WO2017163900A1

WO2017163900A1 - Two-part curable laminate adhesive, cured product thereof, method for producing laminated film, and amine solution for two-part curable laminate adhesive

Info

Publication number: WO2017163900A1
Application number: PCT/JP2017/009424
Authority: WO
Inventors: 健一島村; 秀興岩波
Original assignee: Dic株式会社
Priority date: 2016-03-25
Filing date: 2017-03-09
Publication date: 2017-09-28
Also published as: JP2018035363A; JPWO2017163900A1; JP6512256B2; JP6233551B1

Abstract

Provided are: a two-part curable laminate adhesive characterized by containing, as essential components, a polyurethane polyurea resin (A) having a primary amino group in the molecular structure thereof, and a polyglycidyl ether of a linear aliphatic polyol as a polyfunctional epoxy compound (B); a cured product thereof; a laminated film having the two-part curable laminate adhesive between a first plastic film and a second plastic film; and an amine solution for the two-part curable laminate adhesive, the amine solution containing a polyurethane polyurea resin (A) having a primary amino group in the molecular structure thereof, and an organic solvent (C) at such a ratio that the solid content concentration is 30-70 mass%.

Description

Two-component curable laminate adhesive, cured product thereof, method for producing laminated film, and amine solution for two-component curable laminate adhesive

The present invention relates to a two-component curable laminate adhesive, a cured product thereof, a laminated film obtained by laminating various films using the adhesive, and an amine solution for a two-component curable laminate adhesive. More specifically, the present invention relates to an adhesive for laminating used in the production of composite films mainly used for packaging materials such as foods, pharmaceuticals, and detergents by laminating various plastic films, metal vapor deposited films, aluminum foils and the like.

For packaging materials for food packaging materials, pharmaceuticals, and daily necessities, a multi-layer film by so-called dry lamination, in which the adhesive is applied to the surface of the film substrate, the solvent is evaporated to dryness, and other materials are laminated while heating and pressure bonding, It is widely used because any film can be selectively combined according to the required characteristics of each application.

The adhesive used for such dry lamination is mainly a two-component polyurethane adhesive mainly comprising a polyol component having a hydroxyl group at the polymer terminal and a polyisocyanate as a curing agent. Here, polyester polyol and polyester polyurethane polyol are used as the polyol component, and various monomer-type polyisocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and isophorone diisocyanate (IPDI) are used as the polyisocyanate. However, it is used because the curing agent itself functions as a reactive diluent.

However, the isocyanate component used as the curing agent exhibits significant sensitization by inhalation or skin contact, or the primary aromatic amine produced by the reaction of this isocyanate component with moisture in the container is European CLP. Its harmfulness has been pointed out, such as being classified as a carcinogenic substance in the regulations, and in recent years, development of laminate adhesives that do not contain isocyanates has been demanded.

As such a laminating adhesive not containing isocyanate, for example, in Patent Document 1 below, a two-component curing type using tetraglycidyl-m-xylylenediamine as an epoxy compound and an amine compound as a curing agent is used. A laminate adhesive is disclosed.

Although the epoxy / amine curable adhesive described in Patent Document 1 certainly exhibits excellent adhesive strength, the cured product becomes hard and brittle because the epoxy compound itself has a rigid molecular structure. It was inferior in followability to the material film, and after carrying out the boil treatment at 98 ° C., the adhesive strength was remarkably lowered and an appearance defect was caused.

Japanese Patent No. 5651172

Therefore, the problem to be solved by the present invention is a two-component curable laminate adhesive excellent in laminate adhesive strength, particularly laminate adhesive strength after boil treatment, and an adhesive suitable for non-isocyanate-based soft packaging laminates. It is to provide a laminated film used.

As a result of diligent research to solve the above problems, the present inventors have used a polyurethane polyurea resin having an amino group in the molecular structure as a main agent, and using a polyfunctional epoxy compound as its curing agent, As an isocyanate-based soft packaging laminating adhesive, the present inventors have found that the laminating strength, particularly the adhesive strength after the boil treatment of the laminating film and the laminating appearance are remarkably improved, and the present invention has been completed.

That is, the present invention relates to a two-component curable laminate adhesive comprising, as essential components, a polyurethane polyurea resin (A) having a primary amino group in the molecular structure and a polyglycidyl ether (B) of a chain aliphatic polyol. .

The present invention further relates to a cured product obtained by curing the two-component curable laminate adhesive.

The present invention further provides a laminated film characterized in that the two-component curable laminate adhesive is applied to a first plastic film, the second plastic film is laminated on the coated surface, and the adhesive layer is cured. It relates to the manufacturing method.

A two-component curable laminate adhesive comprising a polyurethane polyurea resin (A) having a primary amino group in the molecular structure and an organic solvent (C) in a proportion of a solid content of 30 to 70% by mass. The present invention relates to a pharmaceutical amine solution.

According to the present invention, as an adhesive suitable for a non-isocyanate-based soft packaging laminate, a two-component curable laminate adhesive excellent in laminate adhesive strength, particularly laminate adhesive strength after boil treatment, and a laminate film using the same are provided. it can.

The polyurethane polyurea resin (A) used in the present invention has a primary amino group in the molecular structure, and the primary amino group in the polyglycidyl ether (B) of a chain aliphatic polyol whose curing agent is a curing agent. A cured product can be obtained by reacting with an epoxy group to form a crosslinked structure. Here, the amount of the primary amino group in the polyurethane polyurea resin (A) is within the range of 3.0 to 30 mgKOH / g as the amine value of the polyurethane polyurea resin (A). It is preferable because it has a high film followability and a good film followability, and not only the initial laminate strength and appearance but also the laminate strength and laminate appearance after the boil treatment are good.

Here, the amine value is specifically a value titrated by the following method.
[Amine titration method]
Crystal violet indicator is added to a predetermined amount of polyurethane polyurea resin (A), and this is changed from blue purple to blue (the point where the redness disappears) with 0.1 mol / L perchloric acid (HClO ₄ ) acetic acid solution. Titrate. The test is performed in the same manner, and is a value calculated by the following (formula 1).

(Formula 1)
Amine value (KOHmg) = 56.1 × [( Vs-Vb) / W] × 0.1 × [F 20/1 + W: mass of a polyurethane-polyurea resin used for titration (A) (g)
0.0011 (t-20)]
Vs: titration of 0.1 mol / L perchloric acid (HClO ₄ ) acetic acid solution required for titration

Vb: titration amount of 0.1 mol / L perchloric acid (HClO ₄ ) acetic acid solution required for titration in blank test F ₂₀ : force of 20 mol of 0.1 mol / L perchloric acid (HClO ₄ ) acetic acid solution Value t: Temperature of 0.1 mol / L perchloric acid (HClO ₄ ) acetic acid solution at the time of titration

In addition, the polyurethane polyurea resin (A) having a primary amino group in the molecular structure described above is a polyether polyurethane polyurea resin having a polyether structure site in the molecular structure. It is preferable from an excellent point. Here, the polyether structure part is a structure part derived from the later-described polyether polyol (α1) used as a raw material, and the one having a molecular weight in the range of 100 to 3,500 is described above. This is preferable from the viewpoint of excellent balance between flexibility and laminate strength when the adhesive is cured. The molecular weight of the polyether polyol is a value calculated from the actual value of the hydroxyl value (mgKOH / g) and the valence of the polyol.

The primary amino group-containing polyurethane polyurea resin (A) is reacted with the polyol component (α) and the polyvalent isocyanate compound (β) to obtain a urethane prepolymer (X), and then the urethane prepolymer (X) ) Can be obtained by reacting with an amine compound (Y).

Here, when the polyether polyol (α1) is used as the polyol component (α), the polyurethane polyurea resin becomes a polyether polyurethane polyurea resin (a1) having a polyether structure in the resin structure. When the polyol (α2) is used, the polyester polyurethane polyurea resin (a2) having a polyester structure in the resin structure, and when the polyether polyester polyol (α3) is used, the polyether polyester structure is included in the resin structure. The resulting polyether polyester polyurethane polyurea resin (a3).

Here, as the polyether polyol (α1), an oxirane compound such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran, and a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, and glycerin as an initiator are used. Examples thereof include polyoxyalkylene glycols obtained by polymerization.

Among these, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol are preferable from the viewpoint of excellent laminate strength when the finally obtained polyurethane polyurea resin is used as an adhesive. Since these polyoxyalkylene glycols have good film adhesion, a molecular weight in the range of 100 to 3,500 is preferable from the viewpoint of imparting appropriate flexibility to the adhesive and good laminate appearance. . Here, as described above, the molecular weight of the polyoxyalkylene glycol is a value calculated from the measured value of the hydroxyl value (mgKOH / g) and the valence of the polyol.

Moreover, when using the said polyether polyol ((alpha) 1), another glycol compound ((alpha) ') can be used together.

Moreover, such a glycol compound (α ′) can be used in a proportion of 10 parts by mass or less based on 100 parts by mass in total with the polyether polyol (α1). , 2-propanediol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2-ethyl-2butyl-1,3propanediol, 1,3-butanediol, 1,4-butanediol, Examples thereof include aliphatic diols such as neopentyl glycol, pentanediol, 3-methyl-1,5-pentanediol, hexanediol, octanediol, and 1,4-butanediol.

Next, examples of the polyester polyol (α2) include polyester polyols obtained by esterifying the glycol compound (α ′) with a polyvalent carboxylic acid or an anhydride thereof (α2-1).

Examples of the polyvalent carboxylic acid or its anhydride (α2-1) that can be used here include aliphatic dicarboxylic acids such as adipic acid, succinic acid, oxalic acid, glutaric acid, pimelic acid, speric acid, azelaic acid, and sebacic acid. ; Unsaturated dicarboxylic acids such as maleic acid and fumaric acid; aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid; phthalic anhydride, trimellitic anhydride, pyromellitic acid Acid anhydrides such as anhydrides may be mentioned. Of these, aliphatic dicarboxylic acids are preferred from the viewpoint of obtaining a resin having particularly excellent flexibility.

Here, the polyester polyol (α2) preferably has a weight average molecular weight (Mw) in the range of 400 to 5,000 from the viewpoint of excellent laminate strength after the boil treatment, and can easily be adjusted to such a molecular weight range. In view of this, the reaction ratio between the glycol compound (α ′) and the polyvalent carboxylic acid or anhydride (α2-1) is determined by the number of equivalents of hydroxyl groups in the glycol compound (α ′), the polyvalent carboxylic acid or The ratio [(α ′) / (α2-1)] of the anhydride (α2-1) to the equivalent number of carboxylic acids is preferably in the range of 1 / 0.88 to 1 / 0.95. This esterification reaction is preferably performed under a temperature condition of 180 to 260 ° C. in the presence of an esterification catalyst, for example.

Examples of the esterification catalyst that can be used here include organic tin compounds, inorganic tin compounds, organic titanium compounds, and organic zinc compounds.

Moreover, when using the said polyester polyol ((alpha) 2) as a polyol component ((alpha)), it is preferable to use the said polyether polyol ((alpha) 1) together with the polyester polyol ((alpha) 2), and the usage rate is the lamination strength of an adhesive agent. From this point, the mass ratio [(α2) / (α1)] is preferably in the range of 75/25 to 10/90. Moreover, you may use together the said glycol compound ((alpha) ') in the ratio of 10 mass parts or less per these 100 mass parts in total.

Next, the polyether polyester polyol (α3) is an esterification reaction between the polyether polyol (α1), the glycol compound (α ′), and the polyvalent carboxylic acid or anhydride (α2-1). It is obtained by making it. Its weight average molecular weight (Mw) is in the range of 2,500 to 5,000. The polyurethane polyurea resin finally obtained is moderately flexible and has excellent laminate strength and initial laminate appearance. It is preferable from the point of becoming. The esterification reaction described above can be performed under the same conditions as the synthesis of the polyester polyol (α2), and the total of hydroxyl groups of the polyether polyol (α1) and the glycol compound (α ′) The ratio of the number of equivalents of the polyvalent carboxylic acid or its anhydride (α2-1) as the carboxylic acid [(OH) / (acid group)] may be in the range of 1 / 0.88 to 1 / 0.95. From the viewpoint of easily adjusting the molecular weight of the obtained polyester polyol to the above-mentioned range.

On the other hand, the polyisocyanate (β) to be reacted with the polyol component (α) is various known aromatic diisocyanates, chain aliphatic diisocyanates, alicyclic diisocyanates generally used in the production of polyurethane polyurea resins, and Examples thereof include tri- to tetrafunctional polyisocyanates.

Aromatic diisocyanates include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyl Diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis-chloromethyl-diphenylmethane -Diisocyanate, 2,6-diisocyanate-benzyl chloride and the like, and chain aliphatic Examples of the isocyanate include those having 1 to 9 carbon atoms such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Diisocyanates include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate. Etc.

Examples of the tri- to tetra-functional polyisocyanate include adduct type polyisocyanate having a urethane bond site in the molecule, and nurate type polyisocyanate having an isocyanurate ring structure in the molecule. These may be used alone or in combination of two or more.

The adduct polyisocyanate having a urethane bond site in the molecule can be obtained, for example, by reacting a diisocyanate monomer with a trifunctional or higher polyhydric alcohol. Examples of the diisocyanate monomer used in the reaction include various diisocyanates exemplified as the diisocyanate, and each may be used alone or in combination of two or more. Examples of the trifunctional or higher polyhydric alcohol used in the reaction include trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, etc., each of which may be used alone or in combination of two or more. You may do it.

Examples of the nurate type polyisocyanate having an isocyanurate ring structure in the molecule include those obtained by reacting a diisocyanate monomer trimer, a diisocyanate monomer and a monoalcohol or a dihydric alcohol. Examples of the diisocyanate monomer used herein include various diisocyanate monomers exemplified as the diisocyanate, and each may be used alone or in combination of two or more. Monoalcohols used in the reaction are hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hepta. Decanol, n-octadecanol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol, 2-octyldodecanol, 2-decyltetradecanol and the like, and dihydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propane. Diol, , 2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3- Examples include methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, and 1,4-bis (hydroxymethyl) cyclohesan. In addition, lysine diisocyanate, dimerisocyanate obtained by converting a carboxyl group of dimer acid into an isocyanate group, and the like can also be used as the polyvalent isocyanate (β).

Among these, those having a cyclic structure in the molecular structure such as aromatic diisocyanate, alicyclic diisocyanate, and nurate type polyisocyanate are preferable from the viewpoint of being excellent in boil resistance.

The reaction ratio between the glycol component and the polyvalent isocyanate when the urethane prepolymer (X) is synthesized preferably has an equivalent ratio [OH / NCO] of 1.2 to 3.0. When the ratio is less than 1.2, gelation may occur. When the ratio is more than 3.0, the solubility of the resulting prepolymer tends to decrease.

The urethane prepolymer (X) thus obtained preferably has an isocyanate residual ratio in the range of 1.00 to 5.00% by mass from the viewpoint of good laminate strength. Here, the isocyanate residual rate is a sample of urethane prepolymer (X) taken out, dissolved in ethyl acetate, added with a predetermined concentration and a predetermined amount of amine solution, and then added with an indicator, The mass-based NCO group concentration obtained by titration with hydrochloric acid.

Next, a polyurethane polyurea resin (A) having a primary amino group at the target molecular end is obtained by reacting the obtained urethane prepolymer (X) with a diamine as the amine compound (Y) and, if necessary, a monoamine. be able to. Here, the reaction ratio between the urethane prepolymer (X) and the amine component (Y) is such that the equivalent ratio [NCO / NH ₂ ] is 1.00 / 1.01 to 1/2. Is preferable from the point of adjusting to a proper range.

The diamine described above functions as a chain extender, and the monoamine functions as a reaction terminator. Here, by increasing the equivalent ratio [NCO / NH ₂ ] to a range of 1 / 1.01 to 1/2, a polyurethane polyurea resin (A) having a primary amino group at the terminal is obtained without using a monoamine. However, in the present invention, it is preferable to use diamine and monoamine in combination from the viewpoint of increasing the crosslinking density while ensuring an appropriate pot life as an adhesive. In this case, the proportion of diamine and monoamine is preferably such that the mass ratio [diamine / monoamine] is 90/10 to 60/40.

Examples of diamines that can be used here include ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, 1,2-cyclohexanediamine, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane. , Dicyclohexylmethane-4,4′-diamine, 2-hydroxyethylethylenediamine, 2-hydroxyethylpropyldiamine, 2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylenediamine, di-2- Hydroxyethylpropylenediamine, (N-aminoethyl) -2-ethanolamine, 2-hydroxypyrroleethylenediamine, di-2-hydroxypyrroleethylenediamine, di- - hydroxypropyl ethylenediamine, and the like.

Among these, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, 1,2-cyclohexanediamine, or dicyclohexylmethane-4,4'-diamine (amine having a cyclohexane ring) is preferable.

Examples of monoamines include dialkylamines such as di-n-butylamine, compounds having an alicyclic hydrocarbon group such as N-methylcyclohexylamine, dicyclohexylamine, cyclohexylamine, cyclopentylamine, and cyclohexylethylamine, monoethanolamine, Examples include alkanolamines such as diethanolamine and monoisopropanolamine. Among these, one or more compounds of the group consisting of N-methylcyclohexylamine, dicyclohexylamine, cyclohexylamine, cyclopentylamine, and cyclohexylethylamine are laminated. This is preferable from the viewpoint of good strength.

The polyurethane polyurea resin (A) having a primary amino group thus obtained may be modified with a polyfunctional epoxy resin in order to further increase the crosslinking density when using an adhesive. Examples of the polyfunctional epoxy resin that can be used here include a polyfunctional epoxy compound (B) to be described later, and it is preferable to use the polyfunctional epoxy resin within a range in which the amine value of 3.0 to 30 mgKOH / g can be maintained.

As described above, the polyurethane polyurea resin (A) described in detail above has an excellent solubility in alcohol-based solvent components when the weight average molecular weight (Mw) is in the range of 20,000 to 60,000. From the viewpoint of excellent laminate strength.

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

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

The polyurethane polyurea resin (A) having the primary amino group in the molecular structure described in detail above can be used as an organic solvent solution dissolved in an organic solvent (C) when used as a main component of an adhesive. . Examples of the organic solvent (C) that can be used here include methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, and cyclohexane. Etc. Among these, ethyl acetate is preferable from the viewpoint of solubility.

In the present invention, a resin solution containing the above-described polyurethane polyurea resin (A) and an organic solvent (C) as essential components can be used as a main component of a two-component curable laminate adhesive. Adjustment to the range of 30 to 70% by mass is preferable from the viewpoint of handling and excellent storage stability as an adhesive main agent. Moreover, when using an adhesive agent, the organic solvent (C) is further added to the appropriate viscosity by a coating machine to be used for use. The resin solution described in detail above constitutes the amine solution for a two-component curable laminate adhesive of the present invention.

The amine solution for a two-component curable laminate adhesive described above further has an aminosilane coupling agent and has a good seal strength at the sealant portion when used in a laminate packaging bag, and a good adhesive strength to the printing surface. It is preferable from the point which becomes. Examples of aminosilane coupling agents include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-amino. Examples thereof include propyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and the like, and the blending amount thereof is preferably in the range of 0.3 to 3% by mass in the amine solution for a two-component curable laminate adhesive. .

Next, the polyfunctional epoxy compound (B) used as a curing agent in the two-component curable laminate adhesive of the present invention contains a polyglycidyl ether of a chain aliphatic polyol as an essential component. Among them, a liquid or semi-solid epoxy compound at 25 ° C. is preferable from the viewpoint of handling, and specifically, an epoxy compound having an epoxy equivalent in the range of 100 to 300 g / equivalent is preferable. Specifically, glycerol polyglycidyl ether such as glycerol diglycidyl ether and polyglycidyl ether of polyglycerol; trimethylolpropane triglycidyl ether such as trimethylolpropane diglycidyl ether and trimethylolpropane triglycidyl ether; sorbitol tetraglycidyl ether And polyglycidyl ethers of chain aliphatic polyols such as pentaerythritol tetraglycidyl ether. In particular, the epoxy equivalent is more preferably in the range of 100 to 250 g / equivalent, the epoxy equivalent is more preferably in the range of 100 to 230 g / equivalent, and the epoxy equivalent is most preferably in the range of 150 to 230 g / equivalent.

Among these, sorbitol polyglycidyl ether has excellent compatibility with the main agent, has a high crosslinking density and excellent boil resistance, and has excellent adhesion strength when printing is performed on the surface of the base film, And pentaerythritol tetraglycidyl ether are preferred. Such sorbitol polyglycidyl ether may be a simple substance or a polymer, but in the present invention, those having a viscosity of 4,000 to 23,000 mPa · s at 25 ° C. are compatible with the main agent or coated with the adhesive itself. It is preferable from the viewpoint of excellent workability.

The polyfunctional epoxy compound (B) may be used in combination with other polyfunctional epoxy compounds as long as the effects of the present invention are not impaired. For example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, and hydrogens thereof. Bisphenol-type epoxy resins such as additive-type epoxy resins; 3,4-epoxycyclohexylmethyl- (3,4-epoxy) cyclohexanecarboxylate, vinylcyclohexylene dioxide, bis (3,4-epoxycyclohexylmethyl) adipate, dicycloaliphatic Alicyclic epoxy compounds such as fattic diester diepoxide; diglycidyl ester of dimer acid consisting of castor oil polyglycidyl ether, tall oil fatty acid, linolenic acid, linoleic acid, etc .; epoxidized polybutadiene; epoxidized soybean oil, linseed oil Epoxy resins derived from vegetable oils such as epoxidized products can be used.

The polyfunctional epoxy compound (B) detailed above may be used as a resin solution dissolved in the organic solvent (C) described above, but when using a liquid epoxy compound at 25 ° C. It can be used in combination with the main agent.

The adhesive of the present invention comprises the above-described polyurethane polyurea resin (A) having a primary amino group in the molecular structure and polyglycidyl ether of a chain aliphatic polyol as a polyfunctional epoxy compound (B) as essential components. These blending ratios are such that the solid content of the polyglycidyl ether of the chain aliphatic polyol is 2 to 20 parts by weight, particularly 3 parts per 100 parts by weight of the solid content of the polyurethane polyurea resin (A). A ratio of ˜15 parts by mass is preferable from the viewpoint of boil resistance.

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

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

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

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

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

The mass ratio of the pigment used in the present invention is 1 to 400 parts by mass with respect to 100 parts by mass of the synthetic mass (solid content) of the polyurethane polyurea resin (A) and the polyglycidyl ether of the chain aliphatic polyol. In particular, the content of 10 to 300 parts by mass is more preferable because of excellent adhesion and blocking resistance.

If necessary, the adhesive of the present invention may contain other additives other than those described above. Examples of additives include leveling agents; inorganic fine particles such as colloidal silica and alumina sol; organic fine particles of polymethyl methacrylate; antifoaming agents; anti-sagging agents; wetting and dispersing agents; viscosity modifiers; ultraviolet absorbers; Deactivator; Peroxide decomposing agent; Flame retardant; Reinforcing agent; Plasticizer; Lubricant; Rust preventive agent; Fluorescent whitening agent; Inorganic heat absorber; Flameproof agent; Antistatic agent; Is mentioned.

These pigments, adhesion promoters, and additives are either of the above-described amine solution for a two-component curable laminate adhesive or a solution of the chain aliphatic polyol polyglycidyl ether organic solvent (C). It can be mixed with the components, or can be used as a third component by blending at the time of coating.

The laminated film of the present invention is a laminated film having the two-component curable laminate adhesive between the first plastic film and the second plastic film, specifically, the two-component curable laminate adhesive. A laminated film having a cured product between a first plastic film and a second plastic film, and the production method thereof comprises applying the two-component curable laminate adhesive to the first plastic film and then applying the second adhesive to the coated surface. This is a method of laminating two plastic films and curing the adhesive layer.

Specifically, the two-component curable laminate adhesive of the present invention is applied to the first plastic film using, for example, a gravure coater, a die coater or a lip coater, and then dried and bonded to another substrate. A method is mentioned. In the die coater and the lip coater, the coating width can be freely adjusted by deckles attached to both ends of the die or the lip portion. The coating conditions are preferably about 500 to 2500 mPa · s when heated to about 25 ° C. to 120 ° C. in a normal roll coater. The coating amount is preferably 0.5 to 5 g / m ² , more preferably about 1.5 to 4 g / m ² .

In addition, when the two-component curable laminate adhesive of the present invention is used, the adhesive is cured by aging at 35 to 55 ° C. for 3 to 7 days after lamination, so that practical physical properties can be expressed.

Examples of the first plastic film used here include PET (polyethylene terephthalate) film, nylon film, OPP (biaxially oriented polypropylene) film, base films such as various deposited films, aluminum foil, and the like. Examples of the base material include sealant films such as CPP (unstretched polypropylene) film and LLDPE (linear low density polyethylene) film.

The laminated film of the present invention can be used as a packaging material in foods, detergents, drugs, cosmetics and the toiletry industry. In particular, it is particularly useful as a packaging material for food that requires retort sterilization because of its excellent laminate adhesive strength after boil treatment. It can also be used for a secondary package for packaging a container made of the packaging material.
Of course, other applications such as barrier materials, roofing materials, solar cell panel materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive parts, signs, stickers, etc. It can be suitably used as a decorative sheet used in the method.

The laminated film of the present invention has excellent adhesiveness and content resistance without causing delamination of the laminate structure such as delamination not only during filling of the contents but also after elapse of time after filling.

Hereinafter, the contents and effects of the present invention will be described in more detail with reference to examples. Moreover, the raw material polyol used as a raw material by each Example and a comparative example is shown below.

Example 1 (Preparation of polyurethane polyurea resin solution A)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas inlet tube was charged with polypropylene glycol having a molecular weight of about 3000 (actol “PPG3000” manufactured by Mitsui Chemicals, Inc., molecular weight 3024 (hydroxyl value 37.1 mgKOH / g, Calculated value as the number of functional groups 2)), 192.7 parts by weight of a mixture of 1,3-butanediol (weight ratio = 97/3) and 47.29 parts by weight of isophorone diisocyanate were charged at 90 ° C. under a nitrogen stream. For 5 hours to produce a prepolymer having a free isocyanate value (isocyanate group content) of 3.07% by mass, and then 60 parts by mass of ethyl acetate was added thereto to obtain a uniform solution of a urethane prepolymer. Next, the urethane prepolymer solution was added to a mixture consisting of 14.88 parts by mass of isophoronediamine, 1.25 parts by mass of cyclohexylamine, 2.9 parts by mass of ethyl acetate and 146.7 parts by mass of ethanol, The polyurethane polyurea resin solution A was obtained by stirring for a period of time. The obtained polyurethane polyurea resin solution A had a resin solid content concentration of 55% by mass, a resin amine value of 3.82 mg KOH / g, and a B-type rotational viscometer (“TVB-10M” manufactured by Toki Sangyo Co., Ltd.). The viscosity measured using this was 800 mPa · s (25 ° C.), and the weight average molecular weight (Mw) of the resin solid content was 52,000.

Example 2 (Preparation of polyurethane polyurea resin solution B)
The same production method was carried out except that 1,3-butanediol in Example 1 was changed to 1,4-butane. The obtained polyurethane polyurea resin solution B was designated. The obtained polyurethane polyurea resin solution B has a resin solid content concentration of 55% by mass, a resin amine value of 3.82 mg KOH / g, and a B-type rotational viscometer (“TVB-10M” manufactured by Toki Sangyo Co., Ltd.). The viscosity measured using this was 1,000 mPa · s (25 ° C.), and the weight average molecular weight (Mw) of the resin solid content was 53,000.

Example 3 (Preparation of polyurethane polyurea resin solution C)
A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube was charged with polypropylene glycol having a molecular weight of about 1000 (“Accor PPG 1,000” manufactured by Mitsui Chemicals, Ltd., molecular weight 1001 (hydroxyl value 112.0 mgKOH / g, calculated value as the number of functional groups 2)) and polypropylene glycol having molecular weight 2015 (calculated value from hydroxyl value) (“Accor PPG2000” manufactured by Mitsui Chemicals, Inc.), molecular weight 2015 (hydroxyl value 55.7 mgKOH / g, number of functional groups 2) and a mixture of 185.2 parts by mass of toluene diisocyanate and reacted at 90 ° C. for 5 hours under a nitrogen stream to give a free isocyanate value (isocyanate). (Base content) 6.07% by mass of prepolymer was prepared, And a homogeneous solution of a urethane prepolymer by adding 62.03 parts by weight. Next, the urethane prepolymer was added to a mixture consisting of 24.12 parts by mass of 2- (2-aminoethylamino) ethanol, 0.2 parts by mass of monoethanolamine, 4.9 parts by mass of ethyl acetate and 156.0 parts by mass of ethanol. The solution was added and stirred at 45 ° C. for 5 hours to obtain a polyurethane polyurea resin solution C. The obtained polyurethane polyurea resin solution C has a resin solid content concentration of 55% by mass, a resin amine number of 23 mgKOH / g, and a B-type rotational viscometer (“TVB-10M” manufactured by Toki Sangyo Co., Ltd.). The measured viscosity was 800 mPa · s (25 ° C.), and the weight average molecular weight (Mw) of the resin solid content was 32,000.

Examples 4 to 15 and Comparative Examples 1 to 3
An adhesive and a laminate film were produced by the following methods, and various evaluations were performed. The results are shown in Tables 1 to 3.

[Preparation of laminate sheet for evaluation 1 PET / LLDPE]
After producing an adhesive according to the formulation of Table 1 and Table 3, it was applied to a PET film (“E5100” thickness 12 μm manufactured by Toyobo Co., Ltd.) so that the coating amount was about 3.0 g / m ^{2 in} solid content, A laminated film was prepared by laminating the coated surface of this film with a linear low-density polyethylene film (LLDPE “TUX-HC 60 μm” manufactured by Mitsui Tosero Co., Ltd.) using a laminator. The laminate film was aged for 3 days in a constant temperature bath at 40 ° C.

[Preparation of laminate sheet for evaluation 2 Nylon / LLDPE]
After producing an adhesive according to the formulation of Table 1 and Table 3, it was applied to a nylon film (thickness 15 μm) so that the coating amount was about 3.0 g / m ^{2 in} solid content, and this film was coated with a laminator. The coated surface was bonded to a linear low density polyethylene film (LLDPE “TUX-HC 60 μm” manufactured by Mitsui Tosero Co., Ltd.) to produce a laminate film. The laminate film was aged for 3 days in a constant temperature bath at 40 ° C.

[Preparation of laminate sheet for evaluation 3 2-color printing PET / LLDPE]
According to the composition of Table 2, each resin solution and an aminosilane coupling agent are blended to adjust the main component, and then an adhesive is produced by blending an epoxy compound and ethyl acetate, and then printing ink (Sun Chemical Co., Ltd.) Applied to a PET film flexibly printed in the order of blue and white with “Duralam PF” (made by Toyobo Co., Ltd., “E5100” thickness 12 μm) so that the coating amount is about 3.0 g / m ^{2 in} solid content, A laminated film was prepared by laminating the coated surface of this film with a linear low-density polyethylene film (LLDPE “TUX-HC 60 μm” manufactured by Mitsui Tosero Co., Ltd.) using a laminator. The laminate film was aged for 3 days in a constant temperature bath at 40 ° C.

[Preparation of laminate sheet for evaluation 4 2-color printing nylon / LLDPE]
According to the composition of Table 2, each resin solution and an aminosilane coupling agent are blended to adjust the main component, and then an adhesive is produced by blending an epoxy compound and ethyl acetate, and then printing ink (Sun Chemical Co., Ltd.) “Duralam PF” manufactured in Japan) is applied to a nylon film (thickness 15 μm) flexographically printed in the order of blue and white so that the coating amount is about 3.0 g / m ^{2 in} solid content, and this film is applied with a laminator. The laminate was bonded to the surface and a linear low-density polyethylene film (LLDPE “TUX-HC 60 μm” manufactured by Mitsui Tosero Co., Ltd.). The laminate film was aged for 3 days in a constant temperature bath at 40 ° C.

(Peel strength before boil treatment)
The peel strength of a sample cut out from each of the above laminated films with a width of 15 mm was set to a peel rate of 300 mm / min using a tensile tester at an ambient temperature of 25 ° C., and the adhesive strength by a tensile test using a T-type peel method. (N / 15 mm) was measured.

(Peel strength after boil treatment)
Each of the above laminated films is folded so that the LLDPE is on the inside, and heat-sealed at 1 atm, 180 ° C. for 1 second to produce a pouch in which the contact portion of the contents is 200 cm ^2. : Meat sauce: salad oil (mass ratio) = 1: 1: 1 solution].
The packed pouch is immersed in high-temperature water at 98 ° C. for 60 minutes, taken out, and the peel strength of the sample cut out from the laminated film part of the pouch from which the contents have been removed is cut to a width of 15 mm using a tensile tester at an ambient temperature of 25 ° C. The peeling strength was set to 300 mm / min, and the adhesive strength (N / 15 mm) was measured by a tensile test when measured by a T-type peeling method.

(Early appearance)
The state of the laminate film obtained by the aging treatment was visually observed, and those having a good laminate appearance such as tunneling were defined as “good”.

(Appearance evaluation after boil processing)
The appearance of the pouch after the boil treatment was evaluated.
○: No delamination ×: Delamination

In each of the above-mentioned Tables 1 to 3, “break” means a state in which the base film is broken without peeling at the adhesive layer because of excellent adhesive strength. For example, “break at PET” in the PET / LLDPE after the boil treatment in Example 4 indicates a state in which the PET is broken before peeling occurs in the adhesive layer. Moreover, the strength of the base film to break is roughly 12 N / 15 mm for the nylon film and 7 N / 15 mm for the PET film.
The details of each raw material and base film described in Tables 1 to 3 are as follows.
Aminosilane coupling agent: “Dynasylan AMEO” manufactured by Evonik
Pentaerythritol polyglycidyl ether: Polyglycidyl ether of pentaerythritol (3-4 functional, epoxy equivalent 229 g / eq.)
TMP-based polyglycidyl ether: polyglycidyl ether of trimethylolpropane (2 to 3 functional, epoxy equivalent 134 g / eq.)
BPA-based polyglycidyl ether: Diglycidyl ether of bisphenol A (“EPICLON850” epoxy equivalent of 188 g / eq. Manufactured by DIC Corporation)
Sorbitol-based polyglycidyl ether: Polyglycidyl ether of sorbitol (3-4 functional, epoxy equivalent 173 g / eq., Viscosity 5,000 mPa · s)
N, N, N ′, N′-tetraglycidyl-1,3-benzenedi (methanamine): “TETRAD-X” (viscosity 1600-3000 mPa · s) manufactured by Mitsubishi Gas Chemical Company, Inc.
N, N, N ′, N′-tetrakis (2,3-epoxypropyl) cyclohexane-1,3-dimethylamine: “TETRAD-C” (viscosity 1600-3000 mPa · s) manufactured by Mitsubishi Gas Chemical Company, Inc.
Ny: Nylon film ("emblem ON" thickness 15 µm, manufactured by Unitika)
PET: PET film (Toyobo “E5100” thickness 12 μm)
LLDPE: Linear low-density polyethylene film (“TUX-HC” 60 μm thick, manufactured by Mitsui Tosero)

Claims

A two-component curable type comprising a polyurethane polyurea resin (A) having a primary amino group in the molecular structure and a polyglycidyl ether of a chain aliphatic polyol as a polyfunctional epoxy compound (B) as essential components Laminate adhesive.
The two-component curable laminate adhesive according to claim 1, wherein the polyurethane polyurea resin (A) having a primary amino group in the molecular structure has an amine value of 3.0 to 30 mgKOH / g.
The two-component curable laminate adhesive according to claim 1, wherein the polyurethane polyurea resin (A) having a primary amino group in its molecular structure is a polyether polyurethane polyurea resin.
The two-component curable laminate adhesive according to claim 3, wherein the polyether polyurethane polyurea resin has a molecular weight of 100 to 3,500 in a raw material of a polyether structure portion present in the resin.
The two-component curable laminate adhesive according to any one of claims 1 to 4, wherein an epoxy equivalent of the polyglycidyl ether of the chain aliphatic polyol is in a range of 100 to 300 g / equivalent.
The two-component curable laminate adhesive according to any one of claims 1 to 5, comprising an organic solvent (C).
The two-component curable laminate adhesive according to any one of claims 1 to 6, comprising an aminosilane coupling agent.
A cured product obtained by curing the two-component curable laminate adhesive according to any one of claims 1 to 7.
A laminated film comprising the two-component curable laminate adhesive according to any one of claims 1 to 7 between a first plastic film and a second plastic film.
A two-component curable laminate adhesive comprising a polyurethane polyurea resin (A) having a primary amino group in the molecular structure and an organic solvent (C) in a proportion of a solid content of 30 to 70% by mass. Amine amine solution.
The amine solution for two-component curable laminate adhesives according to claim 10 containing an aminosilane coupling agent.