KR100274915B1 - Adhesive composition for lamination and method for preparing laminated film therewith - Google Patents

Abstract

The present invention provides a laminating adhesive composition which can be cured in a short time at room temperature and has excellent productivity and workability, and a method for producing a laminated film using the same.

That is, it is an adhesive composition for lamination which consists of an isocyanurate group, a ureidodione group, and an isocyanate-reactive group containing organic compound (A), an organic isocyanate compound (B), a catalyst (C), and a coupling agent (D) as needed. . The organic compound (A) has a molecular weight and polyisocyanate component (a) consisting of a ureidodione group and an isocyanurate group-containing polyisocyanate compound (a1) and, if necessary, a polyisocyanate compound (a2) having two or more isocyanate groups. Obtained by reacting component (b) having two or more isocyanate reactive groups which are 18 to 20,000. Moreover, it is a manufacturing method of the laminated | multilayer film using this adhesive composition.

Description

Adhesive composition for lamination and manufacturing method of laminated film using the same

The present invention relates to a preferred adhesive composition for laminating a film and a method for producing a laminated film using the same.

In recent years, as a packaging method, composite soft packaging has been remarkably developed due to its strength, product protection, workability in packaging, propagation effect by packaging, reduction of packaging cost due to large-scale supply of plastic materials, and the like. .

As an adhesive used for laminating | stacking a film for this, it is excellent in adhesiveness and cold resistance, and generally has active hydrogen groups, such as a hydroxyl group, for the reason of being wide adaptable range to base materials, such as various plastics and metal foils. The two-component polyurethane adhesive which consists of a hardening | curing agent which has a main body and an isocyanate group is mainstream.

However, at present, the two-component polyurethane-based laminating adhesive hardly reacts with the adhesive after adhesion, and requires a curing promoting process called aging. Specifically, it is necessary to cure the adhesive by storing the laminated film in a thermal insulation chamber at 35 to 60 ° C. for about 3 to 5 days and aged. At this time, since the curing degree of the adhesive is changed according to the aging conditions, it affects the adhesive strength of the laminated film, and if the aging is insufficient, it causes a layer peeling phenomenon due to poor curing of the adhesive. In particular, aliphatic polyurethane-based adhesives require a very long time for this curing reaction. Therefore, such a aging process is an unavoidable process in the dry lamination process, and the cost of equipment investment for the installation of the aging thermal insulation chamber and the useful materials for subsequent thermal insulation were required.

An object of the present invention is to provide an adhesive composition for lamination which can complete a curing reaction in a short time at room temperature and has excellent productivity and workability, and a method for producing a laminated film using the adhesive composition for lamination.

The present inventors have diligently studied to solve these conventional problems, and as a result, at least the organic compound (A), the organic isocyanate compound (B), the catalyst (C) and the necessity containing the isocyanurate group, the ureidodione group and the isocyanate reactive group Therefore, it discovered that the adhesive composition which consists of a coupling agent (D) can complete hardening reaction in a short time at normal temperature in the adhesion of a film verb, and completed this invention.

That is, this invention is an organic compound (A) and an organic isocyanate compound (B) which contain a ureidodione group and an isocyanate-reactive group in an equivalence ratio of a ureidodione group / isocyanate-reactive group = 0.25-1.0 with the isocyanurate group at least. And an adhesive composition for lamination comprising a catalyst (C), wherein the organic compound (A) contains a polyisocyanate compound (a1) containing at least a ureidodione group and an isocyanurate group and, if necessary, two or more isocyanate groups in the molecule. A polyisocyanate component (a) consisting of a polyisocyanate compound (a2) containing and a component (b) having two or more isocyanate-reactive groups in a molecule having a molecular weight of 18 to 20,000, the component (b) to the isocyanate group of the polyisocyanate component (a) Equivalent proportion of isocyanate-reactive groups of It is the said adhesive composition for lamination | stacking characterized by the organic compound obtained by making it react on the conditions to make.

The present invention also provides an organic compound (A), an organic isocyanate compound (B), containing at least an isocyanurate group and an ureidodione group and an isocyanate-reactive group in an equivalent ratio of ureidodione group / isocyanate-reactive group = 0.25 to 1.0, A laminating adhesive composition comprising a catalyst (C) and a coupling agent (D), wherein the organic compound (A) contains at least a polyisocyanate compound (a1) containing a ureidodione group and an isocyanurate group and, if necessary, in a molecule. A polyisocyanate component (a) consisting of a polyisocyanate compound (a2) having two or more isocyanate groups and a component (b) having two or more isocyanate reactive groups in a molecule having a molecular weight of 18 to 20,000 are added to the isocyanate group of the polyisocyanate component (a). The equivalent ratio of isocyanate reactive groups of component (b) to It is the said adhesive composition for lamination | stacking characterized by the organic compound obtained by making it react on the conditions exceeding 1.0.

Moreover, this invention is said each laminated adhesive composition in which the said component (b) contains rosin polyol (b1).

In addition, the present invention is a method for producing a laminated film, characterized in that the adhesive composition for lamination is applied to the first film and dried, and then the second film is bonded thereto and aged at room temperature.

First, the organic compound (A) containing the isocyanurate group, the ureidodione group, and the isocyanate-reactive group which are essential components in this invention is described.

The organic compound (A) is a polyisocyanate component (a) consisting of a polyisocyanate compound (a1) containing at least a ureidodione group and an isocyanurate group and a polyisocyanate compound (a2) having two or more isocyanate groups in a molecule as necessary. ) And component (b) having two or more isocyanate-reactive groups in a molecule having a molecular weight of 18 to 20,000 under conditions where the equivalent ratio of isocyanate-reactive groups of component (b) to isocyanate groups of polyisocyanate component (a) exceeds 1.0 It is obtained by reaction.

The reaction conditions for which the isocyanate-reactive group is excessive are conditions necessary for the end of the isocyanate-reactive group so that the isocyanate group does not remain in the produced organic compound (A), and the component to the isocyanate group in the polyisocyanate component (a) when the adhesive performance is considered As for the equivalence ratio of the isocyanate-reactive group in (b), 1.0-2.0 are preferable. Actually, the conditions which do not gel at the time of these reactions are determined according to the average number of functional groups of the polyisocyanate component (a) resulting from isocyanurate group content, etc., and the average number of functional groups of the component (b) resulting from triol introduction etc. Therefore, it is important to mix these conditions as appropriate and hold the reaction at or below the temperature condition at which the ureidodione group is ring-opened.

The organic compound (A) is an inert solvent commonly used in the polyurethane industry, either in a molten state or in a bulk state or, if necessary, for example, an aromatic hydrocarbon solvent such as toluene, xylene, or an ester such as ethyl acetate or butyl acetate. Ketone solvents such as solvents, methyl ethyl ketone and cyclohexanone, glycol ether ester solvents such as ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, ethyl-3-ethoxypropionate, tetrahydrofuran and dioxane Temperature conditions under which the ureidodione group is not ring-opened using one or two or more kinds of polar solvents such as ether solvents such as dimethylformamide, dimethylacetone, N-methylpyrrolidone, and furfural Below 100 ° C., the components may be prepared by uniformly mixing the components in the above mixing condition.

The reaction apparatus may be any apparatus as long as the above-mentioned homogeneous reaction can be achieved, and examples thereof include a mixing and kneading apparatus such as a reaction unit or a kneader with a stirring device, a uniaxial or multiaxial extrusion reactor, and the like. In order to advance reaction quickly, you may use metal catalysts, such as dibutyltin dilaurate, or tertiary amine catalysts, such as triethylamine, which are common in polyurethane manufacture as a catalyst.

The organic compound (A) prepared in this way is a urethane group, urea group, in addition to the functional group (isocyanate-reactive group) that reacts with the ureidodione group, isocyanurate group and isocyanate group according to the polyisocyanate compound (a1) to be used. It may contain a group derived from an isocyanate group such as carbodiimide group, ureidone imine group, oxazolidone group, hydantoin group, etc., but does not substantially contain an isocyanate group and a ureidodione group and an isocyanate-reactive group ureidodione group / Isocyanate reactive groups = 0.25 to 1.0, preferably 0.35 to 0.75 equivalent ratio.

In addition, in consideration of workability and adhesive performance, the molecular weight of the organic compound (A) is preferably 3,000 to 60,000, particularly 5,000 to 40,000.

The polyisocyanate compound (a1) in the polyisocyanate component (a) contains at least a ureidodione group and an isocyanurate group.

The polyisocyanate compound (a1) may be one kind or a mixture of two or more kinds as long as it contains at least a ureidodione group and an isocyanurate group. For example, a ureidodione group containing polyisocyanate compound, an isocyanurate group containing polyisocyanate compound, or a mixture of a ureidodione group and an isocyanurate group containing polyisocyanate compound may be sufficient. 3-25 weight% is preferable and, as for the ureidodione group content of a polyisocyanate compound (a1), 5-23 weight% is more preferable. 1-24 weight% is preferable and, as for isocyanurate group content, 3-20 weight% is more preferable.

The polyisocyanate compound (a1) may contain groups other than the ureidodione group and isocyanurate group derived from an isocyanate group as needed. Examples of groups other than the ureidodione group and the isocyanurate group derived from such isocyanate groups include urethane groups, urea groups, carbodiimide groups, ureidoneimine groups, oxazolidone groups, and hydantoin groups, and the like. You may contain 1 type or in mixture of 2 or more types.

The polyisocyanate compound (a2) used as needed in the polyisocyanate component (a) is a polyisocyanate compound having two or more isocyanate groups in the molecule.

As a polyisocyanate compound or polyisocyanate compound (a2) for forming the polyisocyanate compound (a1) of this invention, polyisocyanate compounds, such as its polymer, etc. are mentioned besides a polyisocyanate monomer, 1 type, or 2 or more types are mixed Can be used.

Specifically, for example, 2,4-triylene diisocyanate, 2,6-triylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4'- diphenylmethane diisocyanate , 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, 2-nitrodiphenyl-4,4'- diisocyanate, 2,2'-diphenylpropane-4,4 ' -Diisocyanate, 3,3'- dimethyl diphenylmethane-4,4'- diisocyanate, 4,4'- diphenyl propane diisocyanate, m-phenylenedi isocyanate, p-phenylene diisocyanate, naphthylene-1, Aromatic diisocyanates such as 4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, or tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter , Abbreviated as HDI), lysine diisocyanate, etc. Diisocyanates such as isocyanates or alicyclic diisocyanates such as isophorone diisocyanate (hereinafter abbreviated as IPDI), hydrogenated triylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethyl xylene diisocyanate The polyisocyanate compound obtained by reaction of the isocyanate, the polymer of the said diisocyanate, the bifunctional or more than polyol, etc., and the said diisocyanate or its polymer is suitable.

As a polyisocyanate monomer for forming a polyisocyanate compound (a1), 1, 6- hexamethylene diisocyanate is especially suitable at the point which the polyisocyanate compound produced turns into a liquid state, or becomes sulfur-free denaturation.

The polyisocyanate compound (a1) is generally formed by dimerization reaction (ureidodionation reaction), trimerization reaction (isocyanurate reaction), etc. of polyisocyanate monomers, and specifically, for example, Can be.

From the corresponding polyisocyanate compounds, known ureidodione catalysts such as triethylphosphine, dibutylethylphosphine, tributylphosphine, tri-n-propylphosphine, triamylphosphine, tribenzylphosphate Inert solvents, such as toluene, xylene and other aromatic solvents, methylethylketone, which are usually free of solvents or commercially available in the polyurethane industry, in the presence of trialkylphosphines such as pins or pyridine, at a reaction temperature of usually 0 to 90 ° C. In the presence and case of ketone solvents such as methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, glycol ether ester solvents such as propylene glycol methyl ether acetate and ethyl-3-ethoxypropionate Therefore, it can be prepared in a solvent such as polyol or DOP that is liquid at the reaction temperature.

To the reaction solution, a solution of, for example, phosphoric acid, methyl paratoluenesulfonic acid, sulfur, and the like is added to the reaction solution at a time when 20 to 50 mol% of the isocyanate group is reacted with the isocyanate group content. Stop it. Depending on the kind of polyisocyanate compound to be used, it may precipitate as crystal | crystallization in this reaction process. In particular, aromatic polyisocyanates are usually crystallized and separated from the reaction system.

According to this method, ureidodione group-containing polyisocyanate compounds (ie dimers or polyureidodiones), isocyanurate group-containing polyisocyanate compounds (ie trimers or polyisocyanurate bodies), ureido A mixture of a diision group and an isocyanurate group-containing polyisocyanate compound, and a polyisocyanate monomer as a raw material is produced. By removing the polyisocyanate monomer which is a raw material from this mixture by thin film distillation etc., the target ureido dione group containing polyisocyanate compound, the isocyanurate group containing polyisocyanate compound, and the ureido dione group and isocyanurate group containing polyisocyanate compound A mixture of these is obtained.

The production rate of isocyanurate group becomes high, so that the high temperature reaction at the time of manufacture and the content of polyisocyanate compound at the time of stop of reaction are high.

As the amount of the catalyst such as triethylphosphine increases, the production rate of the ureidodione group increases. By controlling these reaction conditions, a polyisocyanate compound (a1) containing a ureidodione group and an isocyanurate group in a specific ratio can be obtained.

Actively introducing isocyanurate groups as well as ureidodione groups as in the present invention can exhibit excellent heat resistance and durability.

In addition, when a polyisocyanate compound molecule contains a certain ratio of isocyanurate groups in addition to the ureidodione group, branching points of a degree which does not reach gelation can be introduced into the product compound molecules. Due to the structure having the branched chain, when used as a laminating adhesive, excellent physical properties can be exhibited at a low reaction rate in a short time, compared with that obtained from a conventionally known ureidodione group-containing polyurethane compound in the curing process.

Furthermore, before the polyisocyanate compound (a1) used in the present invention is partially reacted with a bifunctional polyol having a side chain structure before producing a ureidodione group and an isocyanurate group, the polyisocyanate compound (a1) may react with the component (b) or the solvent. It may be preferable for reasons such as improving compatibility and adhesion with a film.

The bifunctional polyol having this side chain structure has a hydrocarbon group (i.e., a branched hydrocarbon group) bonded to the dihydric alcohol molecular skeleton by linearly connecting two hydroxy groups and at least one hydrocarbon group between them in the shortest linear direction. Compound. Preferred are those having two or more branched structures or dihydric alcohols having long branched hydrocarbon groups. In particular, the dihydric alcohol of the molecular weight 100-1000 is preferable. Neopentylglycol (hereinafter abbreviated as NPG), 3-methyl-1,5-pentanediol, 1,3-butanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl- 2-ethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-n-hexadecane-1,2-ethylene glycol , 2-n-eichoic acid-1,2-ethylene glycol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, hydrogenated bisphenol A, etc. may be mentioned. . In addition, these dihydric alcohols can also be used in combination of 2 or more type.

The reaction of the ureidodione group and the isocyanurate group-containing polyisocyanate compound (a1) and the polyisocyanate compound (a2) except for the unreacted polyisocyanate monomer to react with the component (b) in a form in which the number of functional groups is reduced Problems such as gelation do not occur during the reaction, which is preferable, and may be effective in relation to control of reactivity and expression properties.

The isocyanate group equivalent ratio of the polyisocyanate compound (a1) and the polyisocyanate compound (a2) except for the unreacted polyisocyanate monomer is usually the isocyanate group equivalent of the polyisocyanate compound (a2) / isocyanate group equivalent of the polyisocyanate compound (a1) = Selected from 0 to 5.70, 0.10 to 4.00 are preferred, and 0.15 to 3.00 are more preferred.

Component (b) is a compound containing two or more isocyanate-reactive groups, preferably active hydrogen groups, in molecules having a molecular weight of 18 to 20,000.

Specifically, it is preferable to contain one or two or more selected from polyamines, urea resins, melamine resins, polyester resins, rosin resins, acrylic resins, polyvinyl alcohols, and the like, which contain polyols, amino groups and the like in addition to water.

Examples of such polyols include polyols known in the polyurethane industry such as polyester polyols, polyester amido polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, and rosin polyols (b1).

Specific examples include dicarboxylic acids such as known succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, acid esters thereof, acid anhydrides, and the like, and ethylene glycol (hereinafter, EG). Abbreviated), 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,5-pentane glycol, 1,6-hexane glycol, 3-methyl-1,5-pentane Glycol, 2-butyl-2-ethyl-1,3-propanediol, NPG, 1,8-octane glycol, 1,9-nonanediol, diethylene glycol, cyclohexane-1,4-diol, cyclohexane-1 Glycols or triols, such as, 4-dimethanol, dimer acid diol, trimethylolpropane, glycerin, hexanetriol, or ethylene oxide or propylene oxide adducts of bisphenol A, or hexamethylenediamine, N, N, N ', N′-tetrakis (2-hydroxypropyl) ethylenediamine, xylenediamine, isophoronediamine, mother Polyester polyol and polyesteramide polyol obtained by dehydration condensation reaction with diamine, such as noethanolamine and isopropanol triamine, alone or a mixture thereof, such as triamine or amino alcohol, are mentioned.

In addition, lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (ie, lactone) monomers such as ε-caprolactone, alkyl substituted ε-caprolactone, δ-valerolactone, and alkyl substituted δ-valerolactone have.

Examples of the polyether polyols include polyethylene glycol, polypropylene ether polyols, polytetramethylene ether polyols, and the like. Examples of the polyether ester polyols include those produced from these polyether polyols and the aforementioned dicarboxylic acids and acid anhydrides.

The polycarbonate polyol is obtained, for example, from the reaction of hexane glycol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol and the like, diethyl carbonate, diphenyl carbonate, and the like. Polyurethane high bridge Nippon 980, Nippon 981, etc. can be mentioned.

Further, monomolecular glycols or triols listed as raw materials for the polyester polyols, ie, EG, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,5-pentane glycol , 1,6-hexane glycol, 3-methyl-1,5-pentane glycol, NPG, 1,8-octane glycol, 1,9-nonanediol, diethylene glycol, cyclohexane-1,4-diol, cyclohexane Ethylene oxide or propylene oxide adducts of -1,4-dimethanol, dimer acid diol, trimethylolpropane, glycerin, hexanetriol, quodrol or bisphenol A and the like can also be used as the polyol.

Examples of the polyamine containing the amino group include monoether diamines such as hexamethylenediamine, ethylenediamine, and isophoronediamine, triamines, aromatic diamines, and polyether polyamines in which the terminal of the polyether is an amino group.

In addition, urea resin, melamine resin, epoxy resin, polyester resin, acrylic resin, polyvinyl alcohol, etc. are generally known in the polyurethane industry, and if it contains two or more isocyanate-reactive groups, such as an active hydrogen group, a component It can be used as part or all of (b).

Although the molecular weight of this component (b) is 18-20,000, it is especially preferable that it is water and molecular weight 400-10,000. If the molecular weight is large, the amount of the urethane group or the like to be introduced decreases, and thus the toughness and coagulation force of the organic compound (A) decrease. If the molecular weight is small, the organic compound (A) tends to be soft, which is not preferable. It is necessary to select such a molecular weight suitably according to a use, and in order to raise heat resistance and aggregation energy, it is preferable to use a low molecular weight thing.

In addition, when the adhesive performance with a base film is considered, the aromatic polyester polyol using terephthalic acid, isophthalic acid, etc., and the polyester polyol using adipic acid are preferable.

Further preferred in the case where the adhesive performance is considered, the rosin polyol (b1) is used as part or all of the component (b).

The rosin polyol (b1) has a functional group which reacts with an isocyanate group and is a rosin ester obtained from rosin and a polyhydric alcohol (see Japanese Patent Laid-Open No. 155978/1990) or a rosin ester obtained from an epoxy compound and a rosin (Japanese Patent Laid-Open). 155972/1993). Also preferred are polyethers having a rosin skeleton.

Among these, especially rosin ester (refer to Unexamined-Japanese-Patent No. 263059/1993) consisting of 1 molecule of diepoxy compound and 2 molecules of hydrogenation disproportionation refinement | purification is easy to introduce into the molecule | numerator of organic compound (A), Molecular weight control of an organic compound is easy and preferable. As these rosin polyol (b1), KE-601, KE-615-3, KE-622, KE-623, KE-624, etc. made by Kokawa Chemical Industries, Ltd. are mentioned specifically ,.

As the organic isocyanate compound (B), which is an essential component in the present invention, the above-mentioned compounds and the like may be used as the polyisocyanate component (a). Specifically, Nihon Polyurethane Co., Ltd., Coronate L, Coronate 3041, Coronate HL, Coronate HX, etc. are mentioned.

It is preferable that the compounding quantity of this organic isocyanate compound (B) shall be 1-30 weight part in particular, 3-15 weight part in conversion of solid content with respect to 100 weight part of solid content of the said organic compound (A).

Next, the catalyst (C) which is an essential component in this invention is described.

The catalyst (C) includes those generally known as transesterification catalysts, urethaneization catalysts, block isocyanate dissociation catalysts, isocyanurate catalysts, and the like, and specific examples thereof include tin-based dibutyltin dilaurate and stanasoctoate Catalyst, triethylenediamine, triethylamine, N, N, N ', N'-tetramethylpropylenediamine, N, N, N', N'-tetrakis (2-hydroxypropyl) ethylenediamine, N-methyl Morpholine, 1,2-dimethylimidazole, 1,5-diazabicyclo (4,3,0) nonene-5, 1,8-diazabicyclo (5,4,0) -undecene-7 ( (Hereinafter abbreviated as DBU), various amine salt catalysts such as borane salts of these amine catalysts, DBU phenol salts, DBU octylate salts and DBU carbonate salts, carboxylates such as magnesium naphthenate, lead naphthenate, and CH ₃ COOK; triethylphosphine, tri-benzyl-phosphonium alkoxides, organic zinc-based metal such as trialkyl phosphines, CH ₃ ONa, such as pins It may be a sheet or the like.

Among these, DBU and various acid salts of DBU can be used preferably, considering the catalyst effect and the stability of the adhesive composition after addition.

Although the hardening rate largely depends on the kind, quantity, etc. of the added catalyst, a practical hardening rate can be obtained even if it is selected suitably even in the temperature range near room temperature, Preferably it is 15-35 degreeC.

However, for example, when the amount of the catalyst added is less than 0.01% by weight relative to the solid content of the organic compound (A), it is difficult to promote the curing reaction by the addition of the catalyst, and when the amount is more than 5.00% by weight, the curing rate is increased. It is not preferable because there is such a problem that it may become difficult to apply the coating quickly and may promote hydrolysis of the adhesive after curing.

Therefore, it is preferable that the addition amount of the ureidodione group dissociation catalyst with respect to solid content of organic compound (A) shall be 0.01-5.00 weight%, especially 0.05-2.00 weight%.

As a coupling agent (D) which can be used in this invention, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. are mentioned.

As for the addition amount of a coupling agent with respect to 100 weight part of solid content of an organic compound (A), 0.05-10.00 weight part is preferable. More preferred is 0.1 to 5.00 parts by weight. The amount added as described above is calculated in consideration of the base film coating area of the coupling agent, the coating efficiency, the adhesive performance, and the like.

Examples of the silane coupling agent include vinylsilane compounds such as ν-methacryloxypropyltrimethoxy silane and vinyltriethoxy silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy silane and ν-glycidoxypropyl. Epoxysilane compounds such as trimethoxy silane, aminosilane compounds such as ν-aminopropyltriethoxy silane, N-β-aminoethyl-ν-aminopropylmethyldimethoxy silane, or ν-mercaptopropyltrimethoxy silane Mercaptosilane compounds, such as these, etc. can be used preferably.

As titanate coupling agent, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite ) Titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecylphosphite) titanate, bis (dioctylpyrophosphate ) Oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacrylic isostearoyl titanate, isopropyl isostearoyl diacryl titanate, Isopropyltri (dioctylphosphate) titanate, isopropyltricumylphenyl titanate, isopropyltri (N-amidoethylaminoethyl) titane , Dicumylphenyloxyacetate titanate, diisostearoylethylene titanate, and the like, and specific examples are Phenacto KR TTS, KR 46B, KR 55, KR 41B, KR 38S manufactured by Minoso Chemical Co., Ltd. , KR 138S, KR 238S, KR 338X, KR 12, KR 44, KR 9SA, KR 34S and the like can be preferably used.

Acetoalkoxy aluminum diisopropylate etc. are mentioned as an aluminum coupling agent, As a commodity, Phenol-acto AL-M etc. by the Minoso Chemical Co., Ltd. can be used preferably.

Among the above coupling agents, epoxysilane compounds, aminosilane compounds, phosphate titanates and the like are preferable in consideration of the improvement in adhesion to polyethylene terephthalate films, aluminum films, nylon films, polyolefin films and the like which are widely used.

Especially, especially preferable is a case where the epoxy silane compound is used as a coupling agent (D), and various acid salts of DBU and DBU are used as a catalyst (C). Since DBU and various acid salts of DBU are the usual urethanation catalyst and the isocyanurate catalyst which passes through a ureidodione group, it is estimated that it accelerates the hardening rate of the organic compound (A) containing a ureidodione group. . In addition, DBU and various acid salts of DBU are presumed to have a desirable influence on the adhesive strength because they are catalysts for promoting the reaction of the epoxy and isocyanate groups of the epoxysilane compound.

Films used for lamination in the present invention include stretched polypropylene, unstretched polypropylene (hereinafter abbreviated as CPP), polyester (hereinafter abbreviated as PET), nylon (hereinafter abbreviated as NY), low density Polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, polyvinyl alcohol, ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVOH), plastic film such as polystyrene, polycarbonate, polyvinylidene chloride, polyvinyl chloride, Al And metal foils such as Cu, paper, and the like and films coated with polymers thereon can be mentioned.

These films are preferably subjected to proper surface treatment such as corona discharge treatment before lamination to improve adhesion.

In addition, the polymer coated film may cause problems such as bubble generation and lowering of adhesive strength, and it is necessary to consider in advance the kind, coating amount, surface characteristics, and the like of the coated polymer.

Next, the lamination method of a film is described.

The adhesive composition for lamination of the present invention can be used in known lamination methods such as dry lamination, hot melt lamination, extrusion lamination, and the like. In addition, the laminated film can complete the curing reaction at room temperature (preferably 15 to 35 ° C.) by aging for a predetermined time (preferably within 24 hours).

By the method of this invention, not only the film in which two sheets were laminated | stacked, but also the thing in which three or more sheets were laminated | stacked can be manufactured.

Next, although the Example of this invention is described in detail, this invention is not limited to these Examples. Unless otherwise mentioned, parts and percentages in the synthesis examples, examples and comparative examples mean parts by weight and% by weight, respectively.

In addition, the ureidodione group content and the isocyanurate group content in a synthesis example are what converted each functional group into the isocyanate group content.

Synthesis of Polyisocyanate Compound (a1)

Synthesis Example 1

Into a reactor equipped with a stirrer, a thermometer, a nitrogen sealing tube and a cooler, 3,000 parts of HDI (made by Nippon Polyurethane Co., Ltd., isocyanate group = 49.9%, solids = 100%) and 6.5 parts of trioctylphosphine as a catalyst were added. After the reaction was conducted at 50 to 55 ° C. for 8 hours with stirring, 1.9 parts of phosphoric acid was added to stop the reaction.

The isocyanate group content of the product was 37.3%, and it was confirmed by FT-IR and ¹³ C-NMR that the isocyanate group, ureidodione group and isocyanurate group were present in the product. Isocyanate group content obtained by reverse titration in aqueous hydrochloric acid solution by reaction with dibutylamine (hereinafter abbreviated as DBA) at the boiling point of high boiling point solvent propylene glycol methyl ether acetate (hereinafter abbreviated as PGM-Ac) is 44.5%. Therefore, the isocyanate group content produced by dissociation of the ureidodione group was 7.2%. In addition, the isocyanurate group content was 5.5%.

This ureidodione group and isocyanurate group containing polyisocyanate compound are made into polyisocyanate A.

Synthesis Example 2

3,000 parts of HDI (Nippon Polyurethane Co., Ltd., isocyanate group content = 49.9%, solid content = 100%) and 2-n-butyl-2-ethyl- in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a cooler 23 parts of 1,3-propanediol were added, the inside of a reactor was nitrogen-substituted, it heated at reaction temperature 60-70 degreeC, stirring, and made it react at the same temperature for 3 hours. At this time, the isocyanate group content of the reaction solution was 49.1%.

Next, 6.0 parts of trioctylphosphine was added as a catalyst, heated to 65 to 70 ° C while stirring, and reacted at the same temperature for 6 hours, and then 3.5 parts of phosphoric acid was added to stop the reaction. An isocyanate group content was 30.3%, yielding a pale yellow reaction product. Unreacted HDI was removed from this reaction product by thin film distillation at 120 degreeC and 0.01 Torr.

The isocyanate group content of the product was 21.1%, and it was confirmed by FT-IR and ¹³ C-NMR that the isocyanate group, ureidodione group and isocyanurate group were present in the product. The isocyanate group content determined by reverse titration in an aqueous hydrochloric acid solution by reacting with DBA at the boiling point of PGM-Ac was 37.5%. Therefore, the isocyanate group content produced by dissociation of ureidodione group was 16.4%. In addition, the isocyanurate group content was 12.5%.

This ureidodione group and the isocyanurate group containing polyisocyanate compound are made into polyisocyanate B.

Synthesis of Organic Compound (A)

Synthesis Example 3

Number average molecular weight synthesized from 100 parts of polyisocyanate A and dimethyl terephthalate / sebacic acid = 1/1 (molar ratio) and EG / NPG = 3/7 (molar ratio) in a reactor equipped with a stirrer, thermometer, nitrogen seal tube and cooler 987 parts of 2000 polyester polyol and 1087 parts of ethyl acetate were added and reacted at 75 degreeC. After 4 hours, the absorption peak of the isocyanate group was confirmed to disappear by FT-IR, and the reaction was terminated to obtain a polyurethane resin containing a ureidodione group, an isocyanurate group, and an active hydrogen group. Let this be PU-1.

Synthesis Example 4

Synthesized from 100 parts of polyisocyanate B, 150 parts of IPDI, isophthalic acid / azelanic acid = 1/1 (molar ratio) and EG / NPG = 3/7 (molar ratio) in a reactor equipped with a stirrer, a thermometer, a nitrogen seal tube and a cooler 2058 parts of polyester polyols (hereinafter abbreviated as polyol A) having a number average molecular weight of 2000 and 2308 parts of ethyl acetate were added and reacted at 75 ° C. After 4 hours, the absorption peak of the isocyanate group was confirmed to disappear by FT-IR, and the reaction was terminated to obtain a polyurethane resin containing a ureidodione group, an isocyanurate group, and an active hydrogen group. Let this be PU-2.

Synthesis Example 5

100 parts of polyisocyanate B, 150 parts of IPDI, 1646 parts of polyol A, rosin polyol KE-601 (manufactured by Kokawa Chemical Co., Ltd., hydroxy group 111.2 KOHmg in a reactor equipped with a stirrer, a thermometer, a nitrogen sealing tube and a cooler) / g, an acid value of 1.8 KOHmg / g, a number average molecular weight of 1010) 205 parts, and 2100 parts of ethyl acetate were added and reacted at 75 ° C. After 4 hours, the absorption peak of the isocyanate group was confirmed to disappear by FT-IR, and the reaction was terminated to obtain a polyurethane resin containing a ureidodione group, an isocyanurate group, and an active hydrogen group. Let this be PU-3.

Synthesis Example 6

100 parts of polyisocyanate B, 150 parts of IPDI, 1 part of polyol A, rosin polyol KE-615-3 (manufactured by Kokawa Chemical Industries, Ltd., hydroxy group 58.5 KOHmg / g, acid value 1.5 KOHmg / g, number average molecular weight 2000) 385 parts, and 2281 parts of ethyl acetate were added and reacted at 75 degreeC. After 4 hours, the absorption peak of the isocyanate group was confirmed to disappear by FT-IR, and the reaction was terminated to obtain a polyurethane resin containing a ureidodione group, an isocyanurate group, and an active hydrogen group. Let this be PU-4.

Examples 1-5 and Comparative Examples 1-4

Preparation of adhesive composition for lamination

A polyurethane resin containing an ureidodione group, an isocyanurate group and an active hydrogen group, an organic isocyanate compound, a catalyst, and optionally a coupling agent were blended to prepare an adhesive composition for lamination. These are shown in Table 1 below.

Fabrication of Laminated Films

Under the conditions shown below, the adhesive compositions of Examples 1 to 5 and Comparative Examples 1 to 4 were applied by drying on a first plastic film, and then a second plastic film or metal foil was bonded thereon in a nip roll, and thereon After applying and drying the adhesive composition, a third plastic film was bonded thereon in a nip roll and aged to prepare a laminated film.

Solid content of adhesive composition: 25% (diluted with ethyl acetate)

μ: 25μ NY / 15μ EVOH / 50μ CPP

12μ PET / 7μ Al / 70μ CPP

Application amount of adhesive composition: 3.5g / m ² (after drying)

Drying condition: 80 ℃ × 15 seconds

Aging condition: 25 ℃ × 24 hours

Evaluation of Laminated Film

Evaluation of the laminated film was performed under the conditions shown below. The results are shown in Tables 2 to 6 below.

Peel Adhesion Strength: T-type Peel Test (according to JIS K 6854)

Tensile Speed: 300 mm / min

Self-treatment: The laminated | multilayer film which consists of NY / EVOH / CPP was heat-sealed, the pouch was made, and after filling with water, it boiled for 30 minutes at 95 degreeC.

Retort Treatment: The laminated film made of PET / Al / CPP was heat sealed to prepare a pouch, and filled with water, followed by a retort treatment at 120 ° C. for 30 minutes.

Synthesis of Polyurethane Resin (Does not Contain Ureidodione Group and Isocyanurate Group)

Synthesis Example 7

100 parts of IPDI, polyol A 720 parts, rosin-containing polyol KE-615-3 (manufactured by Kokawa Chemical Co., Ltd., 58.5 KOHmg / g, 168 parts of acid value 1.5 KOHmg / g, number average molecular weight 2000) and 988 parts of ethyl acetate were added and reacted at 75 degreeC. After 4 hours, it was confirmed by FT-IR that the absorption peak of the isocyanate group had disappeared, and the reaction was terminated to obtain a polyurethane resin (containing no ureidodione group and isocyanurate group). Let this be PU-RF.

Comparative Example 5

Preparation of adhesive composition for lamination

100 parts of polyurethane resin PU-RF (without ureidodione group and isocyanurate group), 5 parts of coronate HL, 0.05 parts of DBU phenol salt and 0.5 parts of v-glycidoxypropyltrimethoxysilane An adhesive composition was prepared. It compares with Example 3 and shows in Table 7 below.

Fabrication of Laminated Films

Under the conditions shown below, the adhesive compositions of Example 3 and Comparative Example 5 were applied and dried on a first plastic film, and then a second plastic film was bonded thereon in a nip roll, and the adhesive composition was applied thereon. After drying by drying, a third plastic film was bonded thereon in a nip roll and aged to prepare a laminated film.

Solid content of adhesive composition: 25% (diluted with ethyl acetate)

Composition of Laminated Film: 25μ NY / 15μ EVOH / 50μ CPP

Application amount of adhesive composition: 3.5g / m ² (after drying)

Drying condition: 80 ℃ × 15 seconds

Aging condition: 25 ℃ × each hour (12 hours, 16 hours and 24 hours)

Evaluation of Laminated Film

The laminated film was evaluated on the conditions shown below. These results are shown in Table 8 below.

Peel Adhesion Strength: T-type Peel Test (according to JIS K 6854)

Tensile Speed: 300 mm / min

Laminated films, such as plastic films or metal foils, prepared using the adhesive composition for lamination of the present invention, exhibit good adhesion strength within a short time at room temperature, and shorten the aging time and lower the aging temperature as compared with conventionally known adhesive compositions. I can do it. In addition, even after the boiling process or the retort treatment, no abnormality such as layer peeling was observed on the appearance of the laminated film, and it was confirmed that it had a practical high adhesive strength.

Therefore, according to this invention, the productivity and workability of a laminated | multilayer film were improved significantly, and cost reduction and short delivery time became possible.

Claims (6)

With an organic compound (A), an organic isocyanate compound (B) and a catalyst (C) containing at least an isocyanurate group and an ureidodione group and an isocyanate-reactive group in an equivalent ratio of ureidodione group / isocyanate-reactive group = 0.25 to 1.0 A laminating adhesive composition comprising: a polyisocyanate component (a) consisting of a polyisocyanate compound (a1) containing at least a ureidodione group and an isocyanurate group and a molecule having a molecular weight of 18 to 20,000 Characterized in that it is an organic compound obtained by reacting component (b) having two or more isocyanate-reactive groups with the equivalent ratio of isocyanate-reactive groups of component (b) to isocyanate groups of polyisocyanate component (a) exceeding 1.0 The adhesive composition for lamination. With an organic compound (A), an organic isocyanate compound (B) and a catalyst (C) containing at least an isocyanurate group and an ureidodione group and an isocyanate-reactive group in an equivalent ratio of ureidodione group / isocyanate-reactive group = 0.25 to 1.0 A laminating adhesive composition comprising: the organic compound (A) consists of a polyisocyanate compound (a1) containing at least a ureidodione group and an isocyanurate group and a polyisocyanate compound (a2) having two or more isocyanate groups in a molecule The equivalent ratio of the isocyanate-reactive group of component (b) to the isocyanate group of the polyisocyanate component (a) is 1.0 in the polyisocyanate component (a) and the component (b) having two or more isocyanate-reactive groups in a molecule having a molecular weight of 18 to 20,000. By reacting under conditions exceeding The adhesive composition for lamination, characterized in that the organic compound obtained. An organic compound (A), an organic isocyanate compound (B), a catalyst (C) containing at least an isocyanurate group and an ureidodione group and an isocyanate-reactive group in an equivalent ratio of ureidodione group / isocyanate-reactive group = 0.25 to 1.0 A laminating adhesive composition comprising a coupling agent (D), wherein the organic compound (A) has a molecular weight of polyisocyanate component (a) made of a polyisocyanate compound (a1) containing at least a ureidodione group and an isocyanurate group Obtained by reacting component (b) having two or more isocyanate-reactive groups in the molecule having from 18 to 20,000 under conditions in which the equivalent ratio of isocyanate-reactive groups of component (b) to isocyanate groups of polyisocyanate component (a) exceeds 1.0 The adhesive composition for lamination characterized in that the organic compound . An organic compound (A), an organic isocyanate compound (B), a catalyst (C) containing at least an isocyanurate group and an ureidodione group and an isocyanate-reactive group in an equivalent ratio of ureidodione group / isocyanate-reactive group = 0.25 to 1.0 A laminating adhesive composition comprising a coupling agent (D), wherein the organic compound (A) contains a polyisocyanate compound (a1) containing at least a ureidodione group and an isocyanurate group and a polyisocyanate having two or more isocyanate groups in a molecule thereof. Isocyanate reactivity of component (b) with polyisocyanate component (a) consisting of compound (a2) and component (b) having two or more isocyanate reactive groups in a molecule having a molecular weight of 18 to 20,000 Half under the condition that the equivalence ratio of groups exceeds 1.0 The laminated adhesive composition, characterized in that the organic compound is obtained by. The method according to any one of claims 1 to 4, Adhesive composition for lamination in which a component (b) contains a rosin polyol (b1). A method for producing a laminated film, wherein the adhesive composition for lamination according to any one of claims 1 to 5 is applied to a first film and dried, and then the second film is bonded thereto and aged at room temperature.