JP6278166B1 - Urethane adhesive, polyol composition for urethane adhesive, polyisocyanate composition for urethane adhesive, cured product of urethane adhesive, and laminated film - Google Patents

Abstract

Polyol (A) selected from the group consisting of polyester polyol, polyester polyether polyol, polyester polyurethane polyol, polyether polyurethane polyol, and polyester polyether polyurethane polyol, polyisocyanate (B), and SP value of 20 to 32 (J / Cm3) 1/2 and the carboxyl group-containing compound (C) having an acid value of 250 to 1,000 mgKOH / g as an essential component, and the carboxyl group-containing compound (C) is 0 per 100 parts by mass of the polyol (A). A urethane-based adhesive contained at a ratio of 0.01 to 1.5 parts by mass.

Description

  The present invention relates to a urethane-based adhesive, a polyisocyanate mixture, a polyol mixture, and a laminated film obtained by laminating various films using the 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.

  As the adhesive used for such dry lamination, a two-component polyurethane adhesive mainly containing a polyol component having a hydroxyl group at a polymer terminal and a polyisocyanate as a curing agent is mainly used. 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, when a laminate film for packaging is prepared using a urethane-based adhesive using such polyester polyol or polyester polyurethane polyol as a main ingredient, the adhesive layer of the multilayer film is an acid component contained in food or the like as a content. It was easily destroyed by erosion of alkali components.

  In particular, when food packaging (e.g. snacks, frozen foods) using aluminum-deposited films is increasing in recent years, acid components such as vinegar and free fatty acids contained in the food, or alkaline foods are packaged. However, after the boil sterilization treatment, while being displayed at the store, the aluminum deposition layer disappeared, and the printed pattern disappeared or the contents could be seen.

  Therefore, conventionally, for example, in Patent Document 1 below, as an adhesive for laminating an aluminum foil and an unstretched polypropylene film in a multilayer film for food packaging, a polyol obtained by modifying a polymer polyol with styrene-maleic anhydride, A technique for improving the compatibility between the polyol component and the polyisocyanate component by using a urethane-based adhesive composed of a polyisocyanate and preventing the disappearance of the adhesive layer due to vinegar or free fatty acids from the contents is disclosed. Yes.

  However, the adhesive described in Patent Document 1 uses a large amount of styrene-maleic anhydride and uses about 6 parts by mass with respect to 100 parts by mass of the polymer polyol. In addition to the appearance of the film being lowered, such as sometimes embracing air, the adhesive layer became solid and brittle, and eventually the adhesive strength over a long period of time could not be obtained, and the above-described disappearance of the aluminum vapor-deposited layer was inevitable during long-term use.

Japanese Patent No. 3206946

  Accordingly, the problem to be solved by the present invention is an adhesive used for laminating a laminate film, particularly a metal surface such as an aluminum foil or an aluminum vapor-deposited film, and a resin film, and is a laminate obtained for excellent workability. In addition to having a good appearance of the film, an adhesive that has excellent adhesive strength over a long period of time, and can suppress the disappearance of the metal deposited layer over a long period of time when the metal vapor deposited film is used as a base film, the adhesive It is an object of the present invention to provide a multilayer film excellent in long-term stability and appearance, which is laminated with the main agent or curing agent usable in the above-mentioned method and the adhesive.

  As a result of intensive studies to solve the above problems, the present inventors have found that a polyol / polyisocyanate adhesive contains 0.01 to 1.5 parts by weight of a carboxyl group-containing compound having a specific SP value per 100 parts by mass of the polyol. By using it as an additive component at a ratio of parts by mass, the multilayer film has excellent long-term stability and good processability, so that the appearance of the multilayer film is also excellent. The headline and the present invention were completed.

That is, the present invention provides a polyol (A) selected from the group consisting of polyester polyol (a1), polyester urethane polyol (a2), and polyether urethane polyol (a3), polyisocyanate (B), and SP value of 20 To 32 (J / cm ³ ) ^1/2 and an acid value of 250 to 1,000 mg KOH / g of the carboxyl group-containing compound (C), and the carboxyl group-containing compound (C) is 0 per 100 parts by mass of the polyol (A). Provided is a urethane-based adhesive contained at a ratio of 0.01 to 1.5 parts by mass.

The present invention also includes a polyol (A) selected from the group consisting of polyester polyol (a1), polyester urethane polyol (a2), and polyether urethane polyol (a3), and an SP value of 20 to 32 (J / cm ³ ) ^1/2 and the carboxyl group-containing compound (C) having an acid value of 250 to 1,000 mgKOH / g, and 0.01 to 1.5 of the carboxyl group-containing compound (C) per 100 parts by mass of the polyol (A). Provided is a polyol composition for urethane-based adhesive, which is contained in a ratio of parts by mass.

The present invention also includes a polyisocyanate (B) and a urethane containing a carboxyl group-containing compound (C) having an SP value of 20 to 32 (J / cm ³ ) ^1/2 and an acid value of 250 to 1,000 mgKOH / g. A polyisocyanate composition for a system adhesive is provided.

  The present invention also provides a cured product obtained by curing the urethane adhesive.

  The present invention also provides a laminated film obtained by coating the urethane-based adhesive on a first base film, then laminating a second base film on the coated surface, and curing the adhesive layer.

  According to the present invention, an adhesive used for laminating a laminate film, particularly a metal surface such as an aluminum foil or an aluminum vapor-deposited film, and a resin film, which has excellent workability and a good appearance of the laminate film. In addition, an adhesive having excellent adhesive strength over a long period of time, a main agent or a curing agent thereof, and a multilayer film having excellent long-term stability and appearance laminated by the adhesive can be provided.

As described above, the urethane-based adhesive of the present invention includes a polyol (A) selected from the group consisting of polyester polyol (a1), polyester urethane polyol (a2), and polyether urethane polyol (a3), polyisocyanate (B ) And a carboxyl group-containing compound (C) having an SP value of 20 to 32 (J / cm ³ ) ^1/2 and an acid value of 250 to 1,000 mgKOH / g, and the carboxyl group-containing compound ( C) is contained at a ratio of 0.01 to 1.5 parts by mass per 100 parts by mass of the polyol (A). Such a urethane-based adhesive is a two-component adhesive of polyol (A) / polyisocyanate (B), and the carboxyl group-containing compound (C) is used as a polyol composition blended with the polyol (A). Or it can be used as a polyisocyanate composition blended with the polyisocyanate (B). Or when using an adhesive agent, it can mix | blend simultaneously when mix | blending a polyol (A) and a polyisocyanate (B).

  In the present invention, it is important to use the carboxyl group-containing compound (C) at a ratio of 0.01 to 1.5 parts by mass with respect to 100 parts by mass of the polyol (A). When the amount of the carboxyl group-containing compound (C) used is less than 0.01 parts by mass, the effect of preventing delamination by blending the carboxyl group-containing compound (C) is not expressed, and 1.5 parts by mass If it exceeds, the adhesive layer itself becomes solid and brittle, and long-term adhesive strength cannot be obtained. For example, when a metal vapor deposition film is used, the vapor deposition layer is subjected to erosion by the acid or alkali contained in the contents. In addition to the loss of the film, the workability during coating is poor and the film appearance is poor.

  The polyol (A) used here is selected from the group consisting of the polyester polyol (a1), the polyester urethane polyol (a2), and the polyether urethane polyol (a3) as described above. The urethane-based adhesive composed of these polyol components exhibits excellent adhesion performance and processability, while the content easily contains an adhesive layer when an acidic substance or an alkaline substance is contained in the contents. By using the carboxyl group-containing compound (C) as an additive, disappearance of the adhesive layer due to an acidic substance or an alkaline substance can be effectively prevented.

  Specifically, the polyester polyol (a1) constituting the polyol (A) is a polyester polyol (a1-1) obtained by reacting an aliphatic polyol with an aliphatic polyvalent carboxylic acid, an aliphatic polyol, and Polyester polyol (a1-2) obtained by reacting with aromatic polycarboxylic acid, and polyester polyol (a1) which is a reaction product of polyester and aliphatic polyol obtained by ring-opening polymerization reaction of an aliphatic cyclic ester compound -3).

  Here, as an aliphatic polyol used as a raw material for the polyester polyols (a1-1) to (a1-3), 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 Aliphatic glycols such as glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol; glycerin, trimethylolpropane, pentaerythritol A trifunctional or tetrafunctional aliphatic alcohol such as dimer diol; an aliphatic polyether polyol that is a ring-opening polymer of an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc. .

  On the other hand, examples of the aliphatic polycarboxylic acid used as a raw material for the polyester polyol (a1-1) include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclohexane. Examples thereof include pentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and dimer acid, and examples of the aromatic polyvalent carboxylic acid used as a raw material for the polyester polyol (a1-2) include terephthalic acid, isophthalic acid, and 1,4-naphthalene. Examples include dicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p′-dicarboxylic acid.

  Examples of the aliphatic cyclic ester compound that is a raw material for the polyester polyol (a1-3) include propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, and β-methyl-σ-valerolactone.

  The polyester polyol (a1) described in detail above is resistant to acidic substances and alkaline substances and has excellent content resistance, so that the number average molecular weight (Mn) is 3,000 to 5,000, and the weight average molecular weight (Mw). ) Is preferably in the range of 8,000 to 15,000. Moreover, it is preferable from the point which is excellent in the wettability to a base material that a hydroxyl value is the range of 3-50 mgKOH / g.

  In the present invention, the number average molecular weight (Mn) or the weight average molecular weight (Mw) is a value 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 x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

  Next, the polyester polyurethane polyol (a2) is a polyol having a urethane bond in the molecular structure obtained by modifying the above-described polyester polyol (a1) with polyisocyanate.

  Examples of the polyisocyanate used herein include polyisocyanates having an alicyclic structure in the molecular structure such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane; Linear aliphatic polyisocyanates such as 6-hexamethylene diisocyanate, lysine diisocyanate, and trimethylhexamethylene diisocyanate; aromatics such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and triphenylmethane triisocyanate Polyisocyanate etc. are mentioned.

  Here, in the present invention, the polyester polyurethane polyol (a2) has a side chain having an alkyl chain having 6 or more carbon atoms derived from dimer acid or dimer diol, and the branch point concentration of the side chain is an adhesive. Polyester polyurethane polyol (a2-1) of 0.2 mmol (hereinafter referred to as mmol / g) or more per gram of the solid content of the composition has good initial adhesiveness, and has heat resistance, water resistance and oil resistance. From the viewpoint of providing an adhesive having excellent hot water resistance and alkali resistance.

  Here, dimer acid is a product of Diels-Alder dimerization reaction of long-chain unsaturated fatty acids such as oleic acid and linoleic acid, and there are various types such as those obtained by adding hydrogen to an unsaturated bond to be saturated. For example, C18 monocarboxylic acid 0 to 5 wt%, C36 dimer acid 70 to 98 mass% and C54 trimer acid 0 to 30 wt%. The dimer diol is obtained by reducing the dimer acid described above.

  Further, if the branching point concentration of the side chain having a molecular weight of 70 or more is small, the change in dynamic viscoelastic modulus is small, and desired physical properties cannot be obtained. g or more is preferable.

  The polyester urethane polyol (a2-1) detailed above has a number average molecular weight (Mn) in the range of 8,000 to 15,000 and a weight average molecular weight (Mw) of 25,000 in terms of adhesive strength and fluidity. It is preferably in the range of ˜35,000. Moreover, it is preferable from the point which is excellent in the wettability to a base material that a hydroxyl value is the range of 2-15 mgKOH / g.

  The polyester polyurethane polyol (a2) uses the above-mentioned polyester polyurethane polyol (a2-1) as well as the above-mentioned aliphatic glycol and trifunctional or tetrafunctional aliphatic alcohol as raw material alcohol components, and azelain as a raw material carboxylic acid component. A polyester obtained by esterification using a C9-C12 long-chain aliphatic dicarboxylic acid and an aromatic dicarboxylic acid such as acid, sebacic acid (c10), dodecanedicarboxylic acid, etc. Since the polyester polyurethane polyol (a2-2) obtained by reacting with the polyisocyanate possessed has excellent adhesive strength and appropriate flexibility, it is preferable because it can be applied to a retort pouch having excellent retort resistance.

  The polyester urethane polyol (a2-2) described in detail above has a number average molecular weight (Mn) of 7,000 to 10,000 and a weight average molecular weight (Mw) of 25,000 to 40 from the above-mentioned retort resistance. , Preferably in the range of 1,000. Moreover, it is preferable from the point which is excellent in the wettability to a base material that a hydroxyl value is the range of 2-15 mgKOH / g.

  Next, the polyether polyurethane polyol (a3) is 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 -Ethylene oxide, propylene oxide, butylene in the presence of a polymerization initiator such as glycol such as cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol, etc. A urethane polyol-containing polyether polyol having a resin structure in which a polyether polyol obtained by addition polymerization of an alkylene oxide such as oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene or the like is further polymerized with the aromatic or aliphatic polyisocyanate is provided. Can be mentioned.

  The polyether polyurethane polyol (a3) detailed above has a number average molecular weight (Mn) in the range of 4,000 to 6,000, a weight average molecular weight (Mw), because it has excellent fluidity and can be used for high-speed lamination. ) Is preferably in the range of 14,000 to 20,000. Moreover, it is preferable from the point which is excellent in the wettability to a base material that a hydroxyl value is the range of 3-25 mgKOH / g.

  Next, the carboxyl group-containing compound (C) having an SP value of 13.00 to 15.00 and an acid value of 250 to 1,000 mgKOH / g has excellent laminate strength, particularly excellent adhesion performance to a metal deposition surface and a metal film. It is a component for expressing.

  Here, SP value is the following formula according to Fedors' calculation method.

ここで、Fedorsの計算方式とは、下記文献
に従い化学構造の凝集エネルギー密度とモル分子容から計算される値（δ）である。

Here, the Fedors calculation method is a value (δ) calculated from the cohesive energy density of the chemical structure and the molar molecular volume according to the following document.

[Reference]
R. F. Fedors, Polym. Eng. Sci. , 14 [2], 145-154, 1974
In the formula, Ecoh represents the cohesive energy density of each structural unit constituting the chemical structure. For example, —CH ₂ — is 4,940 J / mol, —CH ₃ is 4,710 J / mol, —CO— is 17,360 J / mol, —COO— is 18,000 J / mol, —COOH is 27,630 J / mol. Mol, = CH- is 4,310 J / mol, -CH <is 3,430 J / mol, -OH is 29,800 J / mol, -O- is 3,350 J / mol, and the like.

On the other hand, V is the molar molecular volume of each structural unit constituting the chemical structure. For example, —CH ₂ — is 16.1 cm ³ / mol, —CH ₃ is 33.5 cm ³ / mol, and —CO— is 10.8 cm. ³ / mol, —COO— is 18.0 cm ³ / mol, —COOH is 28.5 cm ³ / mol, ═CH— is 13.5 cm ³ / mol, —CH <is −1.0 cm ³ / mol, —OH Is 10.0 cm ³ / mol, —O— is 3.8 cm ³ / mol, and the like.

Since the carboxyl group-containing compound (C) used in the present invention has an SP value of 20 to 32 (J / cm ³ ) ^1/2 , it has excellent compatibility with the polyol (A) or the polyisocyanate (B). It is possible to effectively remove the influence of the contents from acidic substances and alkaline substances.

  In the present invention, since the carboxyl group-containing compound (C) has an acid value in the range of 250 to 1,000 mgKOH / g, it has excellent adhesion to the substrate, and in particular, a metal foil substrate or a metal Excellent adhesion to the deposition surface.

  Here, as the carboxyl group-containing compound (C), specifically, a copolymer (c1) of aromatic vinyl and maleic anhydride, a hydroxyl group-containing aliphatic carboxylic acid (c2), and tetrahydrophthalic anhydride And a skeleton (c3).

  The aromatic vinyl / maleic anhydride copolymer (c1) is a monomer composition ratio ([aromatic vinyl / maleic anhydride] molar ratio) constituting the aromatic vinyl / maleic anhydride copolymer (c1). Is preferably in the range of 1.5 / 1 to 5/1 because it is excellent in compatibility with the polyol (A) and can exhibit excellent laminate strength even after long-term storage of the adhesive. Moreover, it is preferable that it is the range of the weight average molecular weight 1000-4000 especially from a compatible point with a polyol (A), and the acid value of 0.1-20 mgKOH / g is preferable from the point of adhesive strength or PAA elution prevention. A range is preferable.

  Specific examples of the aromatic vinyl constituting the aromatic vinyl / maleic anhydride copolymer (c1) include styrene, α-methylstyrene, divinylbenzene, and the like. Styrene is preferred from the viewpoint of excellent compatibility with B).

The SP value of the aromatic vinyl / maleic anhydride copolymer (c1) is the SP value of the structural unit (s) attributed to the aromatic vinyl and the structural unit (m) attributed to the maleic anhydride. (Δ) may be calculated and calculated according to the abundance ratio of aromatic vinyl and maleic anhydride. For example, in the case of a 1: 1 molar ratio copolymer of aromatic vinyl and maleic anhydride, the SP value of the structural unit (s) simply derived from the aromatic vinyl and the structural unit attributable to maleic anhydride In the case of a copolymer having a molar ratio of aromatic vinyl to maleic anhydride of 2: 1, the SP value of the structural unit (s) is doubled to obtain the structure. What is necessary is just to total with the SP value of a unit (m).
Specifically, in the case of a 1: 1 (molar ratio) reaction product of styrene / maleic anhydride, the SP value is 31.4 (J / cm ³ ) ^1/2 .

Next, the hydroxyl group-containing aliphatic carboxylic acid (c2) used as the carboxyl group-containing compound (C) is 2,2-bis (hydroxymethyl) propionic acid [SP value 28.7 (J / cm ³ ) ^1/2 , Acid value 414-418 mgKOH / g], 2,2-bis (hydroxymethyl) butyric acid SP value 27.4 (J / cm ³ ) ^1/2 , acid value 374-378 mgKOH / g], and the like.

Next, the tetrahydrophthalic anhydride skeleton-containing compound (c3) used as the carboxyl group-containing compound (C) has the following structural formula 1

で表される、３ａ，４，５，７ａ−テトラヒドロ−７−メチル−５−（テトラヒドロ−２，５−ジオキソ−３−フラニル）−１，３−イソ−ベンゾフランジオン［ＳＰ値２９．１（Ｊ／ｃｍ^３）^１／２、酸価８４９ｍｇＫＯＨ／ｇ］が挙げられる。

3a, 4,5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3-iso-benzofurandione [SP value 29.1 ( J / cm ³ ) ^1/2 , acid value 849 mg KOH / g].

  Here, the aromatic vinyl / maleic anhydride copolymer (c1) is a solvent widely used when used as a dry laminate adhesive, in order to exhibit excellent solubility in ethyl acetate, As the main agent in the dry laminate adhesive, it is preferable to blend in the polyester polyol (a1), polyester urethane polyol (a2), or polyether urethane polyol (a3) and use it as an ethyl acetate solution.

  Further, since the hydroxyl group-containing aliphatic carboxylic acid (c2) exhibits excellent solubility in the polyether urethane polyol (a3), it is blended in the polyether urethane polyol (a3) and dissolved in ethyl acetate. Use as a main component polyol component is preferable because an adhesive for high-speed lamination can be adjusted.

  Moreover, since the said tetrahydrophthalic anhydride skeleton containing compound (c3) has favorable compatibility with a polyol (A) or a polyisocyanate (B), as an adhesive for dry laminates and a non-solvent type adhesive, Although it can be used widely, for example, it can be used in combination with polyisocyanate (B) as a curing agent component of an adhesive for dry laminate, so that the present invention can be applied to various product variations. preferable.

  Next, the polyisocyanate (B) used in the present invention has an aromatic structure in a molecular structure such as tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate, and the like. Polyisocyanate; polyisocyanate having an alicyclic structure in the molecular structure such as isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,3- (isocyanatomethyl) cyclohexane, 1,6-hexamethylene diisocyanate, Linear aliphatic polyisocyanates such as lysine diisocyanate and trimethylhexamethylene diisocyanate; among the various polyisocyanates described above, 1 mol of trimethylolpropane Adduct type polyisocyanate obtained by adding 3 mol of diisocyanate compound; Burette type polyisocyanate obtained by reacting 3 mol of diisocyanate at a rate of 1 mol of water, or isocyanurate obtained by trimerization of diisocyanate compound Type polyisocyanate; a polyurethane polyisocyanate compound (b3) obtained by reacting a polyisocyanate with a polyester polyol, a polyether polyol, or a low molecular polyol, and the like.

  Here, examples of the polyester polyol used as a raw material for the polyurethane polyisocyanate compound (b3) include the polyester polyol (a1) described above. Examples of the polyether polyol include 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 Ethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, triethyl Aliphatic glycols such as glycol and the like.

  Among these polyisocyanates (B), particularly as a solvent-type adhesive, a polyisocyanate nurate having an alicyclic structure in the molecular structure from the viewpoint of excellent curability and good adhesive strength. Body: Adduct type polyisocyanate with 3 mol of xylene diisocyanate added to 1 mol of trimethylolpropane: Adduct type polyisocyanate with 3 mol of tolylene diisocyanate added to 1 mol of trimethylolpropane; Polypropylene glycol of methylene diisocyanate Denatured products are preferred.

  As described above, the urethane-based adhesive of the present invention composed of the components described in detail above can be used as a solvent-type adhesive or as a solventless adhesive.

  The solvent used in the case of using as a solvent-type adhesive can be used as a reaction medium during the production of the polyol (A) and the polyisocyanate (B), and further as a diluent during coating. Examples of solvents that can be used here include esters such as ethyl acetate, butyl acetate, and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatic carbonization such as toluene and xylene. Examples thereof include hydrogens, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, and dimethyl sulfoamide. Among these, it is preferable to use ethyl acetate or methyl ethyl ketone because it can be easily recovered and reused.

  As described above, the urethane-based adhesive of the present invention is a two-component curable urethane-based adhesive, and the carboxyl group-containing compound (C) is a polyol composition (X) previously blended with the polyol (A). Alternatively, the carboxyl group-containing compound (C) can be used as a polyisocyanate composition (Y) in which the polyisocyanate (B) is blended.

  That is, in the case of a solvent-type two-component urethane adhesive, the polyol composition (X) is used as a two-component base and the polyisocyanate (B) is used as a curing agent, or the polyol ( A) can be used as a main agent, and the polyisocyanate composition (Y) can be used as a curing agent.

  On the other hand, in the case of a solventless two-component urethane-based adhesive, the polyisocyanate composition (Y) is used as a main agent and the polyol (A) is used as a curing agent, or the polyisocyanate ( B) can be used as a main agent, and the polyol composition (X) can be used as a curing agent.

Here, as described above, the polyol composition (X) contains the polyol (A) and the carboxyl group-containing compound (C) as essential components. In the case of a solvent-type adhesive, Organic solvents can be used.
On the other hand, the polyisocyanate composition (Y) comprises the polyisocyanate (B) and the carboxyl group-containing compound (C) as essential components. In the case of a solvent-type adhesive, an organic solvent is further used. be able to.

  As described above, the urethane-based adhesive of the present invention can be used as a solvent-type adhesive or a solventless-type adhesive, but has excellent long-term storage stability and good workability. It is preferable to use it as a solvent-type adhesive. Here, in order to adjust the solvent-type two-component urethane adhesive, the main agent and the curing agent described above were adjusted to a solid content of 50 to 80% by mass with the organic solvent, and two-component blended at the time of use. It is preferable from the point which is excellent in lamination processability to add an organic solvent further as needed in the state, and finally make it the range of 20-40 mass% of solid content.

  In the present invention, whether the carboxyl group-containing compound (C) is used as the polyol composition (X) or the polyisocyanate composition (Y), the carboxyl group-containing compound (C ) Is a ratio of 0.01 to 1.5 parts by mass with respect to 100 parts by mass of the polyol (A), whereby a laminated film obtained with good processability at the time of laminating. In addition to being good in appearance, acid and alkali erosion from the contents can be prevented over a long period of time.

  In the urethane adhesive of the present invention, the equivalent ratio of the isocyanate group in the polyisocyanate (B) to the hydroxyl group in the polyol (A) [isocyanate group / hydroxyl group] is in the range of 1.5 to 2.5. The strength and flexibility of the adhesive layer are in an appropriate range, which is preferable from the viewpoint that the initial adhesive strength, the adhesive strength over a long period of time, and the laminate appearance are good.

  Therefore, the use ratio of the polyol composition (X) and the polyisocyanate (B), or the use ratio of the polyol (A) and the polyisocyanate composition (Y) is the equivalent ratio [isocyanate group / hydroxyl group]. ] Is preferably in the range of 1.5 to 2.5.

  The urethane-based adhesive of the present invention is further blended with an aliphatic cyclic amide compound to effectively dissolve the contents of harmful low-molecular chemical substances typified by aromatic amines in the laminate package. Can be suppressed. Whether such an aliphatic cyclic amide compound is blended with either the polyol composition (X) or the polyisocyanate (B), or mixed with either the polyol (A) or the polyisocyanate composition (Y). Or it can mix | blend and use at the time of coating as a 3rd component.

  Examples of the aliphatic cyclic amide compound used here include δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, β-propiolactam, and the like. Among these, ε-caprolactam is preferable because it is excellent in the effect of reducing the elution amount of low molecular chemical substances. Moreover, it is preferable that the compounding quantity mixes an aliphatic cyclic amide compound in the range of 0.1-5 mass parts per 100 mass parts of polyol compositions (X).

  The urethane-based adhesive of the present invention may be used in combination with a pigment 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; these metal flake pigments, mica flake pigments; mica flakes coated with metal oxides Pigments, metallic pigments and pearl pigments such as micaceous iron oxide pigments; graphite, carbon black and the like.

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

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

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

  The mass ratio of the pigment used in the present invention is 1 to 400 parts by mass, particularly 10 to 300 parts by mass with respect to 100 parts by mass in total of the polyisocyanate composition (X) and the polyol (Y). It is more preferable because of its excellent blocking resistance.

  An adhesion promoter can also be used for the urethane adhesive of the present invention. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, and epoxy resins.

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

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

  Moreover, as an aluminum coupling agent, acetoalkoxy aluminum diisopropylate etc. can be mentioned, for example.

  As epoxy resins, there are generally commercially available Epbis type, novolak type, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycidyl ester type, polyglycol ether type, glycol ether type, epoxidized fatty acid ester type, many Various epoxy resins such as carboxylic acid ester type, aminoglycidyl type, resorcin type and the like can be mentioned.

  If necessary, the urethane 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 can be mixed with one of the components of the polyol composition and the polyisocyanate, or can be blended and used as the third component at the time of coating.

  The cured product of the present invention can be obtained by curing the urethane-based adhesive of the present invention described above in detail under normal polyol / isocyanate curing conditions.

  The laminated film of the present invention is obtained by applying the urethane adhesive of the present invention detailed above to the first plastic film, then laminating the second plastic film on the coated surface, and curing the adhesive layer. It is obtained.

  Specifically, when the urethane adhesive of the present invention is used as a solvent-type adhesive, the urethane adhesive of the present invention is applied to the first plastic film by, for example, a roll coater coating method, and then The method of bonding other base materials after drying on the conditions which are 60-90 degreeC is mentioned. The coating condition is preferably about 500 to 2500 mPa · s in a state where it is heated to about 25 ° C. to 120 ° C. in a normal roll coater.

  On the other hand, in the case of a solventless type, the urethane adhesive of the present invention is applied to the first plastic film by, for example, a roll coater coating method, and then bonded to another substrate without passing through a drying step. A method is mentioned. The coating condition is preferably about 500 to 2500 mPa · s in a state where it is heated to about 25 ° C. to 120 ° C. in a normal roll coater.

  Further, the coating amount may be about 1.0 to 4.0 g / m 2 for the solvent type and about 0.5 to 3.0 g / m 2 for the solventless type. In the case of the solventless type, when the urethane adhesive of the present invention is used, the adhesive is cured in 6 to 24 hours at room temperature or under heating after lamination, and expresses practical physical properties.

  Examples of the first plastic film used here include base films such as PET (polyethylene terephthalate) film, nylon film, OPP (biaxially stretched polypropylene) film, aluminum vapor deposition film, 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.

  In the present invention, as described above, in order to have excellent adhesion performance to the metal surface and durability / stability, the first plastic film is particularly preferably an aluminum foil or an aluminum vapor deposition film.

  The laminated film thus obtained can be industrially used as a packaging material mainly filled with detergents and drugs. Specific examples of the detergent and detergent include laundry liquid detergent, kitchen liquid detergent, bath liquid detergent, bath liquid soap, liquid shampoo, and liquid conditioner.

  The packaging material produced using the urethane-based adhesive of the present invention causes delamination of the laminate structure such as delamination not only when the contents such as detergents and drugs are filled, but also after the lapse of time after filling. It has excellent adhesion and content resistance.

  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. The number average molecular weight (Mn) shown in each example, comparative example, and synthesis example is a value 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 x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)

Example 1 (Production of polyol composition (x1))
In a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction tube, rectification tube, moisture separator, etc., 198 parts by mass of terephthalic acid, 162 parts by mass of isophthalic acid, 171 parts by mass of adipic acid, 127 parts by mass of ethylene glycol, 159 parts by mass of diethylene glycol and 0.14 parts by mass of dibutyltin dilaurate were charged, and the inner temperature was kept at 250 ° C. by gradually heating so that the rectifying tube upper temperature did not exceed 100 ° C.
When the acid value reached 2.5 mgKOH / g, xylene was added, and xylene was refluxed at 240 ° C. using a water separator, and the reaction was further continued to an acid value of 1.5 mgKOH / g or less. The pressure was reduced to 1333 Pa or less and the xylene was removed by holding for 1.5 hours to complete the esterification reaction to obtain a polyester polyol having a number average molecular weight (Mn) of about 4,000.
Styrene / maleic anhydride copolymer (“SMA 1000” manufactured by Clay Valley, styrene / maleic anhydride = 1/1 copolymer, molecular weight 5,500 SP value is 31.4 (J / cm ³ ) ^1/2 ) is added at a ratio of 0.5 parts by mass in terms of solid content to 100 parts by mass of the polyester polyol, and further dissolved and diluted with ethyl acetate to adjust to a solid content concentration of 75% by mass to obtain a polyol composition (Hereinafter, abbreviated as “polyol composition (x1)”).

Example 2 (Production of polypole composition (x2))
According to the production method shown in Example 1, a similar polyester polyol was synthesized from the same raw material, and 2,2-bis (hydroxymethyl) propionic acid (DMPA) [SP value 28.7 (J / cm ³ ) ^1/2 , Acid value 414-418 mgKOH / g] is added at a ratio of 0.5 parts by mass in terms of solid content to 100 parts by mass of the polyester polyol, and further dissolved and diluted with ethyl acetate to obtain a solid content concentration of 75% by mass solution. Thus, a polyol composition (hereinafter abbreviated as “polyol composition (x2)”) was obtained.

Example 3 (Production of polyol composition (x3))
According to the production method shown in Example 1, a similar polyester polyol was synthesized from the same raw material, and 2,2-bis (hydroxymethyl) butyric acid (DMBA) [SP value 27.4 (J / cm ³ ) ^1/2 , Acid value 374-378 mg KOH / g] is added at a ratio of 0.5 parts by mass with respect to 100 parts by mass of the polyester polyol in terms of solid content, and further dissolved and diluted with ethyl acetate to adjust to a solid content concentration of 75% by mass solution. Thus, a polyol composition (hereinafter abbreviated as “polyol composition (x3)”) was obtained.

Example 4 (Production of polyol composition (x4))
A flask equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube is 170 parts by mass of tolylene diisocyanate and 410 parts by mass of polypropylene glycol ("DIOL-700", bifunctional polypropylene glycol manufactured by Mitsui Chemicals) with an average molecular weight of 700 and an average molecular weight. 70 parts by weight of 3,000 polypropylene glycol ("DIOL-3000" manufactured by Mitsui Chemicals, Inc., bifunctional polypropylene glycol with an average molecular weight of 3,000) is charged, and the mixture is heated to 95 ° C and stirred for 1 hour. The temperature was lowered to 70 ° C., and 25 parts by mass of dipropylene glycol, 2,2-bis (hydroxymethyl) propionic acid (DMPA) [SP value 28.7 (J / cm ³ ) ^1/2 , acid value 414 to 418 mgKOH / g] 7 parts by mass was added and dissolved until transparent.

  Further, the temperature was lowered to 65 ° C., 27 parts by mass of diethanolamine (DEA) and 0.04 part by mass of dibutyltin dilaurate were added, and the mixture was stirred for 1 hour, a polyester polyol having a number average molecular weight (Mn) of about 4,600, A polyol composition (hereinafter referred to as “polyol composition (x4)”) which is a mixture with 2-bis (hydroxymethyl) propionic acid (1 part by mass with respect to 100 parts by mass of the polyether urethane polyol in terms of solid content) Is abbreviated as).

Synthesis Example 1 (Production of polyol (x5) (polyester urethane polyol))
In a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectifying tube, a water separator, etc., 123.5 parts by mass of terephthalic acid, 123.5 parts by mass of isophthalic acid, 139.5 parts by mass of adipic acid, 47 parts by weight of dimer acid, 62 parts by weight of ethylene glycol, 131 parts by weight of neopentyl glycol, 59 parts by weight of 1,6-hexanediol, and 0.12 parts by weight of dibutyltin dilaurate are added, and the upper temperature of the rectifying tube is 100 ° C. The internal temperature was kept at 240 ° C. by gradually heating so as not to exceed.
When the acid value reached 2.5 mgKOH / g, xylene was added, and xylene was refluxed at 230 ° C. using a water separator, and the reaction was further continued to an acid value of 1.5 mgKOH / g or less. The pressure was reduced to 1333 Pa or less, and the xylene was removed by holding for 1.5 hours to complete the esterification reaction to obtain an intermediate polyester polyol having an acid value of 0.5 mgKOH / g. This was dissolved and diluted with ethyl acetate to obtain a 60% by mass solid content solution. Furthermore, 3 parts by mass of isophorone diisocyanate and 0.05 parts by mass of dibutyltin dilaurate are added to 100 parts by mass of the obtained intermediate polyester polyol, and the mixture is heated to 80 ° C. to substantially eliminate free NCO groups. The urethanization reaction was carried out to obtain a polyester urethane polyol having a hydroxyl value of 5 (hereinafter abbreviated as “polyol (x5)”). The number average molecular weight (Mn) of this polyester urethane polyol was about 11,000.

Synthesis Example 2 (Production of polyol (x6) (polyester urethane polyol))
In a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas inlet tube, a rectifying tube, a water separator, etc., 827 parts by mass of isophthalic acid, 725 parts by mass of sebacic acid, 154 parts by mass of ethylene glycol, 720 parts by mass of neopentyl glycol In addition, 0.15 parts by mass of dioctyltin dilaurate was charged, and the inner temperature was maintained at 260 ° C. by gradually heating so that the rectifying tube upper temperature did not exceed 100 ° C. When the acid value reached 5 mgKOH / g, xylene was added, and xylene was refluxed at 250 ° C. using a water separator, and the reaction was further continued to an acid value of 2 mgKOH / g or less. The pressure was reduced to 1333 Pa or less, and the xylene was removed by holding for 1.5 hours to complete the esterification reaction to obtain an intermediate polyester polyol having an acid value of 1 mgKOH / g. This was dissolved and diluted with ethyl acetate to obtain a 60% by mass solid content solution. Furthermore, 4 parts by mass of isophorone diisocyanate and 0.025 parts by mass of dioctyltin dilaurate are added to 100 parts of the obtained intermediate polyester polyol, and heated to 80 ° C. until substantially no free NCO groups are present. A urethanization reaction was performed to obtain a polyester urethane polyol having a hydroxyl value of 7 (hereinafter abbreviated as “polyol (x6)”). The number average molecular weight (Mn) of this polyester urethane polyol was about 9,000.

Example 5 (Preparation of polyisocyanate composition (y1) [polyisocyanate + tetrahydrophthalic anhydride skeleton-containing compound (c3)])
In a flask equipped with a stirrer, thermometer, and nitrogen gas introduction tube, 15 parts by mass of isophorone diisocyanate nurate (functional group number 3 to 4), xylene diisocyanate trimethylolpropane adduct ("Takenate D-110N" manufactured by Mitsui Chemicals, Inc.) 49), 3a, 4,5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3-iso-benzofuranone [SP value 29. 1 (J / cm ³ ) ^1/2 , acid value 849 mgKOH / g] and 3 parts by mass of methyl ethyl ketone were charged. The mixture was heated to 60 ° C. and stirred for 1 hour to obtain a polyisocyanate composition (polyisocyanate composition). Thing (y1)) was obtained.

Example 6 (Preparation of polyisocyanate composition (y2) [polyisocyanate + tetrahydrophthalic anhydride skeleton-containing compound (c3)])
In a flask equipped with a stirrer, a thermometer, and a nitrogen gas introduction tube, 30 parts by mass of isophorone diisocyanate, 32 parts by mass of trimethylolpropane adduct of xylene diisocyanate (“Takenate D-100N” manufactured by Mitsui Chemicals), 3a, 4 , 5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3-iso-benzofurandione [SP value 29.1 (J / cm ³ ) ^1/2 , Acid value 849 mgKOH / g] and 37 parts by mass of methyl ethyl ketone were charged, and this mixture was heated to 60 ° C. and stirred for 1 hour to obtain a polyisocyanate composition (polyisocyanate composition (y2)).

Synthesis Example 3 (Production of polyol (x7) (polyester polyol))
In a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction tube, rectification tube, moisture separator, etc., 198 parts by mass of terephthalic acid, 162 parts by mass of isophthalic acid, 171 parts by mass of adipic acid, 127 parts by mass of ethylene glycol, 159 parts by mass of diethylene glycol and 0.14 parts by mass of dibutyltin dilaurate were charged, and the inner temperature was kept at 250 ° C. by gradually heating so that the rectifying tube upper temperature did not exceed 100 ° C. When the acid value reached 2.5 mgKOH / g, xylene was added, and xylene was refluxed at 240 ° C. using a water separator, and the reaction was further continued to an acid value of 1.5 mgKOH / g or less. The pressure was reduced to 1333 Pa or less, and the xylene was removed by holding for 1.5 hours to complete the esterification reaction, and a polyester polyol having a number average molecular weight (Mn) of about 4,000 (hereinafter, abbreviated as “polyol (x7)”). ). This was dissolved and diluted with ethyl acetate to obtain a 75% by mass solid content solution.

Comparative Example 1 (Production of polyol composition (x8))
In a polyester reaction vessel equipped with a stirrer, thermometer, nitrogen gas introduction tube, rectification tube, moisture separator, etc., 198 parts by mass of terephthalic acid, 162 parts by mass of isophthalic acid, 171 parts by mass of adipic acid, 127 parts by mass of ethylene glycol, 159 parts by mass of diethylene glycol and 0.14 parts by mass of dibutyltin dilaurate were charged, and the inner temperature was kept at 250 ° C. by gradually heating so that the rectifying tube upper temperature did not exceed 100 ° C. When the acid value reached 2.5 mgKOH / g, xylene was added, and xylene was refluxed at 240 ° C. using a water separator, and the reaction was further continued to an acid value of 1.5 mgKOH / g or less. The pressure was reduced to 1333 Pa or less, and the xylene was removed by holding for 1.5 hours to complete the esterification reaction, and a polyester polyol having a number average molecular weight of about 6,000 was obtained.

Styrene / maleic anhydride copolymer (“SMA 1000” manufactured by Clay Valley, styrene / maleic anhydride = 1/1 copolymer, molecular weight 5,500 SP value is 31.4 (J / cm ³ ) ^1/2 ) is added at a ratio of 5.3 parts by mass in terms of solid content with respect to 100 parts by mass of the polyester polyol, and further dissolved and diluted with ethyl acetate to prepare a solution having a solid content concentration of 75% by mass. (Hereinafter, abbreviated as “polyol composition (x8)”).

Examples 7-14 and Comparative Examples 2-3
According to the composition of Table 1 or Table 2, the main agent and the curing agent were blended, and the adhesives A to J were prepared by adjusting with ethyl acetate so that the solid content concentration would be Table 1 or Table 2. Then, the following test for preventing aluminum deposition loss and the laminate appearance evaluation test were performed.

  In Tables 1 and 2, “polyisocyanate (y3)” is an adduct type polyisocyanate in which 3 moles of tolylene diisocyanate is added to 1 mole of trimethylolpropane (ethyl acetate solution, non-volatile content: 75% by mass), “Isocyanate (y4)” is methylene diisocyanate-modified polypropylene glycol (ethyl acetate solution, non-volatile content: 75 mass%, viscosity at 25 ° C .: 1500-2500 mPa · s, NCO content: 3.4 mass%).

(Aluminum deposition loss prevention test)
Using a test laminator (made by Musashino), apply to an OPP (biaxially stretched polypropylene) film printed with transparent ink and indigo ink so that the coating amount is 3.0 g / m ² and dry to remove the solvent. After that, it was laminated with an aluminum vapor-deposited surface of VMPET (aluminum vapor-deposited PET) and further laminated with an LLDPE film so as to have a coating amount of 3.0 g / m ² to prepare a laminate.
Next, the composite film was aged at 40 ° C. for 3 days to cure the adhesive coating, and a three-layer composite film of OPP film / adhesive / VMPET / adhesive / LLDPE film was obtained. The following films and inks were used.

OPP film: Pyrene film-OT P2161 20 μm manufactured by Toyobo Co., Ltd.
VMPET film: Toray Film Processing Co., Ltd. VM-PET1310 12 μm
LLDPE film: manufactured by Tosero Co., Ltd. TUX-HC 60 μm
Ink used:
(Indigo ink) "Univia NT R507 Genshoukui K1" manufactured by DIC
(White ink) "XS-824 R794 white K1" manufactured by DIC

  Using this composite film after aging, a pouch having a size of 120 mm × 120 mm was prepared, and as a content, 70 g of pseudo food containing vinegar, salad oil, and meat sauce in a mass ratio of 1: 1: 1 was filled. The prepared pouch was boil sterilized at 98 ° C. for 60 minutes and then stored in an oven at 50 ° C. for 6 months, and the appearance of the plain and indigo ink portions was visually evaluated.

○: No change in appearance ×: Disappearance of aluminum deposition

(Laminate appearance confirmation test)
DL-600DX dry laminator (Orient Sogyo Co., Ltd.) using the same base film and the same coating amount as those used in the “aluminum deposition loss prevention test” using the adhesive prepared in each Example and Comparative Example Manufactured) and laminated at 250 m / min to obtain a three-layer composite film of OPP film / adhesive / VMPET / adhesive / LLDPE film. The appearance of the composite film immediately after lamination was visually confirmed.
○: Indicates that there is no entrapment of bubbles.
X: There is a bubble hug.

Claims (8)

Polyol (A) selected from the group consisting of polyester polyol (a1), polyester urethane polyol (a2), and polyether urethane polyol (a3), polyisocyanate (B), and aromatic vinyl and anhydrous maleic as additive components A copolymer with acid (c1), 3a, 4,5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -1,3-iso-benzofurandione, or 2,2-bis (hydroxymethyl) propionic acid is an essential component, and the additive component is contained at a ratio of 0.01 to 1.5 parts by mass per 100 parts by mass of the polyol (A). Urethane adhesive. Polyol (A) and copolymer (c1) of aromatic vinyl and maleic anhydride as an additive component , 3a, 4,5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5-dioxo -3-furanyl) -1,3-iso-benzofurandione or 2,2-bis (hydroxymethyl) propionic acid with 0.01 to 1.5 parts by mass of additive component per 100 parts by mass of polyol (A). The polyol composition for urethane adhesives which contains in the ratio which contains and also contains the organic solvent (D) . Copolymer (c1) of polyisocyanate (B) and aromatic vinyl and maleic anhydride as an additive component, 3a, 4,5,7a-tetrahydro-7-methyl-5- (tetrahydro-2,5- A polyisocyanate composition for urethane-based adhesives, which contains dioxo-3-furanyl) -1,3-iso-benzofurandione or 2,2-bis (hydroxymethyl) propionic acid and an organic solvent as essential components. The said polyisocyanate composition for urethane type adhesives is used with a polyol (A), and 0.01-1.5 mass parts with respect to 100 mass parts of the said polyol (A) which uses the said additive component together. The polyisocyanate composition for urethane-based adhesives according to claim 3, which is contained at a ratio of: The use ratio of the polyol (A) and the polyisocyanate (B) is such that the equivalent ratio of the isocyanate group in the polyisocyanate (B) and the hydroxyl group in the polyol (A) [isocyanate group / hydroxyl group]. The urethane-based adhesive according to claim 1, which has a ratio of 1.5 to 2.5 . Hardened | cured material formed by hardening the urethane type adhesive agent of Claim 1 or 5 . A laminated film obtained by applying the urethane-based adhesive according to claim 1 or 5 to a first base film, then laminating a second base film on the coated surface, and curing the adhesive layer. The laminated film according to claim 7, wherein the first base film is a metal foil or a metal vapor deposited film, and the second base film is an unstretched polypropylene film or a low density polyethylene film.