WO2021106583A1 - 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 adhesives, laminates and packaging

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

Conventionally, various plastic films have been laminated together, and laminated bodies made by laminating (laminating) plastic films and paper, metal-deposited films, and metal foils have been used for various purposes such as packaging materials for foods, pharmaceuticals, and daily necessities. , Wall material, roofing material, solar cell panel material, battery packaging material, window material, outdoor flooring material, lighting protection material, automobile parts, signboards, stickers, and other outdoor industrial applications, injection molding simultaneous decoration method, etc. It is used for decoration purposes.
For these laminates, various plastic films, metal-deposited films, or metal foils are appropriately combined according to the required characteristics for each application, and the films are further printed, and an adhesive corresponding to the required characteristics is selected for each. Is manufactured. For example, if the product is used for food or daily necessities, it has functions such as strength, resistance to cracking, retort resistance, heat resistance, and content resistance in order to protect the contents from treatments such as refrigerated storage and heat sterilization during distribution. Required. Furthermore, these laminates are not distributed in the form of sheets. For example, in the case of food packaging, they are generally distributed in the form of bags with heat-sealed ends, so heat-sealing properties are also an essential required characteristic. There is.

As an adhesive used for such a laminate, a reactive adhesive (also referred to as a two-component curable adhesive) that reacts a hydroxyl group such as a polyether polyol or a polyester polyol with an isocyanate group of a polyisocyanate has been conventionally known. Has been done. For example, Patent Document 1 describes an adhesion composed of a first component containing one or more polyols selected from a polyether polyol, a polyether polyurethane polyol, a polyester polyol, and a polyester polyurethane polyol, and a second component containing a polyisocyanate. It is described that the agent composition is excellent in heat-sealing strength, and Patent Document 2 describes that an adhesive composition containing polyester polyurethane and polyisocyanate having a structure in which a polyester polyol is chain-extended with isophorone diisocyanate is heat-sealed. It is stated that it has excellent strength. However, a reactive adhesive composed of a combination of a polyol having an ester structure and an ether structure and a polyisocyanate has not been studied so far.

JP 2001-164229 JP 2011-102387

An object to be solved by the present invention is to provide a reactive adhesive which has both an ester structure and an ether structure and is excellent in laminated appearance and heat seal strength.

Polyester polyols and polyether polyols are versatile as components of reactive adhesives, but the physical characteristics obtained are slightly different. For example, a reactive adhesive containing a polyester structure as a main component is excellent in adhesive properties and heat resistance, but is slightly inferior in laminated appearance, and is therefore often used in applications requiring heat resistance such as food retort pouches. On the other hand, a reactive adhesive containing a polyether structure as a main component is often used as a general-purpose product that does not require heat resistance because it has an excellent appearance of lamination but is slightly inferior in adhesive properties and heat resistance.

As a result of diligent studies as a polyol having these advantages, the present inventors have made a difunctional polyol (X1) having a hydrocarbon group having a branched structure and having an ether bond and no ester bond. It has been found that a polyol using the above isocyanate (Y) and a polyol (X2) having an ester bond as reaction raw materials can solve the above problems.

That is, the present invention is a reactive adhesive having a polyol component A and an isocyanate component B, wherein the polyol component A has a hydrocarbon group having a branched structure, has an ether bond, and has an ester bond. Provided is a reactive adhesive containing a polyol (X1) which does not have the above, a bifunctional or higher functional isocyanate (Y), and a polyol (A1) which uses a polyol (X2) having an ester bond as a reaction raw material.

The present invention also provides a laminated body in which a plurality of films or papers are bonded together with an adhesive, wherein the adhesive is a reactive adhesive described in Koreki.

The present invention also provides a laminate in which a film or paper provided with a plurality of printing layers is bonded with an adhesive, wherein the adhesive is the reactive adhesive described above.

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

Since the reactive adhesive of the present invention has excellent heat-sealing strength, the obtained laminated film has an excellent appearance without peeling at the adhesive interface even after the heat-sealing treatment.

(Definition of words Solvent)
The reactive adhesive of the present invention is a reactive two-component type laminated adhesive as described above.
In the present invention, an adhesive that cures by a chemical reaction between an isocyanate group and a hydroxyl group is used.
In the present invention, the solvent may or may not be used. The "solvent" in the present invention refers to a highly soluble and volatile organic solvent capable of dissolving the polyisocyanate or polyol used in the present invention, and the "solvent type" refers to the solubility of these. It means that it contains a highly soluble organic solvent, and "solvent-free" means that it does not contain these highly soluble organic solvents. Specific examples of highly soluble organic solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, and xylol. , N-hexane, cyclohexane and the like. Among them, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate and ethyl acetate are known as highly soluble organic solvents.

When the reactive adhesive of the present invention is required to have a low viscosity or the like, it may be appropriately diluted with the highly soluble organic solvent according to the desired viscosity before use. In that case, either one of the polyol component A or the isocyanate component B may be diluted, or both may be diluted. Examples of the organic solvent used in such a case include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, cyclohexane and the like. .. Among these, ethyl acetate and methyl ethyl ketone (MEK) are preferable from the viewpoint of solubility, and ethyl acetate is particularly preferable. The organic solvent is often diluted and used so as to adjust the solid content to about 20 to 60% by mass, depending on the desired viscosity.
Further, in order to achieve a low viscosity of the adhesive of the present invention, a solvent having a carbonyl group having no hydroxyl group such as triacetin and propylene carbonate and having a boiling point of 200 ° C. or higher may be used. The amount of these high boiling point organic solvents used depends on the required viscosity and physical characteristics of the coating film, but is often in the range of approximately 0.1 to 10% by mass.

(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) It has a hydrocarbon group having a branched structure.
(2) A polyol (X1) having an ether bond and no ester bond, a bifunctional or higher functional isocyanate (Y), and a polyol (X2) having an ester bond are used as reaction raw materials.

(Polyol component A branched structure)
In the above (1), "having a hydrocarbon group having a branched structure" specifically means that the reaction raw material of the polyol component A has a branched structure as a polyhydric alcohol or a polyvalent carboxylic acid. It is preferable to use a compound having a compound, specifically a polyhydric alcohol having a branched structure, a polyvalent carboxylic acid having a branched structure, or an anhydride thereof. Specifically, by using a trifunctional or higher functional alcohol, a trifunctional or higher functional polyvalent carboxylic acid, or an anhydride thereof, a branched structure can be provided in the hydrocarbon group of the main skeleton of the polyol.
As the trifunctional or higher functional alcohol used in the present invention (here, the functional group in the alcohol represents a hydroxyl group, and the divalent, trivalent, polyvalent or the like represents the number of hydroxyl groups) includes glycerin and tri. Examples thereof include trifunctional or tetrafunctional aliphatic alcohols such as methylolpropane and pentaerythritol.
Further, a trifunctional or higher functional polyvalent carboxylic acid or an anhydride thereof (here, the functional group in the carboxylic acid represents a carboxyl group, and the divalent, trivalent, polyvalent or the like value means the number of carboxyl groups. (Represented) 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. Examples thereof include aromatic tribasic acids such as acids, 2,5,7-naphthalentricarboxylic acids and anhydrides thereof.

When the polyol (A1) has the branched structure, the heat seal resistance, which is the effect of the present invention, can be improved. In the present invention, the proportion of the trifunctional or higher functional alcohol, or the trifunctional or higher functional polyvalent carboxylic acid or its anhydride is used as the polyhydric alcohol or polyvalent carboxylic acid as the reaction raw material that causes the branched structure in the polyol component A. , 0.1 to 2.0 mol% is preferable.

(Polyol component A Polyol (X1) having an ether bond and no ester bond)
The polyol (X1) having an ether bond and not having an ester bond (hereinafter sometimes referred to as "polyol (X1)") used as a reaction raw material for the polyol (A1) in the present invention has an ester bond. If not, a known ether-based polyol can be used without particular limitation. For example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol. , Methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1,4-cyclohexanedi Bifunctional alcohols (glycols) such as methanol; trifunctional or tetrafunctional aliphatic alcohols such as glycerin, trimethylolpropane, pentaerythritol; bisphenols such as bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F;

A polyether polyol obtained by addition-polymerizing an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or cyclohexylene in the presence of a polymerization initiator such as the glycol trifunctional or tetrafunctional aliphatic alcohol. Examples thereof include polyether urethane polyols obtained by further increasing the molecular weight of the polyether polyol with the aromatic or aliphatic polyisocyanate.
Among them, a mixture of a bifunctional alcohol and a trifunctional or higher functional alcohol is preferable, and a mixture of a bifunctional alcohol and a trifunctional or tetrafunctional aliphatic alcohol is still more preferable.

(Polyol component A polyol having an ester bond (X2))
The polyol (X2) having an ester bond (hereinafter sometimes referred to as "polyol (X2)") used as a reaction raw material for the polyol (A1) in the present invention is not particularly limited as long as it has an ester bond. Known ester-based polyols can be used. For example, a polyester obtained by a ring-opening polymerization reaction of a cyclic ester compound such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone and the glycol, glycerin, trimethylolpropane, penta Polyester polyol (1) which is a reaction product with a polyhydric alcohol such as erythritol; the divalent alcohol such as the glycol, dimerdiol, or bisphenol is reacted with a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride. The obtained polyester polyol (2); the polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride; and the divalent polyol. , Polyester polyol (4) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride; Polyester polyol (5), which is a polymer;

Polyester polyether polyols obtained by reacting the polyester polyols (1) to (5) with the polyether polyols and aromatic or aliphatic polyisocyanates; the polyester polyols (1) to (5) are aromatic or fatty. Polyester polyurethane polyol obtained by increasing the molecular weight with group polyisocyanate; castor oil, dehydrated castor oil, castor oil, which is a hydrogenated additive of castor oil, castor oil-based polyol such as an adduct of 5 to 50 mol of alkylene oxide of castor oil. And so on.

Of these, polyester polyol is preferable. Further, it is a reaction product of a polyhydric alcohol and a polyhydric carboxylic acid or a polyvalent carboxylic acid anhydride, and at least one of the polyhydric alcohol, the polyvalent carboxylic acid, or the polyvalent carboxylic acid anhydride is a hydroxyl group. Alternatively, it is preferably a compound having 3 or more carboxyl groups. Specifically, the polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride, the divalent polyol, and the above. Examples thereof include polyester polyol (4) obtained by reacting a trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid or a polyvalent carboxylic acid anhydride.
The weight average molecular weight (Mw) of the polyol used is preferably 1000 to 30,000.

Here, examples of the polyvalent carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecandicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Aliphatic dicarboxylic acids such as acids and tetrahydrophthalic anhydride; terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyl Aromatic dicarboxylic acids such as dicarboxylic acids, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acids; and anhydrides or ester-forming derivatives of these aliphatic or aromatic dicarboxylic acids; p-hydroxybenzoic acid , P- (2-Hydroxyethoxy) benzoic acid, ester-forming derivatives of these dihydroxycarboxylic acids, and polybasic acids such as dimer acid.
Among them, an aliphatic dicarboxylic acid is preferable because the residual solvent after coating can be further reduced when used as a solvent-type adhesive diluted with an organic solvent. Of these, adipic acid is preferable.

More preferably, the polyol (X2) is, for example, a polyester polyol which is a reaction product of a bifunctional polyol and an aliphatic dicarboxylic acid, or a polyester which is a reaction product of a bifunctional polyol, a trifunctional polyol and an aliphatic dicarboxylic acid. Polyesters and polyester polyols, which are reaction products of trifunctional polyols and aliphatic dicarboxylic acids, are preferable.

(Polyol component A bifunctional or higher isocyanate (Y))
Bifunctional or higher functional isocyanate (Y) used as a reaction raw material for the polyol (A1) in the present invention (where, the functional group in isocyanate represents an isocyanate group and has a divalent, trivalent, polyvalent or the like value. (Represents the number of isocyanate groups) (hereinafter, may be referred to as “isocyanate (Y)”) can be a known bifunctional or higher functional isocyanate without particular limitation. For example, polyisocyanates having an aromatic structure in the molecular structure such as tolylene diisocyanate, diphenylmethane diisocyanate, polypeptide diphenylmethane diisocyanate, 1,5-naphthalenediocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, NCO groups of these polyisocyanates. A compound in which a part of the above is modified with carbodiimide; a polyisocyanate having an alicyclic structure in the molecular structure such as isophorone diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,3- (isocyanatomethyl) cyclohexane; , 6-Hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate and other linear aliphatic polyisocyanates, compounds in which some of the NCO groups of these polyisocyanates are modified with carbodiimide;

Isocyanurates of the various polyisocyanates; allophanates derived from the various polyisocyanates; billet bodies derived from the various polyisocyanates; trimethylolpropane-modified adducts of the various polyisocyanates; the various polys Examples thereof include polyisocyanate, which is a reaction product of isocyanate and a polyol component. Of these, tolylene diisocyanate is preferable.

(Polyol component A and other reaction raw materials)
The polyol (A1) in the present invention has the hydrocarbon group having the branched structure, the polyol (X1) having an ether bond and no ester bond, and the bifunctional or higher functional isocyanate (Y). The reaction raw material is not particularly limited except that the polyol (X2) having an ester bond is used as a reaction raw material, and a reaction raw material used for a polyurethane resin known as another reaction raw material is reacted within a range that does not impair the effects of the present invention. You may.
For example, examples of the chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4'-diamine, and dimerdiamine. Other molecules such as 2-hydroxyethylethylenediol, 2-hydroxyethylpropylenediol, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediol, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine. Diamines having a hydroxyl group inside, neopentyl glycol, butylethylpropanediol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, triethylene glycol, 1- or 2-methyl -1,3-butylene glycol, 1- or 2-methyl-1,4-pentylene glycol, 2,4-diethyl-1,5-pentanediol, tripropylene glycol, diethylene glycol, 1,2-propylene glycol, 1 , 3-Butanjiol, 1-, 2- or 3-Methyl-1,5-Pentanjiol, diols such as 2-methyl-1,3-propanediol, ethylene oxide of bisphenol A, propylene oxide, ethylene Examples thereof include alkylene oxide adducts such as propylene oxide and other diols. Of these, particularly preferred is isophorone diamine.

Examples of chain extenders other than the above include diols having a tertiary amine structure such as methyldiethanolamine, methyldiisopropanolamine, phenyldiisopropanolamine, 4-methylphenyldiisopropanolamine, and 4-methylphenyldiethanolamine, and diols thereof. Examples include two or more mixtures.

Examples of the chain extension terminator include monoalcohols (methanol, propanol, butanol, 2-ethylhexanol, etc.), monoamines [mono or dialkylamines having 2 to 8 carbon atoms (butylamine, dibutylamine, etc.), and 2 to 6 carbon atoms. Mono or dialkanolamines (monoethanolamine, diethanolamine, propanolamine, isopropanolamine, etc.)] and the like.

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

(1)

In the general formula (1), X ₁ represents the reaction residue of the polyol (X1) having an ether bond and no ester bond, U represents a urethane bond, and Y ₁ represents the bifunctional or higher functional isocyanate (1). Y) represents the reaction residue, X ₂ represents the reaction residue of the polyol (X2) having the ester bond, Z represents the reaction residue of the polyol (X1) or the polyol (X2), and the X _It has a hydrocarbon group having a branched structure in either 1 or X _{2 or both.} n represents a repetitive structure and is a value calculated back from the molecular weight described later.

(Production method of polyol component A polyol (A1))
The method for producing the polyol (A1) is not particularly limited, and the polyol (A1) can be produced by a known method. For example, a one-step method in which the polyol (X1) as a reaction raw material, the isocyanate (Y), and the polyol (X2) are reacted at once at a ratio of an excess hydroxyl group, or the polyol as a reaction raw material ( X1), the isocyanate (Y), and the polyol (X2) are reacted at a ratio of an excess of isocyanate groups to obtain a prepolymer having terminal isocyanate groups, and the obtained prepolymer is placed in a suitable solvent. A two-step method of reacting with a chain extender and / or terminal blocker, or a reaction of polypropylene glycol and a combined polyol, diisocyanate compound, chain extender and / or terminal blocker at once in a suitable solvent among the above. Manufactured by the one-step method.

Further, in the polyol (A1) represented by the general formula (1), specifically, the polyol (X1) which is a reaction raw material, the isocyanate (Y), and the polyol (X2) are alternately arranged. It has a structure that connects them. A polyol having such a structure can be obtained, for example, by the following production method.
(Example 1) When the polyol (X1) and the polyol (X2), which are reaction raw materials, are compatible with each other, it can be obtained by one-step polymerization. "Compatible" refers to a case where turbidity does not occur when the polyol (X1) and the polyol (X2) are mixed at a mass ratio of 1: 1. The turbidity may be visually observed, but it can also be quantified by a method such as a haze meter.

As a combination of the polyol (X1) and the polyol (X2), for example, as a combination of the polyol (X1) and the polyol (X2), for example.
-A combination of polypropylene glycol (corresponding to polyol (X1)) and polyester polyol (corresponding to polyol (X2)) which is a condensate of diethylene glycol, ethylene glycol and adipic acid, and
-A combination of polypropylene glycol (corresponding to polyol (X1)) and polyester polyol (corresponding to polyol (X2)) which is a condensate of diethylene glycol, ethylene glycol, trimethylolpropane and adipic acid, and
-A combination of polypropylene glycol (corresponding to polyol (X1)) and polyester polyol (corresponding to polyol (X2)) which is a condensate of diethylene glycol, ethylene glycol, adipic acid and trimellitic anhydride, and
-Examples include a combination of polypropylene glycol (corresponding to polyol (X1)) and polyester polyol (corresponding to polyol (X2)) which is a condensate of diethylene glycol and adipic acid.

The polyol (A1) is preferably 10% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, and 80% by mass to 100% by mass, based on the total mass of the polyol component A. Is most preferable.
On the other hand, the compound represented by the general formula (1) is contained at least 10% by mass or more with respect to the total mass of the polyol component A because a reaction product having a molecular weight distribution is generally produced in the polymer reaction. Just do it.

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

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

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

(Polyol component A and other components)
In the present application, it is essential to contain the polyol (A1) as described above, but other polyols may be used in combination as long as the effects of the present invention are not impaired. For example, polyols such as simple polyester polyols, polyether polyols, and polyurethane polyols 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. As the polyisocyanate compound used in the present invention, known ones can be used without particular limitation, and they can be used alone or in combination of two or more.

For example, polyisocyanates having an aromatic structure in the molecular structure such as tolylene diisocyanate, diphenylmethane diisocyanate, polyether diphenylmethane diisocyanate, 1,5-naphthalenedi isocyanate, triphenylmethane triisocyanate, xylylene diisocyanate; isophorone diisocyanate, 4,4'. -Polyisocyanate having an alicyclic structure within the molecular structure of methylenebis (cyclohexylisocyanate), 1,3- (isocyanatomethyl) cyclohexane, etc .; 1,6-hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, lysine diisocyanate , Linear aliphatic polyisocyanate such as trimethylhexamethylene diisocyanate,

A compound in which a part of the NCO group of the various polyisocyanates is modified with carbodiimide; an isocyanurate form of the various polyisocyanates; an allophanate form derived from the various polyisocyanates; a billet form derived from the various polyisocyanates. Adducts obtained by modifying the various polyisocyanates with trimethylolpropane; Examples thereof include polyisocyanates which are reaction products of the various polyisocyanates and polyol components.

It may be a polyisocyanate which is a reaction product of the various polyisocyanate compounds described above and a polyhydric alcohol. The polyhydric alcohol in this case is a polyhydric alcohol, a polyester polyol, a polyether polyol, a polyurethane polyol, a polyether ester polyol, a polyester (polyester) polyol, a polyether (polyester) polyol, or a polyester, which is a raw material of the polyol (A1). Polymer polyols selected from amide polyols, acrylic polyols, polycarbonate polyols, polyhydroxyl alcohols, castor oil or mixtures thereof and the like can be used. Above all, it is preferable to use polyisocyanate, which is a reaction product of the various polyisocyanates described above and the polyether polyol, from the viewpoint of adhesive strength, heat resistance and content resistance.
The reaction ratio between the polyisocyanate compound and the polyhydric alcohol is such that the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group to the hydroxyl group is in the range of 1.0 to 5.0, and the adhesion of the adhesive coating film is aggregated. It is preferable from the viewpoint of the balance between force and flexibility.

It is also preferable to use various mixtures of the isocyanates. Polyisocyanates that are reaction products of the various polyisocyanates and the polyether polyols, compounds in which a part of the NCO group of the various polyisocyanates is modified with carbodiimide; isocyanurates of the various polyisocyanates. Allophanate derived from the various polyisocyanates; Bullet derived from the various polyisocyanates; Adducts obtained by modifying the various polyisocyanates with trimethylolpropane; Reaction products of the various polyisocyanates and polyol components A mixture such as polyisocyanate is preferable. Of these, a mixture of the polyisocyanate, which is a reaction product of the various polyisocyanates described above and the polyether polyol, and an adduct body obtained by modifying the various polyisocyanates with trimethylolpropane is preferable, and an alicyclic type is formed in the molecular structure. A mixture of polyisocyanate, which is a reaction product of a polyisocyanate having a structure and a polyether polyol, and an adduct obtained by trimethylolpropane-modified the polyisocyanate having an aromatic structure is preferable.

Here, the isocyanate component B acts as a curing agent for the polyol component A, but when an epoxy compound or a hydroxyl group-containing polycarbonate resin described later is used in combination, the resin contains a hydroxyl group. Can be cured by reacting with the hydroxyl group.

In the isocyanate component B, the polyisocyanate compound is preferably 10% by mass to 100% by mass, more preferably 50% by mass to 100% by mass, and 80% by mass, based on the total mass of the isocyanate component B. Most preferably, it is ~ 100% by mass.

(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 is 1.1 or more. Within this range, heat seal resistance can still be improved. The molar ratio is preferably 1.3 or more, and most preferably 1.5 or more. On the other hand, the upper limit is not particularly limited, but is preferably 3.0 or less from the viewpoint of curing failure.
In the present invention, it is preferable to mix so that the isocyanate group is excessive. It is presumed that the isocyanate group contained in the polyol component A, which cannot completely react with the hydroxyl group, reacts with water to form a urea bond, which further contributes to heat seal resistance.

(Additive)
As described above, the reactive adhesive of the present invention is a reactive adhesive having the polyol component A and the isocyanate component B, but in addition, various additives generally used for the reactive adhesive are used. Can be done.
For example, the curing reaction can be promoted by using a catalyst.
The catalyst used in the present invention is not particularly limited as long as it is for promoting the urethanization reaction, and for example, a metal catalyst, an amine catalyst, diazabicycloundecene (DBU), and an aliphatic cyclic amide compound. , A catalyst such as a titanium chelate complex can be used.

Examples of the metal-based catalyst include a metal complex-based catalyst, an inorganic metal-based catalyst, and an organic metal-based catalyst. Specifically, the metal-based catalyst includes Fe (iron), Mn (manganese), Cu (copper), and Zr (zirconium). ), Th (thorium), Ti (titanium), Al (aluminum) and Co (cobalt), which are acetylacetonate salts of metals selected from the group, for example, iron acetylacetoneate, manganese acetylacetonate, copper acetyl. Examples thereof include acetonate and zirconia acetylacetoneate. Of these, iron acetylacetoneate (Fe (acac) ₃ ) or manganese acetylacetonate (Mn (acac) ₂ ) is preferable from the viewpoint of toxicity and catalytic activity. ..

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

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

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

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

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

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

..
The mass ratio of the catalyst is preferably in the range of 0.001 to 3 parts, preferably in the range of 0.01 to 2 parts, assuming that the mixed solution of the polyisocyanate composition (B) and the polyol composition (A) is 100 parts. More preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Hereinafter, the present invention will be specifically described with reference to examples. In addition, "part" in an Example represents a weight part.

(Synthesis Example 1: Preparation of Polyol (A1-1))
2.6 parts of trimethylol propane and polypropylene glycol (hydroxyl value 280.5 (mgKOH / mgKOH /)) in a 2-liter four-necked flask equipped with a stirrer, a thermometer, a gymrot type reflux cooling tube, and a nitrogen gas introduction tube. g), molecular weight 400) 110.6 parts, polypropylene glycol (hydroxyl value 112.2 (mgKOH / g), molecular weight 1,000) 222.1 parts, polyester which is a condensate of diethylene glycol, ethylene glycol and adipic acid. 123.9 parts of polyol (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 are charged, and nitrogen is charged. Gas was flowed and stirring was started. Subsequently, 160.4 parts of toluene diisocyanate was added and reacted at 90 ° C.
Next, 300 parts of ethyl acetate was added and reacted at 70 ° C. for 4 hours to obtain a polyol (A1-1) having a solid content of 70%.

(Synthesis Example 2: Preparation of Polyol (A1-2))
Polypropylene glycol (hydroxyl value 280.5 (mgKOH / g), molecular weight 400) 112 in a 2-liter four-necked flask equipped with a stirrer, thermometer, diethylene reflux cooling tube, and nitrogen gas introduction tube. .2 parts, polypropylene glycol (hydroxyl value 112.2 (mgKOH / g), molecular weight 1,000) 225.2 parts, polyester polyol (hydroxyl value) which is a condensate of diethylene glycol, ethylene glycol, trimethylolpropane and adipic acid 56.1 (mgKOH / g), molecular weight 2,000) 125.6 parts, dipropylene glycol 73.2 parts, 2,2-bis (hydroxymethyl) propionic acid 6.7 parts were charged, and nitrogen gas was flowed. Stirring was started. Subsequently, 157.1 parts of toluene diisocyanate was added and reacted at 90 ° C. Next, 300 parts of ethyl acetate was added and reacted at 70 ° C. for 4 hours to obtain a polyol (A1-2) having a solid content of 70%.

(Synthesis Example 3: Preparation of Polyol (A1-3))
Polypropylene glycol (hydroxyl value 280.5 (mgKOH / g), molecular weight 400) 115 in a 2-liter four-necked flask equipped with a stirrer, thermometer, diethylene reflux cooling tube, and nitrogen gas introduction tube. .7 parts, polypropylene glycol (hydroxyl value 112.2 (mgKOH / g), molecular weight 1,000) 232.3 parts, polyester polyol (hydroxyl group) which is a condensate of diethylene glycol, ethylene glycol, adipic acid and trimellitic anhydride Charge 56.1 (mgKOH / g), molecular weight 2,000) 129.5 parts, dipropylene glycol 25 parts, 2,2-bis (hydroxymethyl) propionic acid 6.9 parts, flow nitrogen gas, and stir. Started. Subsequently, 162.1 parts of toluene diisocyanate was added, and the reaction was carried out at 90 ° C. until the residual ratio of isocyanate groups, NCO%, reached 1.34%. Next, 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) having a solid content of 70%.

(Synthesis Example 4: Preparation of Polyol (A1-4))
2.5 parts of trimethylol propane and polypropylene glycol (hydroxyl value 280.5 (mgKOH)) in a 2-liter four-necked flask equipped with a stirrer, thermometer, diethylene glycol type reflux cooling tube, and nitrogen gas introduction tube. / G), molecular weight 400) 115.3 parts, polypropylene glycol (hydroxyl value 112.2 (mgKOH / g), molecular weight 1,000) 231.5 parts, polyester which is a condensate of diethylene glycol, ethylene glycol and adipic acid Add 129.1 parts of 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, and add nitrogen gas. Flushing and stirring was started. Subsequently, 161 parts of hexamethylene diisocyanate was added, and the reaction was carried out at 90 ° C. until the residual ratio of isocyanate groups, NCO%, reached 1.34%. Next, 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) having a solid content of 70%.

(Synthesis Example 5: Preparation of Polyol (A1-5))
2.6 parts of trimethylol propane and polypropylene glycol (hydroxyl value 280.5 (mgKOH)) in a 2-liter four-necked flask equipped with a stirrer, a thermometer, a gymrot type reflux cooling tube, and a nitrogen gas introduction tube. / G), molecular weight 400) 110.6 parts, polypropylene glycol (hydroxyl value 112.2 (mgKOH / g), molecular weight 1,000) 222.1 parts, polyester polyol (hydroxyl group) which is a condensate of diethylene glycol and adipic acid Charge 56.1 (mgKOH / g), molecular weight 2,000) 123.9 parts, dipropylene glycol 74.0 parts, 2,2-bis (hydroxymethyl) propionic acid 6.6 parts, and let nitrogen gas flow. , Stirring was started. Subsequently, 160.4 parts of toluene diisocyanate was added and reacted at 90 ° C. Next, 300 parts of ethyl acetate was added and reacted at 70 ° C. for 4 hours to obtain a polyol (A1-5) having a solid content of 70%.

(Comparative Synthesis Example 1: Preparation of Polyol (A1-H1))
Polypropylene glycol (hydroxyl value 280.5 (mgKOH / g), molecular weight 400) 115 in a 2-liter four-necked flask equipped with a stirrer, thermometer, diethylene reflux cooling tube, and nitrogen gas introduction tube. .7 parts, polypropylene glycol (hydroxyl value 112.2 (mgKOH / g), molecular weight 1,000) 232.3 parts, polyester polyol (hydroxyl value 56.1) which is a condensate of diethylene glycol, ethylene glycol and adipic acid. mgKOH / g), molecular weight 2,000) 129.5 parts, dipropylene glycol 25 parts, 2,2-bis (hydroxymethyl) propionic acid 6.9 parts were charged, nitrogen gas was flowed, and stirring was started. Subsequently, 162.1 parts of toluene diisocyanate was added, and the reaction was carried out at 90 ° C. until the residual ratio of isocyanate groups, NCO%, reached 1.34%. Next, 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) having a solid content of 70%.

(Comparative Synthesis Example 1: Preparation of Polyol (A1-H2))
Condensation of 2.8 parts of trimethylolpropane, diethylene glycol, ethylene glycol, and adipic acid in a 2-liter four-necked flask equipped with a stirrer, thermometer, gymrot type reflux condenser, and nitrogen gas introduction tube. 527 parts of polyester polyol (molecular weight 2,000), 25.5 parts of dipropylene glycol, and 6.5 parts of 2,2-bis (hydroxymethyl) propionic acid were charged, and nitrogen gas was flowed to start stirring. Subsequently, 111.5 parts of toluene diisocyanate was added, and the reaction was carried out at 90 ° C. until the residual ratio of isocyanate groups, NCO%, reached 1.34%. Next, 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) having a solid content of 70%.

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

(Synthesis Example 6 [Synthesis of Isocyanate Component B])
228.66 parts of ethyl acetate, 260.66 parts by mass of 4'4-methylene diisocyanate were charged into a reaction vessel, and the temperature was raised to 75 ° C. with stirring under a nitrogen gas stream, and 85.85 parts by mass of polypropylene glycol having a number average molecular weight of about 400. Part, 339.46 parts by mass of polypropylene glycol having a number average molecular weight of about 700 was added, and a urethanization reaction was carried out at 70 to 80 ° C. The reaction was continued until the NCO% was 2.6 to 3.2% and the viscosity was constant between S and V, and then the temperature was lowered to 70 ° C., and the temperature was lowered to trimethylolpropane (TMP) adduct-type tolylene diisocyanate (product name). Death Module L-75 (manufactured by Sumika Bayer Urethane Co., Ltd.) 95.48 parts by mass was added and stirred well to obtain an isocyanate component B having a solid content of 75%.

(Example, comparative example)
Reactive adhesives were obtained according to the combinations shown in Table 1.

(Evaluation method)
[Appearance of polyol component]
The polyol obtained in the synthetic example or the comparative synthetic example was left at 25 ° C. for 30 minutes. After that, the presence or absence of turbidity was confirmed.
Liquid clear ... ○
There is liquid turbidity ... △

[Evaluation of heat seal strength]
Reactive adhesive in which a nylon film (manufactured by Unitica; EMBLEM ON 15 μm) and a linear low-density polyethylene film (LLDPE film manufactured by Tohcello Co., Ltd .; TUX HC-60 μm) are blended as a sealant film in a combination of Examples or Comparative Examples. It was bonded at (solid content: 3 g / m ² ) and aged at 40 ° C. for 72 hours to obtain a laminated film.
Combined sealant film surfaces of the two laminated films, 180 ° C. at a 1cm wide seal bar · 1kgf / cm 2 · ¹ seconds to heat sealing treatment, was heat-sealing strength measurement sample.
The peeling speed was set to 300 mm / min using a tensile tester manufactured by Shimadzu Corporation at an ambient temperature of 25 ° C., and the peak of the tensile strength when both ends of the heat seal strength measurement sample were pulled and measured was defined as the heat seal strength. ..
The unit of heat seal strength is N / 15 mm.

[Film state after heat seal strength measurement]
When the heat seal strength was measured, the case where the film itself broke after showing the peak of the strength was designated as "break", and the case where the film was peeled off by the laminate layer without breaking was designated as "x".
Note that breakage indicates that the adhesive layer is firmly adhered and has physical properties that can withstand implementation, and x indicates that the adhesive layer itself is fragile and has physical properties that cannot withstand implementation.

[Laminate appearance]
Reactivity blended in a polyethylene terephthalate film (hereinafter abbreviated as "PET film") in which a pattern is gravure-printed with printing ink (DIC "Finato F407B Medium Yellow / R794 White") in a combination of Examples or Comparative Examples. The adhesive was applied with a laminator (manufactured by Orient Co., Ltd.) at 250 m / min so ^{that the coating amount was about 2.7 g / m 2 in solid content.} After that, it was laminated with a VMPET (aluminum-deposited polyethylene terephthalate) film to prepare a laminated film.
Immediately after that, the appearance of the laminate was visually evaluated.
Evaluation ○: Good appearance Evaluation △: Bubbles in the gradation part Evaluation ×: Bubbles in the solid part

[Amount of residual solvent]
A combination of Examples or Comparative Examples was blended with a biaxially stretched polypropylene film (hereinafter abbreviated as "OPP film") in which a pattern was gravure-printed with a printing ink (DIC "Finato F407B Medium Yellow / R794 White"). The reactive adhesive was applied with a laminator (manufactured by Orient Co., Ltd.) at 250 m / min so ^{that the coating amount was about 2.7 g / m 2 in solid content.} After that, it was laminated with a VMPET (aluminum-deposited polyethylene terephthalate) film to prepare a laminated film.
Immediately after that, the laminate was ^{sampled 0.2 m 2} and cut into approximately 1.5 cm squares, placed in an Erlenmeyer flask, sealed, allowed to stand in a constant temperature bath at 80 ° C. for 30 minutes, and then gas was sampled from the headspace and gas chromatograph. The amount of residual solvent was measured with (7890A manufactured by Agilent Technologies).

The results are shown in Table 2.

As a result, the laminated film using the reactive adhesive obtained in Examples was excellent in appearance, exhibited sufficient heat-sealing strength, and was excellent in laminated appearance. Furthermore, the amount of residual solvent was small and it was excellent.
Example 5 was an example in which the NCO / OH molar ratio was small, and although the appearance was good, the heat seal strength was slightly inferior, and the two-component compatibility was also slightly inferior.
Comparative Examples 1 and 2 are examples in which the polyester polyol A1 did not contain a branching component. In each case, the heat seal strength was insufficient.

Claims (8)

1. A reactive adhesive having a polyol component A and an isocyanate component B.
   A reactive adhesive, wherein the polyol component A contains a polyol (A1) that satisfies (1) and (2).
   (1) It has a hydrocarbon group having a branched structure.
   (2) A polyol (X1) having an ether bond and no ester bond, a bifunctional or higher functional isocyanate (Y), and a polyol (X2) having an ester bond are used as reaction raw materials.
2. The reactive adhesive according to claim 1, wherein the polyol (X2) having an ester bond is a reaction product of a bifunctional polyol and an aliphatic dicarboxylic acid.
3. The reactive adhesive according to claim 1 or 2, wherein the polyol (A1) contains a polyhydric alcohol having a branched structure or a polyvalent carboxylic acid having a branched structure as a reaction raw material.
4. The reactive adhesive according to any one of claims 1 to 3, wherein the polyol (X1) is a mixture of a bifunctional alcohol and a trifunctional or higher functional alcohol.
5. The polyol (X2) is a reaction product of a polyhydric alcohol and a polyhydric carboxylic acid or a polyvalent carboxylic acid anhydride, and the polyhydric alcohol, the polyvalent carboxylic acid, or the polyvalent carboxylic acid anhydride. The reactive adhesive according to any one of claims 1 to 4, wherein at least one of the above is a compound having three or more hydroxyl groups or carboxyl groups.
6. A laminate obtained by laminating a plurality of films or papers with an adhesive, wherein the adhesive is the reactive adhesive according to any one of claims 1 to 5.
7. A laminate obtained by laminating a film or paper provided with a plurality of printing layers with an adhesive, wherein the adhesive is the reactive adhesive according to any one of claims 1 to 5. Laminated body.
8. A package obtained by molding the laminate according to claim 6 or 7 into a bag shape.