WO2018186383A1 - Hardener for two-pack type adhesive, two-pack type adhesive, laminated film, and package - Google Patents

Abstract

A hardener for two-pack type adhesives which comprises a reaction product (B-1) obtained by reacting a polyol with one or more isocyanate compounds comprising 4,4'-diphenylmethane diisocyanate and at least one isocyanate compound (B-2) selected from the group consisting of isocyanates each in the forms of isocyanurate, biuret, allophanate, and adduct; a two-pack type adhesive which comprises a polyol component A comprising a polyol compound and an isocyanate component B comprising one or more isocyanate compounds, wherein the isocyanate component B includes the isocyanate compound (B-2); and a laminated film and a package each obtained using the two-pack type adhesive.

Description

Curing agent for two-component adhesive, two-component adhesive, laminated film, and package

The present invention relates to a curing agent for a two-component adhesive, a two-component adhesive, a laminated film using the same, and a package.

Laminate films (sometimes referred to as laminate films) used for various packaging materials, labels, etc. are designed, functional, storable, and convenient by laminating various types of plastic films, metal foil, paper, etc. A package that is provided with transportability and is formed by forming the laminated film into a bag shape is used as a package for foods, pharmaceuticals, detergents, and the like.

For conventional laminate films, an adhesive (sometimes called a solvent-type laminate adhesive) dissolved in a volatile organic solvent is applied to the film, and the organic solvent is volatilized while passing through an oven. However, in recent years, from the viewpoint of reducing the environmental burden and improving the working environment, reactive two-component laminate bonding that does not contain volatile organic solvents has been the mainstream. The demand for adhesives (sometimes called two-component adhesives or solventless laminate adhesives) is increasing. (For example, see Patent Document 1)

Although the two-component adhesive described in Patent Document 1 is effective in reducing the adhesive strength and aging time in a solventless adhesive, it combines an aromatic isocyanate that is a curing agent and a polyester diol that is a main agent, The resin for solventless adhesives has a relatively short pot life. If the pot life is short, variations in the coating amount are likely to occur. As a result, the appearance of the laminate may be significantly impaired, and when the laminating machine stops temporarily, such as when replacing the raw material, the adhesive is replaced or the roll is cleaned. Therefore, workability may be significantly impaired. In particular, when 4,4′-diphenylmethane diisocyanate (MDI), which is one of aromatic isocyanates, is used as a curing agent, the curing agent itself may be crystallized or precipitated because the compound has high crystallinity. .

Furthermore, since the two-component adhesive uses a reactive monomer having a slightly lower molecular weight than the solvent-type laminating adhesive as a raw material, there is a possibility that it will elute into the contents through the film after lamination. In recent years, in particular, regulations for components that elute (transfer) chemical substances from plastic containers have been finely defined in Europe and the like, and products with less chemical substance elution components from containers have been demanded. In general, SML (Specific migration limit) is prescribed for elution of chemical substances used in adhesives, and the eluate can be easily controlled, but it is an unintentionally added substance (NIAS) produced by synthesis or the like. Elution is a problem that cannot be easily cleared.

In contrast, an isocyanate end which is a reaction product with a modified diphenylmethane diisocyanate (MDI) selected from the group consisting of carbodiimide modified diphenylmethane diisocyanate, allophanate modified diphenylmethane diisocyanate, biuret modified diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate and combinations thereof It is known that an adhesive containing a polyurethane prepolymer and a polyol is an adhesive that produces a low concentration of extractable primary aromatic amine (PAA) (see, for example, Patent Document 2). However, the adhesive is used by reacting the modified diphenylmethane diisocyanate with a polyol, so that the viscosity tends to be high and the pot life still tends to be short.
Therefore, at present, a two-pack type adhesive with little unintentional substance elution and a long pot life has not yet been obtained that is practically satisfactory.

JP 2014-159548 A Special table 2014-516321 gazette

The problem to be solved by the present invention is that the curing agent itself is excellent in long-term storage, and when used as a two-component adhesive, there are very few unintentional substances that elute into the contents through the film after lamination, Another object is to provide a two-component adhesive having a long pot life.

The present inventors have prepared a reaction product (B-1) of a polyol and an isocyanate compound containing at least 4,4′-diphenylmethane diisocyanate and curing for a two-component adhesive containing the isocyanate compound (B-2). It has been found that a two-component adhesive using an agent and the curing agent can solve the above problems.

That is, the present invention is a curing agent for a two-component adhesive, a reaction product (B-1) of a polyol and an isocyanate compound containing at least 4,4′-diphenylmethane diisocyanate, an isocyanurate of diisocyanate, Provided is a curing agent for a two-component adhesive containing at least one isocyanate compound (B-2) selected from the group consisting of a burette body, an allophanate body and an adduct body.

The present invention also includes a polyol component A containing a polyol compound and an isocyanate component B containing an isocyanate compound, wherein the isocyanate component B comprises a polyol and an isocyanate compound containing at least 4,4′-diphenylmethane diisocyanate. A two-component adhesive comprising a reaction product (B-1) and at least one isocyanate compound (B-2) selected from the group consisting of an isocyanurate body, a burette body, an allophanate body and an adduct body of diisocyanate; provide.

The present invention is also a laminated film obtained by laminating an adhesive layer between a first plastic film and a second plastic film, wherein the adhesive layer is a layer of the two-component adhesive described above. Provide a laminated film.

Moreover, this invention is a package formed by shape | molding the laminated film formed by laminating | stacking an adhesive bond layer between a 1st plastic film and a 2nd plastic film in a bag shape, Comprising: The said adhesive bond layer is the said description. A package that is a layer of the two-component adhesive is provided.

According to the present invention, the curing agent itself is excellent in long-term storage, and when used as a two-component adhesive, there are very few unintentional substances that elute into the contents through the film after lamination. During the filling of the contents such as, and after the elapse of time after filling, the laminate structure such as delamination does not peel off and has excellent adhesiveness and contents resistance. Moreover, since it has a low viscosity and a long pot life, it is excellent in workability after blending an adhesive.

(Definition of words Solvent)
The two-component adhesive of the present invention is a reactive two-component laminate adhesive as described above, and is also referred to as a solventless laminate adhesive because it does not use a conventional volatile organic solvent.
In the present invention, an adhesive that cures by a chemical reaction between an isocyanate group and a hydroxyl group is used. The “solvent” of the solventless adhesive referred to in the present invention refers to a highly soluble and volatile organic solvent capable of dissolving the polyisocyanate and polyol used in the present invention. "" Refers to the absence of these highly soluble organic solvents. Specific examples of highly soluble organic solvents include toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, and xylol. , N-hexane, cyclohexane and the like. Of these, toluene, xylene, methylene chloride, tetrahydrofuran, methyl acetate, and ethyl acetate are known as organic solvents having particularly high solubility.

On the other hand, when there is a demand for low viscosity or the like, the adhesive of the present invention may be appropriately diluted with the organic solvent having high solubility according to the desired viscosity. In that case, either one of the polyol component A or the isocyanate component B may be diluted, or both may be diluted. Examples of the organic solvent used in such a case include methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, and cyclohexane. . Among these, ethyl acetate and methyl ethyl ketone (MEK) are preferable from the viewpoint of solubility, and ethyl acetate is particularly preferable. The amount of the organic solvent used depends on the required viscosity, but is generally in the range of 0.1 to 10% by mass.
Moreover, in order to achieve the low viscosity of the adhesive of the present invention, a solvent having a boiling point of 200 ° C. or higher having a carbonyl group having no hydroxyl group such as triacetin and propylene carbonate may be used. The amount of these high-boiling organic solvents used depends on the required viscosity and physical properties of the coating film, but is generally in the range of 0.1 to 10% by mass.

(Definition of words main agent, hardener)
In general, there are various expressions representing “two liquids” in a two-component adhesive. In the present invention, an isocyanate component B containing an isocyanate compound is referred to as a “curing agent” and a polyol containing a polyol compound. Component A is referred to as “main agent”.

(Polyol component A containing a main component polyol compound)
In the present invention, a known polyol can be used as the polyol compound contained in the polyol component A which is the main agent without any particular limitation. For example, selected from polyester polyol, polyether polyol, polyurethane polyol, polyether ester polyol, polyester (polyurethane) polyol, polyether (polyurethane) polyol, polyester amide polyol, acrylic polyol, polycarbonate polyol, polyhydroxyl alkane, castor oil or mixtures thereof And polymer polyols.

Specifically, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexane Diol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4-cyclohexanediol, 1 , 4-cyclohexanedimethanol, triethylene glycol and other glycols; glycerin, trimethylolpropane, pentaerythritol, polypropylene glycol triols, etc. Functional or tetrafunctional aliphatic alcohols; dimer diol; bisphenol A, bisphenol F, hydrogenated bisphenol A, bisphenol such as hydrogenated bisphenol F;

Polyether polyol obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene in the presence of a polymerization initiator such as glycol, trifunctional or tetrafunctional aliphatic alcohol. A polyether urethane polyol obtained by further increasing the molecular weight of the polyether polyol with the aromatic or aliphatic polyisocyanate;

Polyester obtained by ring-opening polymerization reaction of cyclic ester compounds such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone, and the above-mentioned glycol, glycerin, trimethylolpropane, pentaerythritol, etc. Polyester polyol (1) which is a reaction product of polyhydric alcohol with
Polyester polyol (2) obtained by reacting a bifunctional polyol such as the glycol, dimer diol or the bisphenol with a polycarboxylic acid:
A polyester polyol (3) obtained by reacting the trifunctional or tetrafunctional aliphatic alcohol with a polyvalent carboxylic acid;
A polyester polyol (4) obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or the bisphenol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid;
Polyester polyol (5), which is a polymer of hydroxyl acid such as dimethylolpropionic acid and castor oil fatty acid;
A polyester polyether polyol obtained by reacting the polyester polyols (1) to (5), the polyether polyol and an aromatic or aliphatic polyisocyanate;
A polyester polyurethane polyol obtained by increasing the molecular weight of the polyester polyols (1) to (5) with an aromatic or aliphatic polyisocyanate;
A mixture of polyester polyols (1) to (5) and a polyether polyol;
Castor oil, dehydrated castor oil, castor oil which is a hydrogenated product of castor oil, castor oil-based polyol such as 5-50 mol adduct of castor oil alkylene oxide, castor oil-based polyol and glycol, dimer diol, or bifunctional such as bisphenol And a copolymer with a type polyol.

Examples of the polyvalent carboxylic acid include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid. Aliphatic dicarboxylic acids such as acids; terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis Aromatic dicarboxylic acids such as (phenoxy) ethane-p, p'-dicarboxylic acid; and anhydrides or ester-forming derivatives of these aliphatic or dicarboxylic acids; p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid Acids and ester-forming derivatives of these dihydroxycarboxylic acids, dyes It includes polybasic acids such as over acid

The polyurethane polyol is a reaction product of a polyether polyol having a number average molecular weight of 200 to 20,000 and an organic polyisocyanate, and NCO / OH is preferably less than 1, more preferably 0.9 or less.

Polyether (polyurethane) polyols and polyester (polyurethane) polyols are reaction products of polyester polyols, polyether ester polyols, and the like with organic polyisocyanates, preferably having an NCO / OH of less than 1, more preferably 0.9 or less. Can be mentioned.

The polyesteramide polyol can be obtained, for example, by subjecting an aliphatic diamine having an amino group such as ethylenediamine, propylenediamine, hexamethylenediamine or the like as a raw material to an esterification reaction.
Examples of acrylic polyols include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyhydroxybutyl, etc., or their corresponding methacrylic acid derivatives containing one or more hydroxyl groups in one molecule, such as acrylic acid, methacrylic acid, etc. It is obtained by copolymerizing an acid or its ester.

Examples of the polycarbonate polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and 1,9-nonane. One selected from diol, 1,8-nonanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A, hydrogenated bisphenol A or The thing obtained by reaction of 2 or more types of glycol with dimethyl carbonate, diphenyl carbonate, ethylene carbonate, phosgene, etc. is mentioned.

Examples of the polyhydroxyalkane include butadiene or liquid rubber obtained by copolymerization with butadiene and acrylamide.
Among these, a polyether (polyurethane) polyol is particularly preferable.

As the polyol compound used in the present invention, a reaction product of polyisocyanate and bis (hydroxyalkyl) amine having a urea bond group at the terminal can also be preferably used.

In the present invention, among others, a polyester polyol (4) obtained by reacting a bifunctional polyol, the trifunctional or tetrafunctional aliphatic alcohol, and a polyvalent carboxylic acid, a castor oil-based polyol and the glycol, Dimer diol or a copolymer with a bifunctional polyol such as bisphenol is preferred. As the trifunctional or tetrafunctional aliphatic alcohol, a triol form of glycerin or polypropylene glycol is preferable.

The number average molecular weight of the polyol component A is not particularly limited, but is usually adjusted in the range of 500 to 3000 from the viewpoint of an appropriate resin viscosity at the time of coating.

In the present invention, the number average molecular weight (Mn) 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 × 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)

(Isocyanate component B containing isocyanate compound)
In the present invention, the isocyanate component B which is a curing agent includes a reaction product (B-1) of a polyol and an isocyanate compound containing at least 4,4′-diphenylmethane diisocyanate, an isocyanurate body, a burette body, and an allophanate body of diisocyanate. And at least one isocyanate compound (B-2) selected from the group consisting of adducts.

(Reaction product of polyol and isocyanate compound containing at least 4,4′-diphenylmethane diisocyanate (B-1))
4,4′-diphenylmethane diisocyanate is essential as a reaction raw material for the reaction product (B-1).
Other isocyanate compounds that may be included as reaction raw materials include, for example, aromatic diisocyanates other than 4,4′-diphenylmethane diisocyanate, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, and burettes of the diisocyanates, Examples thereof include a nurate body, an adduct body, an allophanate body, a carbodiimide-modified isocyanate, a urethane prepolymer obtained by reacting an isocyanate and a polyol, and these can be used alone or in combination.

For example, aromatic diisocyanates include, for example, 2,2′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 2,4 -Tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'- Examples thereof include, but are not limited to, diphenyl ether diisocyanate and 4,4 ′, 4 ″ -triphenylmethane triisocyanate.

For example, an araliphatic diisocyanate means an aliphatic isocyanate having one or more aromatic rings in the molecule, such as m- or p-xylylene diisocyanate (also known as XDI), α, α, α ′, α Examples include, but are not limited to, '-tetramethylxylylene diisocyanate (also known as TMXDI).

For example, aliphatic diisocyanates include, for example, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (also known as HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate. , Dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like, but are not limited thereto.

For example, as the alicyclic diisocyanate, for example, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, isophorone diisocyanate (also known as IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1, Examples include 4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanatomethyl) cyclohexane, and the like. However, it is not limited to these.

In the present invention, 4,4′-diphenylmethane diisocyanate which is a raw material of the reaction product (B-1) is in the range of 50 to 99% by weight based on the total weight of all isocyanate compounds in the reaction product (B-1). It is preferable to use in the range of 90 to 99% by weight.

The polyol that is a raw material of the reaction product (B-1) is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and other alkylene glycols; bisphenol Bisphenols such as A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F; dimer diol; bishydroxyethoxybenzene; diethylene glycol, triethylene glycol, other polyethylene glycols A polyalkylene glycol such as polypropylene glycol and polybutylene glycol; a urethane bond-containing polyether polyol obtained by further polymerizing the polyalkylene glycol with the aromatic or aliphatic polyisocyanate; the alkylene glycol or polyalkylene glycol and oxalic acid , Malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, etc. in the range of 2 to 13 carbon atoms Polyester polyol obtained by reacting with an aliphatic dicarboxylic acid which is: by ring-opening polymerization reaction of a cyclic ester compound such as propiolactone, butyrolactone, ε-caprolactone, σ-valerolactone, β-methyl-σ-valerolactone Examples thereof include polyester polyols, which are a reaction product of the obtained polyester and the above-mentioned polyhydric alcohols such as glycol, glycerin, trimethylolpropane, and pentaerythritol.

Among these, polyalkylene glycol or polyester polyol is preferable from the viewpoint that the adhesive strength can be increased while reducing the viscosity of the adhesive itself, and the polyalkylene glycol is preferably a number average molecular weight ( Mn) is preferably in the range of 200 to 6,000. On the other hand, the polyester polyol is preferably obtained by reacting the alkylene glycol or polyalkylene glycol having a molecular weight of 300 or less with an aliphatic polyvalent carboxylic acid having 2 to 30 carbon atoms. In the latter polyester polyol, a tri- or higher functional alcohol such as glycerin, trimethylolpropane, or pentaerythritol may be used as a raw material alcohol component in a proportion of 10% by mass or less in the polyol component.

Among the reaction products (B-1), for a flexible packaging substrate, poly (4,4′-diphenylmethane diisocyanate and a polyalkylene glycol obtained by reacting a polyalkylene glycol having a number average molecular weight of 200 to 6,000 are reacted. A polyisocyanate obtained by reacting an isocyanate, 4,4′-diphenylmethane diisocyanate and a polyester polyol having a number average molecular weight in the range of 200 to 3,000 is preferable from the viewpoint of imparting appropriate flexibility to the cured product. For this, an isocyanate content by titration method (using di-n-butylamine) of 5 to 20% by mass is preferable from the viewpoint of an appropriate resin viscosity and excellent coating properties.

On the other hand, a polyisocyanate obtained by reacting 4,4′-diphenylmethane diisocyanate with a polyester polyol having a number average molecular weight in the range of 200 to 3,000 for a hard substrate of a two-component adhesive; 4,4′- Polyisocyanate obtained by reacting diphenylmethane diisocyanate with a mixture of a polyester polyol having a number average molecular weight of 200 to 3,000 and a polyalkylene glycol having a number average molecular weight of 200 to 6,000 has excellent adhesive strength. Specifically, an isocyanate content by titration method (using di-n-butylamine) of 5 to 20% by mass is preferable from the viewpoint of an appropriate resin viscosity and excellent coating properties.

Here, the reaction ratio of 4,4′-diphenylmethane diisocyanate and a mixture of polyalkylene glycol or polyester polyol is equivalent ratio of isocyanate in 4,4′-diphenylmethane diisocyanate to hydroxyl group in polyol [isocyanate / hydroxyl group. ] Is preferably in the range of 1.5 to 5.0 because the viscosity of the adhesive is in an appropriate range and the coating property is good.

The number average molecular weight of the reaction product (B-1) is preferably in the range of 500 to 3000, and more preferably 500 to 1500 from the viewpoint of an appropriate resin viscosity at the time of coating.

(Isocyanate compound (B-2))
In the present invention, the isocyanate component B which is a curing agent is at least one isocyanate compound selected from the group consisting of the above-mentioned reaction product (B-1), isocyanurate of diisocyanate, burette, allophanate and adduct. (B-2) is contained. These isocyanate compounds (B-2) may be used alone or in combination of two or more.

The isocyanurate body, the burette body, and the allophanate body are dimers or trimers of diisocyanate compounds. These diisocyanate compounds are butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate. Aliphatic diisocyanate compounds such as 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate;

Cycloaliphatic diisocyanate compounds such as cyclohexane diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate;

1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate And aromatic diisocyanate compounds such as 1,4-phenylene diisocyanate and tolylene diisocyanate. These may be used alone or in combination of two or more.

Further, an adduct obtained by reacting a diisocyanate compound with a trifunctional or higher functional polyol compound is obtained by reacting the aforementioned diisocyanate compound with a trifunctional or higher functional polyol compound. Examples of the tri- or higher functional polyol compound include tri- or higher functional compounds among the compounds exemplified as the polyol that is a raw material of the reaction product (B-1), and each compound may be used alone. Two or more types may be used in combination.

Among these, an isocyanurate body of an aliphatic diisocyanate compound is preferable, and an isocyanurate body of hexamethylene diisocyanate (HDI) is still more preferable.

In the isocyanate component B, the mixing ratio of the reaction product (B-1) and the isocyanate compound (B-2) is such that the reaction product (B-1) / the isocyanate compound (B-2) is 30. It is preferably in the range of / 70 to 99/1, more preferably in the range of 50/50 to 99/1.

The reaction product (B-1) is a reaction product obtained by reacting the polyol, 4,4′-diphenylmethane diisocyanate and the isocyanate compound (B-2) (hereinafter, the reaction product is referred to as a reaction product “B”). May be referred to as “-3”). By containing the reaction product (B-3), the curing agent itself is particularly excellent for long-term storage.

As a more preferable combination of the reaction raw materials of the reaction product (B-3),
(1) A polyether polyol or a polyester polyol or both as a polyol, a combination of 4,4′-diphenylmethane diisocyanate and an isocyanurate of 1,6-hexamethylene diisocyanate as the isocyanate compound (B-2). Reaction product (B-1-1)
(1) A combination of either a polyether polyol or a polyester polyol or both as the polyol, 4,4′-diphenylmethane diisocyanate, and a biuret of 1,6-hexamethylene diisocyanate as the isocyanate compound (B-2). Reaction product (B-1-2)
(1) A combination of either or both of a polyether polyol or a polyester polyol as a polyol, 4,4′-diphenylmethane diisocyanate, and an allophanate of 1,6-hexamethylene diisocyanate as the isocyanate compound (B-2). Reaction product (B-1-3)
(1) A reaction product comprising a combination of either or both of a polyether polyol or a polyester polyol as a polyol, 4,4′-diphenylmethane diisocyanate, and an isocyanurate of isophorone diisocyanate as the isocyanate compound (B-2) ( B-1-4)
Etc.
However, in the present invention, the combination is not limited, and any reaction product obtained by reacting the polyol, 4,4′-diphenylmethane diisocyanate and the isocyanate compound (B-2) can be preferably used.

The number average molecular weight of the reaction product (B-3) is preferably in the range of 500 to 3000, more preferably 500 to 1500 from the viewpoint of an appropriate resin viscosity at the time of coating.

The reaction product (B-3) and the isocyanate compound (B-2) may be used in combination. In the combined method, after the reaction product (B-3) is generated, the isocyanate compound (B-2) can be newly added, or the reaction product (B-3) is synthesized to synthesize the reaction product (B-3). The amount of the isocyanate compound (B-2) charged as a raw material and the reaction time are appropriately adjusted, and the reaction of the reaction product (B-3) is carried out with a portion of the isocyanate compound (B-2) remaining. It may be a method of terminating.

(Other isocyanate compounds (B-4))
The curing agent of the present invention comprises a reaction product (B-1) of the polyol and an isocyanate compound containing at least 4,4′-diphenylmethane diisocyanate, and a general-purpose isocyanate compound other than the isocyanate compound (B-2) ( B-4) may be included. In particular, when an effect as a reactive diluent is expected, a monoisocyanate compound or a diisocyanate compound can be used. From the viewpoint of minimizing elution of unintentional substances, diisocyanate compounds are preferable, and the above-mentioned diisocyanate compounds can be used as appropriate. Of these, carbodiimide-modified diisocyanate and polymethylene polyphenyl polyisocyanate (also referred to as polymeric MDI or crude MDI) are preferable.

When a general-purpose isocyanate compound (B-4) is contained, the blending ratio of the isocyanate compound (B-4) in the isocyanate component B is the reaction product (B-1) / isocyanate compound (B-4). Is preferably in the range of 50/50 to 99/1, and more preferably in the range of 70/30 to 97/3.
The isocyanate compound (B-2) / isocyanate compound (B-4) is preferably in the range of 100/0 to 5/95, more preferably in the range of 100/0 to 20/80.

The number average molecular weight of each isocyanate compound used in the isocyanate component B is not particularly limited, but is usually adjusted in the range of 500 to 3000 from the viewpoint of an appropriate resin viscosity at the time of coating.

The blending ratio of the polyol component A containing the polyol compound and the isocyanate component B containing the isocyanate compound is equivalent to the solid content hydroxyl equivalent (a) of the polyol compound and the solid isocyanate equivalent (b) of the polyisocyanate compound. The ratio [(a) / (b)] is 1.0 to 5.0, more preferably 2.0 to 3.0. Details of the manufacture are described in the examples.
The isocyanate group concentration of the isocyanate component B is preferably in the range of 5 to 20%.

(viscosity)
The two-component adhesive of the present invention preferably has a viscosity of 5000 mPa · s or less after the polyol component A and the isocyanate component B are blended at a weight ratio and left in a 40 ° C. atmosphere for 30 minutes. In the present invention, the viscosity is a value measured by a rotational viscometer under the following conditions.
Measuring device: MCR-302 manufactured by Anton Paar
Measurement conditions: Temperature 40 ° C, cone plate Φ50mm

Further, from the viewpoint of workability such as mixing, the viscosity mPa · s after 40 ° C. for 10 minutes after blending is preferably 3000 mPa · s or less, and variation in coating amount can be reduced. The lower limit of the viscosity is not particularly limited, but is often 500 mPa · s or more in consideration of the viscosity of the raw material itself.

As described in detail, the two-component adhesive of the present invention comprises a polyol component A and an isocyanate component B as essential components, and further comprises an aliphatic cyclic amide compound as a polyol component A and an isocyanate component B. By mixing with one of these components, or by blending at the time of coating as the third component, the elution of harmful low-molecular-weight chemical substances typified by aromatic amines into the contents of the laminate package is effective. Can be suppressed.

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

In the two-component 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, particularly 10 to 300 parts by mass with respect to a total of 100 parts by mass of the isocyanate component B and the polyol component A. More preferable.

Also, an adhesion promoter can be used for the two-component 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, and N-β (aminoethyl) -γ. Amino silanes such as aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycyl Epoxy silanes such as Sidoxypropyltriethoxysilane; Vinylsilanes such as Vinyltris (β-methoxyethoxy) silane, Vinyltriethoxysilane, Vinyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane; Hexamethyldisilazane, γ-Me Mercaptopropyl trimethoxysilane and the like.

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

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

As epoxy resins, commercially available bisphenol type epoxy resins, novolac type epoxy resins, β-methyl glycidyl ether of bisphenol, β-methyl glycidyl ether of novolac resin, cyclic oxirane type epoxy resin, resorcin type epoxy resin, etc. And various epoxy resins.

The two-component adhesive used in the present invention may contain other additives other than those described above, if necessary. 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 either one of the isocyanate component B or the polyol component A, or can be blended and used as a third component at the time of coating. Among these, a premix in which a pigment, an adhesion promoter, and an additive are blended in advance with the polyol component A is prepared as a polyol composition for a laminate adhesive of the present invention and used as a two-component adhesive. It is preferable from the viewpoint of workability.

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

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

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

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

In the present invention, an excellent laminated film appearance can be obtained even when high-speed laminating is performed with a solventless laminating machine. In the case of a film structure of 200 m / min or more and OPP / CPP, a good appearance can be exhibited even at high speed processing of 350 m / min or more.

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

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

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

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

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

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

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

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

The packaging body of the present invention can be industrially used as a packaging body mainly filled with foods, 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, liquid conditioner, and pharmaceutical tablet. Moreover, it can be used also for the secondary package which packages said container. In particular, since the two-component adhesive is used, it can be suitably used as a package for foods and pharmaceuticals where elution is a problem.

Next, the present invention will be specifically described with reference to examples and comparative examples. Unless otherwise indicated, “part” and “%” are based on mass.

Synthesis Example 1 [Synthesis of polyol component A1]
560 parts by mass of diethylene glycol was charged into a reaction vessel and heated to 80 ° C. with stirring under a nitrogen gas stream. Further, 600 parts by mass of adipic acid was charged into a reaction vessel while stirring and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the reaction vessel is gradually depressurized and reacted at 1 mmHg or less and 200 to 240 ° C. for 1 hour to have hydroxyl groups at both ends with an acid value of 0.8 mgKOH / g and a molecular weight of about 840. A polyester polyol resin (hereinafter abbreviated as “polyol component A1”) was obtained.

Synthesis Example 2 [Synthesis of polyol component A2]
690 parts by mass of diethylene glycol and 8 parts by mass of trimethylolpropane were charged into a reaction vessel, and dissolved by heating to 80 ° C. with stirring under a nitrogen gas stream. Further, 810 parts by mass of adipic acid was charged into a reaction vessel while stirring and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the reaction vessel is gradually depressurized and reacted at 1 mmHg or less and 200 to 220 ° C. for 1 hour to have hydroxyl groups at both ends with an acid value of 0.8 mgKOH / g and a molecular weight of about 1270. A polyester polyol resin (hereinafter abbreviated as “polyol component A2”) was obtained.

Synthesis Example 3 [Synthesis of polyol component A3]
A reaction vessel was charged with 333 parts by mass of 2-methyl-propanediol, 179 parts by mass of ethylene glycol, and 39 parts by mass of trimethylolpropane, and dissolved by heating to 80 ° C. with stirring under a nitrogen gas stream. Further, 106 parts by mass of isophthalic acid and 610 parts by mass of adipic acid were charged into a reaction vessel while stirring and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the reaction vessel is gradually depressurized and reacted at 1 mmHg or less and 200 to 240 ° C. for 1 hour to have hydroxyl groups at both ends with an acid value of 0.5 mgKOH / g and a molecular weight of about 2100. A polyester polyol resin (hereinafter abbreviated as “polyol component A3”) was obtained.

Synthesis Example 4 [Synthesis of polyol component A4]
319 parts by mass of diethylene glycol, 121 parts by mass of 2-methyl-propanediol, and 55 parts by mass of trimethylolpropane were charged into a reaction vessel and dissolved by heating to 80 ° C. with stirring under a nitrogen gas stream. Further, 504 parts by mass of adipic acid was charged into a reaction vessel while stirring and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the reaction vessel is gradually depressurized and reacted at 1 mmHg or less and 200 to 220 ° C. for 1 hour, and has hydroxyl groups at both ends with an acid value of 0.8 mgKOH / g and a molecular weight of about 660. A polyester polyol resin (hereinafter abbreviated as “polyol component A4”) was obtained.

Synthesis Example 5 [Synthesis of polyol component A5]
300 parts of polypropylene glycol (molecular weight of about 3000, triol) and 700 parts of castor oil (product name refined castor oil Kakkouichi Ito Oil Co., Ltd.) were charged into a reaction vessel and heated to 60 ° C. with stirring under a nitrogen gas stream to be uniformly dissolved. . A polyether castor oil polyol resin having a hydroxyl value of 130 mgKOH / g (hereinafter abbreviated as “polyol component A5”) was obtained.

Synthesis Example 6 [Synthesis of polyol component A6]
A reaction vessel was charged with 122 parts by weight of ethylene glycol, 267 parts by weight of neopentyl glycol, and 6 parts by weight of trimethylolpropane, and heated to 80 ° C. with stirring under a nitrogen gas stream. Further, 516 parts by mass of adipic acid and 90 parts by weight of isophthalic acid were charged in a reaction vessel while stirring and heated to 150 ° C. to 240 ° C. to carry out an esterification reaction. When the acid value becomes 5 mgKOH / g or less, the reaction vessel is gradually depressurized and reacted at 1 mmHg or less and 200 to 240 ° C. for 1 hour to have hydroxyl groups at both ends with an acid value of 0.8 mgKOH / g and a molecular weight of about 1650. A polyester polyol resin (hereinafter abbreviated as “polyol component A6”) was obtained.

Example 1 [Synthesis of Isocyanate Component B1 as Curing Agent]
1,6-hexamethylene diisocyanate isocyanurate (product name: Desmodur N3300 manufactured by Covestro), 4,4'-diphenylmethane diisocyanate (product name: Millionate MT-F manufactured by Tosoh Corporation), polypropylene glycol (molecular weight of about 1000) 422 parts and polypropylene glycol (molecular weight: about 400) 39 parts were charged in a reaction vessel, heated at 80 ° C. while stirring under a nitrogen gas stream, and the reaction vessel was cooled when the reaction was completed. An isocyanate component B1 having a concentration of about 13.1% was obtained.

Example 2 [Synthesis of Isocyanate Component B2 as Curing Agent]
10 parts of isocyanurate of 1,6-hexamethylene diisocyanate (product name Desmodur N3300 manufactured by Covestro), 400 parts of 4,4′-diphenylmethane diisocyanate (product name: Millionate MT-F manufactured by Tosoh Corporation), polypropylene glycol (about molecular weight) 2000) 536 parts and polypropylene glycol (molecular weight of about 400) 54 parts were charged in a reaction vessel, heated to 80 ° C. with stirring under a nitrogen gas stream, and the reaction vessel was cooled. An isocyanate component B2 having a concentration of about 10.1% was obtained.

Example 3 [Synthesis of Isocyanate Component B3 as Curing Agent]
1,6-hexamethylene diisocyanate burette (product name Desmodur N3200 manufactured by Covestro), 4,4'-diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), 489 parts, polypropylene glycol (molecular weight of about 1000) 422 parts and polypropylene glycol (molecular weight: about 400) 39 parts were charged in a reaction vessel, heated at 80 ° C. while stirring under a nitrogen gas stream, and the reaction vessel was cooled when the reaction was completed. An isocyanate component B3 having a concentration of about 13.1% was obtained.

Example 4 [Synthesis of Isocyanate Component B4 as Curing Agent]
Allophanate of 1,6-hexamethylene diisocyanate (product name: Basonat HA3000, manufactured by BASF) 50 parts, 4,4′-diphenylmethane diisocyanate (product name: Millionate MT-F, manufactured by Tosoh Corporation), polypropylene glycol (molecular weight: about 1000) 422 And 39 parts of polypropylene glycol (molecular weight of about 400) were charged into a reaction vessel, and the reaction was conducted by heating at 80 ° C. with stirring under a nitrogen gas stream. When the reaction was completed, the reaction vessel was cooled, and the isocyanate group concentration was about 13.0% of isocyanate component B4 was obtained.

Example 5 [Synthesis of Isocyanate Component B5 as Curing Agent]
A reaction vessel was charged with 489 parts of 4,4'-diphenylmethane diisocyanate (product name Millionate MT-F, manufactured by Tosoh Corporation), 422 parts of polypropylene glycol (molecular weight of about 1000), and 39 parts of polypropylene glycol (molecular weight of about 400). The reaction was carried out by heating at 80 ° C. while stirring, and when the reaction was completed, the reaction vessel was cooled to obtain a reaction product (B-1-1) of a polyol having isocyanate groups at both ends and isocyanate.
Subsequently, 50 parts of an isocyanurate of 1,6-hexamethylene diisocyanate (product name Desmodur N3300 manufactured by Covestro) is added to the vessel and stirred until uniform, and an isocyanate group having an isocyanate group concentration of about 13.1% is added. Component B5 was obtained.

Example 6 [Synthesis of Isocyanate Component B6 as Curing Agent]
1,6-hexamethylene diisocyanate isocyanurate (product name: Desmodur N3300 manufactured by Covestro), 4,4'-diphenylmethane diisocyanate (product name: Millionate MT-F, manufactured by Tosoh Corporation), 389 parts, polypropylene glycol (about molecular weight) 1000) 422 parts and polypropylene glycol (molecular weight of about 400) 39 parts were charged into a reaction vessel, heated at 80 ° C. with stirring under a nitrogen gas stream, and the reaction vessel was cooled to 60 ° C. when the reaction was completed. . Subsequently, 100 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Luplanate MM103, manufactured by BIP) was added to the vessel and stirred until uniform to obtain an isocyanate component B6 having an isocyanate group concentration of about 12.7%.

Example 7 [Synthesis of Isocyanate Component B7 as Curing Agent]
95 parts of isocyanurate of 1,6-hexamethylene diisocyanate (product name Desmodur N3300 manufactured by Covestro), 371 parts of 4,4′-diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), polypropylene glycol (molecular weight of about 1000) 402 parts and 37 parts of polypropylene glycol (molecular weight of about 400) were charged into a reaction vessel, heated at 80 ° C. while stirring under a nitrogen gas stream, and the reaction vessel was cooled to 60 ° C. when the reaction was completed. . Subsequently, 95 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Luplanate MM103, manufactured by BIP) was added to the vessel and stirred until uniform to obtain an isocyanate component B7 having an isocyanate group concentration of about 13.1%.

Example 8 [Synthesis of Isocyanate Component B8 as Curing Agent]
1,6-hexamethylene diisocyanate isocyanurate (product name: Desmodur N3300 manufactured by Covestro), 4,4'-diphenylmethane diisocyanate (product name: Millionate MT-F, manufactured by Tosoh Corporation), 389 parts, polypropylene glycol (about molecular weight) 1000) 422 parts and polypropylene glycol (molecular weight of about 400) 39 parts were charged into a reaction vessel, heated at 80 ° C. with stirring under a nitrogen gas stream, and the reaction vessel was cooled to 60 ° C. when the reaction was completed. . Subsequently, 50 parts of polymer diphenylmethane diisocyanate (product name: Lupranate M20S BIP) was added to the container and stirred until uniform, to obtain an isocyanate component B8 having an isocyanate group concentration of about 11.9%.

Example 9 [Synthesis of Isocyanate Component B9 as Curing Agent]
95 parts of isocyanurate of 1,6-hexamethylene diisocyanate (product name Desmodur N3300 manufactured by Covestro), 371 parts of 4,4′-diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), polypropylene glycol (molecular weight of about 1000) 402 parts and 37 parts of polypropylene glycol (molecular weight of about 400) were charged into a reaction vessel, heated at 80 ° C. while stirring under a nitrogen gas stream, and the reaction vessel was cooled to 60 ° C. when the reaction was completed. . Subsequently, 50 parts of polymer diphenylmethane diisocyanate (product name: Lupranate M20S BIP) was added to the container and stirred until uniform, to obtain an isocyanate component B9 having an isocyanate group concentration of about 12.5%.

Example 10 [Synthesis of Isocyanate Component B10 as Curing Agent]
1,6-hexamethylene diisocyanate isocyanurate (product name Desmodur N3300 manufactured by Covestro), 4,4'-diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), polypropylene glycol (molecular weight of about 2000) 376 parts, 161 parts of castor oil (product name refined castor oil Kakkouichi Ito Seiyaku Co., Ltd.) was charged into a reaction vessel, heated at 80 ° C. with stirring under a nitrogen gas stream, and the reaction vessel was completed when the reaction was completed. Cooled to 60 ° C. Subsequently, 50 parts of polymer diphenylmethane diisocyanate (product name: Lupranate M20S BIP) was added to the container and stirred until uniform, to obtain an isocyanate component B10 having an isocyanate group concentration of about 11.4%.

Example 11 [Synthesis of Isocyanate Component B11 as Curing Agent]
95 parts of isocyanurate of 1,6-hexamethylene diisocyanate (product name Desmodur N3300 manufactured by Covestro), 371 parts of 4,4′-diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), polypropylene glycol (molecular weight of about 1000) 402 parts and 37 parts of polypropylene glycol (molecular weight of about 400) were charged into a reaction vessel, heated at 80 ° C. while stirring under a nitrogen gas stream, and the reaction vessel was cooled to 60 ° C. when the reaction was completed. . Subsequently, 48 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Rupranate MM103 BIP) and 48 parts of polymer diphenylmethane diisocyanate (product name: Rupranate M20S BIP) are added to the vessel and stirred until uniform, 13.3% isocyanate component B11 was obtained.

Example 12 [Synthesis of Isocyanate Component B12 as Curing Agent]
87 parts of isocyanurate of 1,6-hexamethylene diisocyanate (product name Desmodur N3300 manufactured by Covestro), 390 parts of 4,4′-diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), polyol component A6 (molecular weight) 270 parts of about 1600) and 122 parts of polypropylene glycol (molecular weight of about 2000) are charged into a reaction vessel, heated to 80 ° C. with stirring under a nitrogen gas stream, and reacted, and when the reaction is completed, the reaction vessel is cooled to 60 ° C. did. Subsequently, 130 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Luplanate MM103, manufactured by BIP) was added to the vessel and stirred until uniform to obtain isocyanate component B12 having an isocyanate group concentration of about 16.8%.

Example 13 [Synthesis of Isocyanate Component B13 as Curing Agent]
1,6-hexamethylene diisocyanate burette (product name Desmodur N3200 manufactured by Covestro) 87 parts, 4,4′-diphenylmethane diisocyanate (product name Millionate MT-F manufactured by Tosoh Corporation), polyol component A6 (molecular weight) 270 parts of about 1600) and 122 parts of polypropylene glycol (molecular weight of about 2000) are charged into a reaction vessel, heated to 80 ° C. with stirring under a nitrogen gas stream, and reacted, and when the reaction is completed, the reaction vessel is cooled to 60 ° C. did. Subsequently, 130 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Luplanate MM103, manufactured by BIP) was added to the vessel and stirred until uniform to obtain an isocyanate component B13 having an isocyanate group concentration of about 16.9%.

Example 14 [Synthesis of Isocyanate Component B14 as Curing Agent]
1,6-hexamethylene diisocyanate allophanate (product name: Basonat HA3000, manufactured by BASF) 87 parts, 4,4'-diphenylmethane diisocyanate (product name: Millionate MT-F, manufactured by Tosoh Corporation), polyol component A6 (molecular weight: about 1600) 270 parts and 122 parts of polypropylene glycol (molecular weight of about 2000) were charged into a reaction vessel, and the reaction was conducted by heating at 80 ° C. with stirring under a nitrogen gas stream. When the reaction was completed, the reaction vessel was cooled to 60 ° C. Subsequently, 130 parts of carbodiimide-modified diphenylmethane diisocyanate (product name: Lupranate MM103, manufactured by BIP) was added to the vessel and stirred until uniform to obtain isocyanate component B14 having an isocyanate group concentration of about 16.6%.

Comparative Example 1 [Synthesis of Isocyanate Component C1 as Curing Agent]
A reaction vessel was charged with 539 parts of 4,4′-diphenylmethane diisocyanate (product name Millionate MT-F, manufactured by Tosoh Corporation), 422 parts of polypropylene glycol (molecular weight of about 1000), and 39 parts of polypropylene glycol (molecular weight of about 400). The reaction was carried out by heating at 80 ° C. while stirring, and when the reaction was completed, the reaction vessel was cooled to obtain an isocyanate component C1 having an isocyanate group concentration of about 13.6%.

Comparative Example 2 [Synthesis of Isocyanate Component C2 as Curing Agent]
50/50 mixture of 4,4'-diphenylmethane diisocyanate and 2,4-diphenylmethane diisocyanate (product name: Luplanate MIBP) 200 parts, 4,4'-diphenylmethane diisocyanate (product name: Millionate MT-F, manufactured by Tosoh Corporation) Charge 339 parts polypropylene glycol (molecular weight about 1000) 422 parts and polypropylene glycol (molecular weight about 400) 39 parts in a reaction vessel and heat at 80 ° C. with stirring under a nitrogen gas stream. The container was cooled to obtain an isocyanate component C2 having an isocyanate group concentration of about 13.6%.

(Evaluation method of curing agent solution stability)
Room temperature: The solution stability after 100 g of the curing agent was put in a sealed container and allowed to stand at room temperature was evaluated. The solution stability evaluation at room temperature storage was as follows.
Solution stability evaluation: solution stability evaluation deposited within 1: 1 week 2: solution stability evaluation deposited within 1 to 4 weeks 3: deposition within 4 to 12 weeks
Solution stability evaluation 4: No precipitation for 12 weeks or more. Refrigeration: 100 g of curing agent was put in an airtight container and left standing in a refrigerator (5 ° C.) to evaluate the solution stability. The solution stability evaluation during refrigerator storage was as follows.
Solution stability evaluation: solution stability evaluation deposited within 1: 1 week 2: solution stability evaluation deposited within 1-3 weeks 3: solution precipitation evaluated within 3-8 weeks
Solution stability evaluation 4: Table 1 shows the results of no precipitation for 8 weeks or more.

In Table 1, “reaction product (B-3)” represents the presence of the reaction product (B-3) obtained by reacting the reaction product (B-1) with the isocyanate (B-2). "Reacts the reaction product (B-1) with the isocyanate (B-2)" and "none" reacts the reaction product (B-1) with the isocyanate (B-2). It means not letting. The “reactive diluent (B-4)” represents an isocyanate compound other than the isocyanate (B-2), that is, the isocyanurate body, burette body, allophanate body and adduct body of diisocyanate.

HDI is an abbreviation for 1,6-hexamethylene diisocyanate, PPG is an abbreviation for polypropylene glycol, 4,4MDI is an abbreviation for 4,4′-diphenylmethane diisocyanate, and liquid MDI is an abbreviation for liquid diphenylmethane diisocyanate. .

(Example of two-component adhesive, comparative example)
A two-component adhesive was obtained according to the combinations in Tables 2 and 3.

(Evaluation methods)
[Evaluation of elution amount of harmful components (PAA)]
A two-component adhesive compounded in a combination of Examples or Comparative Examples was applied to a PET film so that the coating amount was about 3.0 g / m ^{2 in} solid content, and the coated surface of this film and a CPP film were laminated with a laminator. And laminated film was produced. This laminated film was stored in a constant temperature bath at 40 ° C. for 3 days.
This laminated film was cut out at 120 mm × 220 mm, bent so that the CPP was inside, and heat sealed at 1 atm, 190 ° C. for 1 second in 10 mm width in 3 directions, and a pouch in which the contents were in contact with ² dm ² was produced. . The contents were 3% vinegar acetate solution. After the filled pouch was sterilized by retort at 121 ° C.-0.5 hr, PAA was measured by LC / MS / MS.

[Measurement of viscosity after blending at 40 ° C. for 30 minutes]
The viscosity was measured with a rotational viscometer under the following conditions, and the value was set to mPa · s.
Measuring device: MCR-302 manufactured by Anton Paar
Measurement conditions: Temperature 40 ° C, cone plate Φ50mm
The viscosity evaluation was as follows.
Viscosity evaluation 1: 1000 to 3000 mPa · s
Viscosity evaluation 2: 3000 to 4000 mPa · s
Viscosity evaluation 3: 4000 to 5000 mPa · s
Viscosity evaluation 4: 5000 mPa · s or more

[Lamination strength]
A two-component adhesive compounded with a combination of the examples or comparative examples on a PET film on which a design is gravure-printed with printing ink Univia NT (manufactured by DIC) so that the coating amount becomes about 3.0 g / m ^{2 in} solid content. Applied. Thereafter, a laminator was used to bond the coated surface of the film and the LLDPE film to produce a laminated film. This laminated film was stored in a constant temperature bath at 40 ° C. for 3 days to prepare a laminated film for a laminate strength test.
A test piece was cut out from the laminated film with a width of 15 mm, and using a tensile tester, the adhesive strength (N / 15 mm) was measured by T-type peeling at a peeling speed of 300 mm / min.

(Lamination strength after storage of isocyanate component B over time)
After the isocyanate components B1 to B14 and C1 to C2 were produced and allowed to stand at 60 ° C. for 10 days, a two-component adhesive was blended according to the combinations in the table, and the laminate strength was measured in the same manner.

[Lamination strength and appearance after retort]
A two-component adhesive compounded with a combination of Examples or Comparative Examples on a PET film on which a design is gravure-printed with printing ink (“Univia NT” manufactured by DIC Corporation), the coating amount is a solid content of 3.0 g / m. It applied so that it might become about ² . Thereafter, a laminator was used to bond the coated surface of the film and the LLDPE film to produce a laminated film. This laminated film was stored in a constant temperature bath at 40 ° C. for 3 days.
This laminated film was cut out at 150 mm × 300 mm, bent so that the LLDPE was inside, and heat-sealed at 1 atm, 180 ° C. for 1 second to prepare a pouch. As a content, 1/1/1 sauce (meat sauce: vegetable oil: vinegar = 1: 1: 1) was added.
The filled pouch was steam sterilized at 121 ° C. for 30 minutes. The content was removed, and a test piece was cut from the laminated film with a width of 15 mm, and using a tensile tester, the adhesive strength (N / 15 mm) was measured at a peeling rate of 300 mm / min by T-type peeling.
Moreover, the external appearance of each pouch after taking out was observed, and the following evaluation was performed by the presence or absence of generation | occurrence | production of delamination.
Evaluation ○: No delamination evaluation △: 5 points or less for delamination points Evaluation: 6 points or more for delamination points

(Laminate strength and appearance after retorting after storage of isocyanate component B over time)
After the isocyanate components B1 to B14 and C1 to C2 were produced and allowed to stand at 60 ° C. for 10 days, a two-component adhesive was blended according to the combinations in the table, and the laminate strength and appearance after retorting were evaluated in the same manner. did.

The results are shown in Table 2 to Table 5.

As a result, the two-component adhesives obtained in the Examples had a viscosity of 5000 mPa · s or less after 40 ° C. for 30 minutes after blending, showed a long pot life, and the PAA elution amount was 10 ppb or less. The laminate strength and appearance were also excellent.
On the other hand, Comparative Examples 3 to 8 are examples that do not contain the isocyanate compound (B-2). In Comparative Example 3, the PAA elution amount was 10 ppb or less, but the viscosity after 40 ° C. for 30 minutes after blending exceeded 6000 mPa · s from the early stage after blending (after 20 minutes). In Comparative Examples 4, 6, and 8, the viscosity at 40 ° C. for 30 minutes after blending was 5000 mPa · s or less, and there was no problem in pot life, but the PAA elution amount was as high as 100 ppb or more. In Comparative Examples 5 and 7, the laminate strength after retorting after storage of the isocyanate component B with time decreased.

Claims (7)

A curing agent for a two-component adhesive, which is a reaction product (B-1) of a polyol and an isocyanate compound containing at least 4,4'-diphenylmethane diisocyanate, an isocyanurate body, a burette body, and an allophanate of diisocyanate A curing agent for a two-component adhesive, comprising at least one isocyanate compound (B-2) selected from the group consisting of a body and an adduct body. The curing agent for a two-component adhesive according to claim 1, wherein the reaction product (B-1) and the isocyanate compound (B-2) are reacted. 3. The reaction product (B-3) comprising the reaction product (B-1) and the isocyanate compound (B-2) and the isocyanate compound (B-2). Curing agent for liquid adhesives. Having a polyol component A containing a polyol compound and an isocyanate component B containing an isocyanate compound,
The isocyanate component B comprises a reaction product (B-1) of a polyol and an isocyanate compound containing at least 4,4′-diphenylmethane diisocyanate, a diisocyanate isocyanurate body, a burette body, an allophanate body and an adduct body. A two-component adhesive comprising at least one isocyanate compound (B-2) selected from: The two-component adhesive according to claim 4, wherein the reaction product (B-1) is a reaction product of a polyol, 4,4'-diphenylmethane diisocyanate, and the isocyanate compound (B-2). A laminated film formed by laminating an adhesive layer between a first plastic film and a second plastic film, wherein the adhesive layer is a layer of the two-component adhesive according to claim 4 or 5. A laminated film characterized by that. 6. A package formed by forming a laminated film formed by laminating an adhesive layer between a first plastic film and a second plastic film into a bag shape, wherein the adhesive layer is defined in claim 4 or 5. A package comprising the two-component adhesive layer.