes a substrate using a roller such as a gravure roller, and heated in an oven to volatilize the organic solvent. , Laminating the molten polymer material by an extruder to obtain the laminated body of the present invention.

The coating amount of the adhesive should be adjusted appropriately. In the case of a solvent-based adhesive, as an example, it is adjusted ^{so that the solid content becomes 1 g/m 2} or more and 10 g/m ² or less, preferably 1 g/m ² or more and 5 g/m ^{2 or less.} In the case of a solvent-free adhesive, an example of 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.

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

The laminate of the present invention may further include other films or substrates in addition to the above-mentioned constitutions (1) to (10). Regarding 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 bonding to other substrates may or may not be the adhesive of the present invention.

The paper is not particularly limited, and well-known paper substrates can be used. Specifically, it is possible to use natural fibers for papermaking such as wood pulp and manufacture by a well-known papermaking machine, but the papermaking conditions are not particularly specified. In terms of natural fibers for papermaking, wood pulps such as conifer pulp and hardwood pulp; non-wood pulps such as manila hemp pulp, qiong hemp pulp, and flax pulp; and pulps that are chemically modified to these pulps. As far as the type of pulp is concerned, chemical pulp, mechanical wood pulp (ground pulp), chemical mechanical wood pulp can be used by kraft digestion, acid/neutral/alkaline sulfite digestion, soda salt digestion, etc. , Thermomechanical wood pulp, etc.

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

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

The laminate of the present invention can be suitably used for various purposes, such as packaging materials for food, medicines, and daily necessities, or paper food utensils such as lids, paper straws or paper towels, paper spoons, paper dishes, paper cups, etc.; wall protection materials, roofs Materials, solar cell panel materials, battery packaging materials, window materials, outdoor floor materials, lighting protection materials, automotive components, signboards, stickers and other outdoor industrial applications; used for injection molding and decorative methods, such as decorative sheets, and washing liquids Packaging materials, such as liquid detergent, kitchen liquid lotion, bath liquid lotion, bath liquid soap, liquid shampoo, liquid conditioner, etc.

＜Packaging material＞ The laminated body of the present invention can be used as a multilayer packaging material for the purpose of protecting foods, medicines, and the like. When used as a multilayer packaging material, its layer composition can be changed depending on the content, use environment, or use form. Moreover, it is also possible to appropriately design an easy-opening process or resealing mechanism in the package of the present invention.

The packaging material of the present invention can be obtained by using the laminate of the present invention, folding the faces of the sealant film of the laminate, and heat-sealing the surrounding edges to form a bag. As for the bag making method, the laminate of the present invention can be folded or overlapped so that the inner layer surface (the surface of the sealant film) is folded in half, and the surrounding edges are formed by, for example, a side-sealing type, two Side sealing type, three-side sealing type, four-side sealing type, sealing cylinder sealing type, palm sealing sealing type, wrinkle sealing type, flat bottom sealing type, corner bottom sealing type, box type , Other heat-sealing types and other forms of forming heat-sealing methods. The packaging material of the present invention can take various forms according to the content, use environment, or use form. It can also be a standing pouch and the like. As far as the heat sealing method is concerned, it can be performed by well-known methods such as rod heat sealing, rotating drum heat sealing, belt heat sealing, pulse heat sealing, high frequency heat sealing, ultrasonic heat sealing, etc.

The packaging material of the present invention can be filled with content from its opening, and then the opening can be heat sealed to produce a product using the packaging material of the present invention. As far as the contents of the filling are concerned, for example, in terms of food, snacks and candies such as rice crackers, bean candies, nuts, biscuits/cakes, muffins candies, marshmallows, pies, semi-cooked cakes, candies, desserts, etc. can be listed. Bread, dim sum noodles, instant noodles, dried noodles, spaghetti, aseptic packaged rice, chowder porridge, porridge, packaged sticky cakes, series foods and other staple foods; pickles, boiled beans, natto, miso, frozen tofu, tofu, enoki mushroom, Konjac, processed mountain vegetables, jams, peanut butter, salads, frozen vegetables, processed potato products and other processed agricultural products; processed livestock products such as ham, bacon, sausages, processed chicken products, and corned beef; fish ham/ Sausages, condensed aquatic products, kamaboko, seaweed, Tsukudani (Japanese-style seasoning), dried bonito, spicy, smoked salmon, spicy cod roe and other processed aquatic products; peaches, tangerines, pineapples, apples, pears, cherries, etc. Fruit meat; corn, asparagus, mushrooms, onions, carrots, radishes, potatoes and other vegetables; frozen side dishes represented by burgers, meatballs, fried aquatic products, dumplings, croquettes, etc.; frozen side dishes and other prepared foods; cream, milk Dairy products such as Malin, cheese, cream, instant cream powder, and adjusted powder for childcare; liquid seasoning; steamed curry; pet food and other foods.

Also, for non-food, it can also be used as cigarettes, disposable warm packs, infusion bags and other medicines, liquid detergents for washing, liquid kitchen detergents, liquid bath detergents, liquid soaps for baths, liquids Various packaging materials such as shampoos, liquid conditioners, cosmetics such as lotions or lotions, vacuum insulation materials, and batteries. [Example]

Hereinafter, the present invention will be explained concretely using examples. Furthermore, "parts" in the examples means parts by weight.

(Synthesis example 1: Preparation of polyol (A1-1)) In a 2-liter four-necked flask equipped with a stirrer, a thermometer, a Dimroth reflux cooling tube, and a nitrogen introduction tube, 2.6 parts of trimethylolpropane and 110.6 parts of polypropylene glycol (hydroxyl value 280.5 (mgKOH/ g), molecular weight 400), 222.1 parts of polypropylene glycol (hydroxyl value 112.2 (mgKOH/g), molecular weight 1,000), 123.9 parts of polyester polyol which is a condensate of diethylene glycol, ethylene glycol and adipic acid (Hydroxyl value 56.1 (mgKOH/g), molecular weight 2,000), 74.0 parts of dipropylene glycol, 6.6 parts of 2,2-bis(hydroxymethyl)propionic acid, flowed nitrogen, and started stirring. Then, 160.4 parts of toluene diisocyanate was added, and it was made to react at 90 degreeC. Then, 300 parts of ethyl acetate was added, and it was made to react at 70 degreeC for 4 hours, and the polyol (A1-1) with a solid content of 70% was obtained.

(Synthesis example 2: Preparation of polyol (A1-2)) In a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dai's reflux cooling tube, and a nitrogen inlet tube, 112.2 parts of polypropylene glycol (hydroxyl value 280.5 (mgKOH/g), molecular weight 400) and 225.2 parts of polypropylene glycol are added (Hydroxyl value 112.2 (mgKOH/g), molecular weight 1,000), 125.6 parts of polyester polyol which is a condensate of diethylene glycol, ethylene glycol, trimethylolpropane and adipic acid (hydroxyl value 56.1 (mgKOH) /g), molecular weight 2,000), 73.2 parts of dipropylene glycol, 6.7 parts of 2,2-bis(hydroxymethyl)propionic acid, flow nitrogen, and start stirring. Then, 157.1 parts of toluene diisocyanate was added, and it was made to react at 90 degreeC. Then, 300 parts of ethyl acetate was added, and it was made to react at 70 degreeC for 4 hours, and the polyol (A1-2) with a solid content of 70% was obtained.

(Synthesis example 3: Preparation of polyol (A1-3)) In a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dai's reflux cooling tube, and a nitrogen introduction tube, 115.7 parts of polypropylene glycol (hydroxyl value 280.5 (mgKOH/g), molecular weight 400), 232.3 parts of poly Propylene glycol (hydroxyl value 112.2 (mgKOH/g), molecular weight 1,000), 129.5 parts of polyester polyol (hydroxyl value 56.1( mgKOH/g), molecular weight 2,000), 25 parts of dipropylene glycol, 6.9 parts of 2,2-bis(hydroxymethyl)propionic acid, flow nitrogen, and start stirring. Then, 162.1 parts of toluene diisocyanate was added and reacted at 90°C until the NCO%, which is the residual rate of isocyanate groups, reached 1.34%. Then, 300 parts of ethyl acetate and 28.5 parts of diethanolamine were added and reacted at 70°C for 4 hours to obtain a polyol (A1-3) with a solid content of 70%.

(Synthesis example 4: Preparation of polyol (A1-4)) Add 2.5 parts of trimethylolpropane and 115.3 parts of polypropylene glycol (hydroxyl value 280.5 (mgKOH/g) to a 2-liter four-necked flask equipped with a stirrer, a thermometer, a Dai's reflux cooling tube, and a nitrogen inlet tube. , Molecular weight 400), 231.5 parts of polypropylene glycol (hydroxyl value 112.2 (mgKOH/g), molecular weight 1,000), 129.1 parts of polyester polyol (hydroxyl Valence 56.1 (mgKOH/g), molecular weight 2,000), 25 parts of dipropylene glycol, 6.9 parts of 2,2-bis(hydroxymethyl)propionic acid, flow of nitrogen, and start stirring. Then, 161 parts of hexamethylene diisocyanate was added and reacted at 90°C until the NCO%, which is the residual rate of isocyanate groups, reached 1.34%. Then, 300 parts of ethyl acetate and 28.7 parts of diethanolamine were added and reacted at 70°C for 4 hours to obtain a polyol (A1-4) with a solid content of 70%.

(Synthesis Example 5: Preparation of Polyol (A1-5)) Add 2.6 parts of trimethylolpropane and 110.6 parts of polypropylene glycol (hydroxyl value 280.5 (mgKOH/g) to a 2-liter four-necked flask equipped with a stirrer, a thermometer, a Dai's reflux cooling tube, and a nitrogen inlet tube. , Molecular weight 400), 222.1 parts of polypropylene glycol (hydroxyl value 112.2 (mgKOH/g), molecular weight 1,000), 123.9 parts of polyester polyol which is a condensate of diethylene glycol and adipic acid (hydroxyl value 56.1 (mgKOH) /g), molecular weight 2,000), 74.0 parts of dipropylene glycol, 6.6 parts of 2,2-bis(hydroxymethyl)propionic acid, flow nitrogen, and start stirring. Then, 160.4 parts of toluene diisocyanate was added, and it was made to react at 90 degreeC. Then, 300 parts of ethyl acetate was added, and it was made to react at 70 degreeC for 4 hours, and the polyol (A1-5) with a solid content of 70% was obtained.

(Comparative Synthesis Example 1: Preparation of Polyol (A1-H1)) In a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dai's reflux cooling tube, and a nitrogen introduction tube, 115.7 parts of polypropylene glycol (hydroxyl value 280.5 (mgKOH/g), molecular weight 400), 232.3 parts of poly Propylene glycol (hydroxyl value 112.2 (mgKOH/g), molecular weight 1,000), 129.5 parts is a polyester polyol of diethylene glycol, a condensate of ethylene glycol and adipic acid (hydroxyl value 56.1 (mgKOH/g), molecular weight 2,000), 25 parts of dipropylene glycol, 6.9 parts of 2,2-bis(hydroxymethyl)propionic acid, flow nitrogen, and start stirring. Then, 162.1 parts of toluene diisocyanate was added and reacted at 90°C until the NCO%, which is the residual rate of isocyanate groups, reached 1.34%. Then, 300 parts of ethyl acetate and 28.5 parts of diethanolamine were added and reacted at 70°C for 4 hours to obtain a polyol (A1-H1) with a solid content of 70%.

(Comparative Synthesis Example 1: Preparation of Polyol (A1-H2)) In a 2 liter four-necked flask equipped with a stirrer, a thermometer, a Dai's reflux cooling tube, and a nitrogen inlet tube, 2.8 parts of trimethylolpropane, 527 parts of diethylene glycol, ethylene glycol, and hexane were added. Polyester polyol (molecular weight 2,000) of diacid condensate, 25.5 parts of dipropylene glycol, 6.5 parts of 2,2-bis(hydroxymethyl)propionic acid, flow nitrogen, and start stirring. Next, 111.5 parts of toluene diisocyanate was added and reacted at 90°C until the NCO%, which is the residual rate of isocyanate groups, reached 1.34%. Then, 300 parts of ethyl acetate and 26.7 parts of diethanolamine were added and reacted at 70°C for 4 hours to obtain a polyol (A1-H2) with a solid content of 70%.

The polyol (A1) obtained in the synthesis example is as follows.

[Table 1] Table 1 Compounds with branched structure Polyols with ether bond but no ester bond (X1) Isocyanates with more than two functions (Y), and polyols with ester bonds (X2) Polyol (A1-1) Trimethylolpropane Polypropylene glycol Polyester polyol which is a condensate of diethylene glycol, ethylene glycol and adipic acid Polyol (A1-2) Trimethylolpropane Polypropylene glycol Polyester polyol which is a condensate of diethylene glycol, ethylene glycol, trimethylolpropane and adipic acid Polyol (A1-3) Trimellitic anhydride Polypropylene glycol Polyester polyol which is a condensate of diethylene glycol, ethylene glycol, adipic acid and trimellitic anhydride Polyol (A1-4) Trimethylolpropane Polypropylene glycol Polyester polyol which is a condensate of diethylene glycol, ethylene glycol and adipic acid Polyol (A1-5) Trimethylolpropane Polypropylene glycol Polyester polyol which is a condensate of diethylene glycol and adipic acid Polyol (A1-H1) without Polypropylene glycol Polyester polyol which is a condensate of diethylene glycol, ethylene glycol and adipic acid Polyol (A1-H2) Trimethylolpropane without Polyester polyol which is a condensate of diethylene glycol, ethylene glycol and adipic acid

(Synthesis Example 6 [Synthesis of Isocyanate Component B]) 228.66 parts of ethyl acetate and 260.66 parts by mass of 4',4-methylene diisocyanate were added to the reaction vessel, stirred under a nitrogen stream, while the temperature was raised to 75°C, and 85.85 parts by mass of polymer with a number average molecular weight of about 400 was added. Propylene glycol, 339.46 parts by mass of polypropylene glycol having a number average molecular weight of about 700, undergoes the urethane reaction at 70 to 80°C. Continue the reaction until the NCO% becomes 2.6-3.2%, and the viscosity becomes stable between SV, then the temperature is lowered to 70°C, and 95.48 parts by mass of trimethylolpropane (TMP) adduct type toluene diisocyanate (product name Desmodur) is added. L-75, manufactured by Sumika Bayer Urethane Co., Ltd.), was thoroughly stirred to obtain an isocyanate component B with a solid content of 75%.

(Examples, Comparative Examples) According to the combination in Table 1, a reactive adhesive was obtained.

(Evaluation method) [Appearance of polyol components] The polyol obtained in the synthesis example or the comparative synthesis example was left at 25°C for 30 minutes. Then, confirm the presence or absence of turbidity. Clear liquid・・・○ The liquid is turbid...△

[Evaluation of heat sealing strength] A nylon film (manufactured by UNITIKA; EMBLEM ON 15μm) and a linear low-density polyethylene film (LLDPE film manufactured by Tohcello; TUX HC-60μm) as a sealant film were used according to the examples Or the reactive adhesive (solid content of 3 g/m ² ) blended in the combination of the comparative example was bonded together, and aged at 40° C. for 72 hours to obtain a laminated film. The sealant film surfaces of the two laminated films are attached to each other, and ^{the heat-sealing treatment is performed at 180°C, 1kgf/cm 2} and 1 second with a 1cm wide sealing rod, to form a sample for heat-sealing strength measurement. At an ambient temperature of 25°C, using Shimadzu's tensile testing machine and setting the peeling speed to 300mm/min, the two ends of the heat-sealing strength measurement sample were stretched, and the peak of the measured tensile strength was used as the heat-sealing strength. The unit of heat sealing strength is N/15mm.

[Film state after heat sealing strength measurement] In the heat-sealing strength measurement, the case where the film itself breaks after the peak of the strength is shown is recorded as "break", and the case where the laminate layer is peeled without breaking is recorded as "x". In addition, fracture means that the adhesive layer is strongly adhered and is a physical property that can withstand implementation, and × means that the adhesive layer itself is fragile and is a physical property that is not resistant to implementation.

[Appearance of the laminate] On a polyethylene terephthalate film (hereinafter referred to as "PET film") with a design drawing printed with gravure printing ink ("Finart F407B Medium Yellow R794 White" made by DIC), Using a laminating machine (manufactured by Orient), the coating amount can make the solid content ^{about 2.7g/m 2} , and the coating is applied at a speed of 250m/min according to the combination of the examples or the comparative examples. Agent. Then, it was laminated with a VMPET (aluminum vapor-deposited polyethylene terephthalate) film to produce a laminated film. The appearance of the laminate immediately after the formation was visually evaluated. Evaluation ○: good appearance evaluation △: evaluation of bubbles in the gradual part ×: bubbles in all parts

[Residual Solvent Amount] On a 2-axis stretched polypropylene film (hereinafter referred to as "OPP film") with a design drawing printed with a printing ink ("Finart F407B Medium Yellow · R794 White" made by DIC), the embodiment or The reactive adhesive blended in the combination of the comparative example was applied with a laminating machine (manufactured by Orient) to achieve a solid content of about 2.7 g/m ² in a coating amount, and coating at a speed of 250 m/min according to the implementation Reactive adhesive blended in combination of Examples or Comparative Examples. Then, it was laminated with a VMPET (aluminum vapor-deposited polyethylene terephthalate) film to produce a laminated film. Then sample 0.2m ^{2 of the} layered material, cut it into about 1.5cm at the corner, put it in a Erlenmeyer flask and seal it, let it stand in a thermostat at 80℃ for 30 minutes, collect gas from the headspace, and perform gas chromatography ( 7890A manufactured by Agilent Technologies), and the amount of residual solvent was measured.

The results are shown in Table 2.

[Table 2] Table 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative example 1 Comparative example 2 Blending Polyol (A1-1) 100 100 Polyol (A1-2) 100 Polyol (A1-3) 100 Polyol (A1-4) 100 Polyol (A1-5) 100 Polyol (A1-H1) 100 Polyol (A1-H2) 100 Polyisocyanate component B 80 80 150 150 80 55 150 150 Polyol OHV 19 19 38 38 19 19 38 38 NCO% 3 3 3 3 3 3 3 3 NCO/OH mol ratio 1.7 1.7 1.6 1.6 1.7 1.2 1.6 1.6 Evaluation Polyol component appearance ○ ○ ○ ○ △ 〇 ○ ○ Heat sealing strength 60 61 61 58 55 56 20 62 Film state after heat sealing strength measurement fracture fracture fracture fracture fracture fracture X fracture Appearance of laminated body ○ ○ ○ ○ ○ ○ ○ X Residual solvent amount (mg/m ² ) 3.87 3.73 4.27 4.13 4.14 4.44 4.51 29.17

As a result, the laminate film using the reactive adhesive obtained in the example has an excellent appearance, exhibits sufficient heat seal strength, and the laminate has an excellent appearance. Furthermore, the amount of residual solvent is also small, which is excellent. Example 5 is an example with a small NCO/OH molar ratio. Although the appearance is good, the heat sealing strength is slightly worse, and the two-liquid phase solubility is also slightly poor. Comparative Examples 1 and 2 are examples in which no branching component is contained in the polyester polyol A1. The heat sealing strength of either is insufficient.

without.

without.

without.

Claims (8)

A reactive adhesive, which is a reactive adhesive having a polyol component A and an isocyanate component B, and is characterized by: The polyol component A contains polyol (A1) satisfying (1) and (2): (1) Contains a hydrocarbon group with a branched structure; (2) A polyol (X1) having an ether bond but no ester bond, a bifunctional or higher isocyanate (Y), and a polyol (X2) having an ester bond are used as reaction raw materials. The reactive adhesive of claim 1, wherein the polyol (X2) having an ester bond is a reaction product of a bifunctional polyol and an aliphatic dicarboxylic acid. The reactive adhesive of claim 1 or 2, wherein the polyol (A1) contains a polyhydric alcohol with a branched structure or a polycarboxylic acid with a branched structure as a reaction raw material. The reactive adhesive of any one of claims 1 to 3, wherein the polyol (X1) is a mixture of a bifunctional alcohol and a trifunctional alcohol. The reactive adhesive of any one of claims 1 to 4, wherein the polyol (X2) is a reaction product of a polyol and a polycarboxylic acid or a polycarboxylic anhydride, the polyol, the polycarboxylic acid, or the At least one of the polycarboxylic acid anhydrides is a compound having 3 or more hydroxyl groups or carboxyl groups. A laminated body, which is a laminated body in which a plurality of films or papers are bonded by an adhesive, is characterized in that the adhesive is a reactive adhesive according to any one of claims 1 to 5. A laminated body, which is a laminated body formed by bonding a plurality of films or papers provided with a printing layer by an adhesive, characterized in that the adhesive is the reaction of any one of claims 1 to 5性adhesive. A packaging body formed by forming a laminated body as claimed in Claim 6 or 7 into a bag shape.