JP3363355B2 - Adhesive composition for two-component dry lamination - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an adhesive composition for dry lamination. More specifically, the curing speed is fast and the stability of the compounding liquid is excellent, and the adhesiveness to various plastic films, metal vapor deposition films, aluminum foils, etc.
The present invention relates to an adhesive composition having excellent acid resistance and heat resistance.

[0002]

2. Description of the Related Art As a packaging material used for food packaging, pharmaceutical packaging, cosmetic packaging, etc., a multi-layer composite obtained by laminating plastic films such as polypropylene, nylon, polyester, polyvinyl chloride, etc., metal vapor deposition films, and metal foils such as aluminum foil. Film is widely used. Conventionally, a polyester adhesive or a polyester polyurethane adhesive has been used for the adhesion between the plastic film and the metal vapor deposition film or the metal foil. However, when used as a food packaging material that requires high-temperature sterilization treatment such as boiling and retort, heat resistance was insufficient. In addition, when the base material to be bonded is an aluminum foil or an aluminum vapor-deposited film, sufficient laminating strength was not obtained. For the purpose of improving these drawbacks, for example, a two-part curable adhesive comprising a polyisocyanate and a polyol having a carboxyl group bonded to the main chain via an ester bond (Japanese Patent Laid-Open No. 3-2.
81589); a hydroxycarboxylic acid having a number average molecular weight of 200 to 5,000, an acid value of 20 to 350, and a hydroxyl value of 20 to 350 as a part of the polyol component accounts for the acid value of the solid content of the adhesive composition. Adhesive composition for dry lamination containing an amount of an acid value derived from a hydroxycarboxylic acid of 1 to 20 (JP-A-8-18394).
3) etc. are proposed.

[0003]

However, since these adhesive compositions have a low curing speed after laminating and a low initial adhesive strength, they are likely to cause floating (so-called tunneling phenomenon) on a part of the laminated film. There was a problem. Further, since the curing speed is slow, it is necessary to take a long curing time, and there is a problem in productivity, and improvement has been desired.

[0004]

[Means for Solving the Problems] The present inventors have obtained an adhesive composition which has a high curing rate, can shorten the curing time, is excellent in the stability of the compounding liquid over time, and is excellent in the finished appearance of a laminated film. As a result of intensive studies, the present invention has been achieved. That is, the present invention relates to the polyol component (A)
And a polyisocyanate component (B) for a dry laminating adhesive, wherein (A) is a carboxyl group-containing organic polymer polyol (A1), and 3 to 80 equivalent% of the carboxyl group is neutralized with a base. A solventless or solvent-type two-component adhesive composition for dry lamination.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, as the carboxyl group-containing organic polymer polyol (A1), for example, carboxyl group-containing polyurethane polyol (a1),
A carboxyl group-containing polyester polyol (a2),
Examples thereof include a carboxyl group-containing acrylic polyol (a3) and a mixture of two or more thereof.

The above (a1) is, for example, a compound having a hydroxyl group at the molecular end and a carboxyl group at the side chain by the urethanization reaction of the organic polyisocyanate (d1) with the polyols (d2) and the dihydroxycarboxylic acid (d3). can get.

Examples of the above (d1) include aromatic polyisocyanate [tolylene diisocyanate (TD
I), diphenylmethane diisocyanate (MDI),
Naphthylene diisocyanate, xylylene diisocyanate (XDI), etc.], modified products of these diisocyanates (isocyanurate, burette, uretdione,
Modified products such as carbodiimide), araliphatic polyisocyanates [α, α, α ', α'-tetramethylxylylene diisocyanate (TMXDI), xylylene diisocyanate (XDI), etc.], aliphatic polyisocyanates (hexamethylene diisocyanate, Lysine diisocyanate), alicyclic polyisocyanate [4,4 '
-Dicyclohexyl methane diisocyanate (hydrogenated MD
I), isophorone diisocyanate (IPDI), cyclohexane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylylene diisocyanate, etc.],
And mixtures of two or more of these. Of these, preferred are TDI and MDI, and particularly preferred is TDI.

The above (d2) includes, for example, a high molecular weight polyol having a number average molecular weight of 500 to 4,000 (for example, polyether polyol, polyester polyol, polycarbonate polyol and a mixture of two or more thereof), a number average molecular weight. Low molecular weight polyols of less than 500 [eg, ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5 pentanediol, glycerin, trimethylolpropane, penta. Erythritol, methyl glucoside, alkylene oxide adduct of these (molecular weight less than 500),
Alkylene oxide adducts (molecular weight less than 500) of bisphenols (bisphenol A, etc.), and mixtures of two or more thereof. The number of hydroxyl groups in (d2) is usually 2-8, preferably 2-3.

Examples of the polyether polyols include alkylene oxide adducts of the above low molecular weight polyols and polyoxytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin and a mixture of two or more of these (block or random addition). Is mentioned.

Examples of the polyester polyol include condensed polyester polyols obtained by polycondensing a dicarboxylic acid or an ester-forming derivative thereof and one or more kinds of the low molecular weight polyols.
Examples of the dicarboxylic acid or its derivative include aliphatic dicarboxylic acids (succinic acid, adipic acid, sebacic acid, azelaic acid, maleic acid, dimer acid, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), And the lower alkyl ester thereof. Among the dicarboxylic acids, preferred are the aliphatic dicarboxylic acids, and particularly preferred is adipic acid. In addition, lactones (eg, ε-caprolactone) may be added to the polyester polyol as the low molecular weight polyol.
Also included are polylactone polyols (polycaprolactone diols, polycaprolactone triols, etc.) obtained by ring-opening polymerization using styrene as an initiator.

As the polycarbonate polyol, for example, one or more of the above-mentioned low molecular weight polyols and carbonic acid diesters (dimethyl carbonate, diethyl carbonate, etc.) are used.
Examples thereof include those obtained by condensation polymerization with

Among these polyols (d2), preferable ones are those having a number average molecular weight of 500 to
4,000 polyether polyol and number average molecular weight 5
A combination with a low molecular weight polyol of less than 00 is more preferable, and a combination of polypropylene glycol and polypropylene triol with dipropylene glycol is more preferable. The weight ratio of the polyether polyol and the low molecular weight polyol when used in combination is usually (20-80) :( 80-2
0), preferably (30 to 70) :( 70 to 30), and the number average molecular weight thereof is preferably 250 to 1,500.

Examples of (d3) include α, α-dimethylolalkanoic acid [dimethylolpropionic acid (molecular weight; 134, acid value; 419, hydroxyl value; 837), dimethylolbutanoic acid (molecular weight; 148, acid Value; 379, hydroxyl value; 758), dimethylolnonanoic acid (molecular weight; 2
18, acid value; 257, hydroxyl value; 515), etc.], tartaric acid (molecular weight; 150, acid value; 748, hydroxyl value; 74
8), an esterified product of 1 mol of citric acid and 1 mol of ethylene glycol (molecular weight; 240, acid value; 468, hydroxyl value; 468), 1 mol of malic acid and 1 ethylene glycol
Esters with moles (molecular weight; 178, acid value; 31
5, hydroxyl value; 630) and the like. Among these, preferable are α, α-dimethylolalkanoic acids, and more preferable are dimethylolpropionic acid and dimethylolbutanoic acid.

The above-mentioned (a1) is the hydroxyl group (O) of (d2).
H) and the total equivalent of hydroxyl groups (OH) of (d3) and (d1)
Equivalent ratio (OH / NC) to isocyanate group (NCO)
O ratio) is usually 1.1 to 3.0, preferably 1.2 to
It can be obtained by carrying out a urethanization reaction by a one-shot method or a multi-step method at 2.0.

The urethanization reaction is carried out without solvent or in the presence of a solvent. Examples of the solvent include aromatic hydrocarbon solvents (toluene, xylene, trimethylbenzene, etc.), ester solvents (ethyl acetate, butyl acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, etc.), ether solvents (cellosolve acetate). , Carbitol acetate, etc.), a ketone-based solvent (methyl ethyl ketone, methyl isobutyl ketone, etc.), and a mixed solvent of two or more thereof. Among these, preferred are ester solvents, and particularly preferred is ethyl acetate. The reaction temperature is usually 30 to 12
The temperature is 0 ° C, preferably 60 to 110 ° C. The reaction time is usually 3 to 30 hours, preferably 5 to 20 hours. It is also possible to use a known polymerization catalyst (for example, an organometallic compound such as dibutyltin dilaurate, stannous octoate or stannas octoate) for promoting the reaction. The amount of the catalyst used is usually (d1),
Usually 0.0 with respect to the total weight of (d2) and (d3)
It is from 01 to 0.5% by weight.

The carboxyl group-containing polyester polyol (a2) in the above (A1) is, for example,
It can be obtained by polycondensing a hydroxycarboxylic acid component having at least one carboxyl group and at least one hydroxyl value in the molecule with a diol component. That is, the equivalent ratio of the carboxyl group (COOH) in the hydroxycarboxylic acid component and the hydroxyl group (OH) in the diol component (COOH /
OH) obtained by polycondensing 1.1 or more (preferably 1.2 to 2); a lactone (ε-caprolactone, γ-valerolactone, etc.) to the dihydroxycarboxylic acid exemplified as the above (d3). Examples thereof include those obtained by ring-opening polyaddition. Examples of the hydroxycarboxylic acid component in the above include lactic acid, tartaric acid, citric acid,
Examples include malic acid and the like. Further, examples of the diol component include the diol in the polymer and / or low molecular weight polyol described in the item (d2). The acid value and the hydroxyl value of the obtained (a2) can be adjusted, for example, by using a polyester polyol composed of the aforementioned dicarboxylic acid or its ester-forming derivative and one or more kinds of the low molecular weight polyols in combination. it can.

As a method for synthesizing the above (a2), a known method can be used, and for example, a method of polycondensing the above-mentioned carboxylic acid component and diol component at a temperature of about 170 to 250 ° C. can be exemplified. In synthesizing this polyester, an esterification or transesterification catalyst usually used for accelerating the reaction, for example, antimony dioxide, zinc acetate, lead acetate, manganese acetate or the like can be used.

As the carboxyl group-containing polyacrylic polyol (a3) of the above (A1), for example, a hydroxyl group-containing polymerizable monomer, α, β-unsaturated carboxylic acid and (meth) acrylic acid alkyl ester are used. Obtained by copolymerization.

Examples of the hydroxyl group-containing polymerizable monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2
-Hydroxybutyl (meth) acrylate and the like can be mentioned. Of these, preferred is 2-hydroxyethyl (meth) acrylate. As the α, β-unsaturated carboxylic acid, monobasic acids such as (meth) acrylic acid and crotonic acid; polybasic acids such as maleic acid, itaconic acid and fumaric acid or acid anhydrides thereof; Examples thereof include monoalkyl esters. Of these, preferred are acrylic acid, methacrylic acid, maleic anhydride and itaconic acid, and particularly preferred is acrylic acid. Examples of the (meth) acrylic acid alkyl ester include (meth) acrylate [methyl (meth) acrylate, n-butyl (meth) acrylate, 2-butyl (meth) acrylate] from an aliphatic alcohol.
t-butyl (meth) acrylate, pentyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, etc.], alicyclic Examples thereof include (meth) acrylates [cyclohexyl (meth) acrylate and the like] from formula alcohols, (meth) acrylates [benzyl (meth) acrylate and the like] from aromatic alcohols, and mixtures of two or more thereof. Of these, particularly preferred are methyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and mixtures of two or more thereof.

(A3) is a known polymerization initiator (azobisisobutyronitrile, azobisisovaleronitrile, etc.) prepared by a known polymerization method (bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, etc.). Polymerization initiators; peroxide polymerization initiators such as benzoyl peroxide, di-t-butyl peroxide, lauryl peroxide, etc.) can be used.

Among the examples exemplified as the above (A1), the carboxyl group-containing polyurethane polyol (a1) is preferable.

The acid value of (A1) is usually from 1 to 20, preferably from 3 to 15, the hydroxyl value is usually from 10 to 80, preferably from 15 to 65, and the number of hydroxyl groups is usually from 2 to 8, preferably. 2-3. When the acid value is less than 1, the adhesion to metal foil such as aluminum and the metal vapor-deposited film becomes insufficient, and when it exceeds 20, the reaction with the polyisocyanate component (B) becomes remarkably slow and the initial adhesive force (immediately after laminating Adhesive strength) is inferior. Further, when the hydroxyl value is less than 10, the hot water resistance is poor because the number of crosslinking points with the polyisocyanate component (B) is small, and when it exceeds 80, the number of crosslinking points with the polyisocyanate component (B) is too large and the coating This is not preferable because the viscosity of the liquid [a mixed liquid of (A) and (B)] increases with time and the stability of the coating liquid deteriorates. The number average molecular weight of the (A1) is usually 3,000 to 100,000, preferably 5,000 to 50,000. If the number average molecular weight is less than 3,000, the resin becomes hard and brittle,
The adhesive strength becomes insufficient, and when it exceeds 100,000, the coating viscosity becomes high, so that the coated film becomes uneven, and the laminated film appearance tends to be poor.

The polyol component (A) in the present invention is
It must be composed of a carboxyl group-containing organic polymer polyol (A1), and 3 to 80 equivalent% of the carboxyl group is neutralized with a base. The carboxyl group in (A1) is preferably 5 to 65 equivalent%, more preferably 10 to 50 equivalent% neutralized with a base. (A
When the neutralization ratio of the carboxyl group in 1) is less than 3 equivalent%, the rate of curing reaction with the polyisocyanate component (B) described later is slow and the initial adhesive force tends to be insufficient.
On the other hand, when the neutralization rate exceeds 80 equivalent%, (A) and (B)
The stability over time of the compounded solution of 1 tends to deteriorate. Examples of the base used for neutralization include tertiary amines and alkali metal hydroxides (eg sodium hydroxide, potassium hydroxide, etc.). Of these, preferably the third
It is a primary amine.

Examples of the tertiary amine include aliphatic amines (trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-octylamine, diethyl-1-propylamine, etc.). Alicyclic amines [N-methylpyrrolidine, N-
Ethylpyrrolidine, N-methylpiperidine, N-ethylpiperidine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, N-methylmorpholine, N
-Butylmorpholine, N, N'-dimethylpiperazine,
N, N′-diethylpiperazine, 1,5-diazabicyclo (4,3,0) -5-nonene, 1,8-diazabicyclo [5,4,0] -7-undecene, pyridine, 4-dimethylaminopyridine, Picolins, 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, 1,2-dimethylimidazoline, 1,2,4-trimethylimidazoline, 1,
4-dimethyl-2-ethylimidazoline and the like]; and a mixture of two or more thereof. Among these, preferred are trimethylamine, triethylamine and tri-n-butylamine among the aliphatic amines, and particularly preferred is triethylamine.

The polyol component (A) and the isocyanate component (B) in the present invention have an NCO / OH equivalent ratio of usually 1.1 to 4, preferably 1.2 to 3, and more preferably 1.3 to 2. It is mixed in the following range. If the NCO / OH equivalent ratio is less than 1.1 or exceeds 4, sufficient adhesive force may not be obtained.

In the present invention, various films (especially metal vapor deposition film, especially metal vapor-deposited film, can be obtained by using phosphoric acid triester (C) together with (A) and (B).
A wettability with respect to a metal foil) is improved, and a composite film having an excellent finished appearance of a laminated film can be obtained.

Examples of (C) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate and the like. Of these, particularly preferred is triethyl phosphate.

The amount of (C) used is usually 1 to 30% by weight, preferably 1 to 20% by weight, based on the weight of (A). If it is less than 1% by weight, sufficient wetting cannot be obtained, and if it exceeds 30% by weight, the cohesive force of the adhesive after curing is deteriorated and the laminate strength is deteriorated. The (C) may be added at the time of mixing the (A) and (B), or may be contained in either (A) or (B) in advance.

The polyisocyanate component (B) used in the present invention is, for example, at least one of the above-mentioned organic polyisocyanates (d1) and at least one of the high molecular weight polyols and low molecular weight polyols exemplified as the polyols (d2). A compound (B1) having a free isocyanate (NCO) group at the terminal, which is obtained by a urethanization reaction with one type, is used.

The equivalent ratio (NCO / OH ratio) of the isocyanate group (NCO) of (d1) to the hydroxyl group (OH) of (d2) of the (B1) is usually 1.1 to 5.0, preferably 1 It is obtained by reacting in the range of 0.2 to 3.0. The urethanization reaction is usually performed without a solvent or in the presence of a solvent. Examples of the solvent include the solvents (toluene,
Ethyl acetate etc.) can be used. The reaction temperature is generally 30 to 120 ° C, preferably 60 to 110 ° C.
The reaction time is generally 3 to 15 hours, preferably 5 to 10 hours. It is also possible to use known polymerization catalysts (eg, organometallic compounds such as dibutyltin dilaurate, stannous octoate, stannas octoate) to accelerate the reaction. The amount of catalyst used is usually (d
It is 0.001 to 0.5% by weight based on the total of 1) and (d2). The NCO content of the (B1) is usually 2 to 10% by weight.

In order to laminate various plastic films and metal vapor-deposited films with the adhesive composition of the present invention, first, (A), (B) and optionally (C), and optionally a solvent. (Ethyl acetate, etc.) is blended in a predetermined blending ratio to prepare a coating liquid. The coating solution is applied to the surface of a non-heat-fusible film (for example, nylon, aluminum vapor-deposited polyester, biaxially oriented polypropylene film, aluminum foil, etc.) by a solvent-type or solvent-free dry laminator that is usually used, and solvent-type. In the case of, the solvent is volatilized through a drier, and in the case of the solventless type, it is directly laminated on a heat-fusion film (for example, low-density polyethylene, unstretched polypropylene film, etc.), and the adhesive composition is heated at room temperature or under heating. A method of curing (curing) is adopted. The coating amount is usually ² to 5 g / m ² in terms of solid content. The laminated composite film is usually cured for 1 to 3 days under the condition of about 40 ° C.

[0032]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the examples, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified.

[Production of Polyol Component (A)] Production Example 1 In a flask, 242.3 parts of polyoxypropylene diol (number average molecular weight: 951), polyoxypropylene diol (number average molecular weight: 403) 171.1 parts, Polyoxypropylene triol (propylene oxide adduct of glycerin, number average molecular weight: 1,000) 127.
4 parts, 13.7 parts of dipropylene glycol, 11.4 parts of dimethylolpropionic acid, 133.0 parts of TDI and 300 parts of ethyl acetate were charged, and under a nitrogen stream, 80 to 10
The reaction was carried out at 0 ° C for 5 hours, and then dibutyltin dilaurate was added.
0.1 part was added and the mixture was further reacted for 10 hours, and it was confirmed by infrared absorption spectrum that the isocyanate group had disappeared. Acid value (solid content conversion) 7, hydroxyl value (solid content conversion) 47, solid content Min 70%, viscosity 730 mPa · s / 25
C. carboxyl group-containing polyurethane polyol (a-
A solution of 1) was obtained. Then, after cooling the content to 50 ° C. or lower, 1.2 parts of triethylamine [15 equivalent% to the carboxyl group of (a-1)] was added, and the mixture was added at 40 to 50 ° C.
A neutralization reaction was carried out for a time. Thus, acid value (solid content conversion)
7, hydroxyl value (solid content conversion) 47, solid content 70%, viscosity 750 mPa · s / 25 ° C. polyol component (A-1)
Got

Production Example 2 35 parts of triethyl phosphate was added to 965 parts of the polyol component (A-1) prepared in Production Example 1 and mixed at 40 to 50 ° C. for 1 hour to give an acid value (in terms of solid content) of 7, hydroxyl group. Value (converted to solid content) 45, solid content 71%, viscosity about 600 mPa · s / 2
A polyol component (A-2) having a temperature of 5 ° C. was obtained.

Production Example 3 Among carboxyl group-containing polyurethane polyols in the same manner as in Production Example 1, except that 12.5 parts of dimethylolbutanoic acid was used instead of 11.4 parts of dimethylolpropionic acid in Production Example 1. A solution of the Japanese product (a-2) was obtained. To 965 parts of the solution, 35 parts of triethyl phosphate was added, and 40 to 5
Mix for 1 hour at 0 ° C. Thus, acid value (solid content conversion)
7, hydroxyl value (solid content conversion) 45, solid content 71%, viscosity 700mPa · s / 25 ° C polyol component (A-3)
Got

Comparative Production Example 1 A solution of the unneutralized carboxyl group-containing polyurethane polyol (a-1) described in Production Example 1 was added to the polyol component (A-
Used as 4).

Comparative Production Example 2 A polyol component (A-5) consisting of a carboxyl group-containing polyurethane polyol was obtained in the same manner as in Example 1 of JP-A-3-281589. That is, a flask was charged with 1,000 parts of an ethylene oxide adduct of trimethylolpropane (molecular weight: about 1,000), 140 parts of phthalic anhydride and 57 parts of methyl ethyl ketone,
The temperature is raised to 150 to 160 ° C. in 1 hour and 30 minutes, and further 15
The reaction was performed at 0 to 160 ° C. for 1 hour and 30 minutes. Thereafter, the inside of the flask was depressurized to 5 to 10 mmHg to remove the solvent and unreacted materials, and a carboxyl group-modified polyester glycol having an acid value of 48 (solid content conversion) and a hydroxyl value of 90 (solid content conversion) was obtained. 100 parts of the above carboxyl group-modified polyester glycol, 1,200 parts of polypropylene glycol having a hydroxyl value of 75 (molecular weight: 1,500), TDI130
And 950 parts of methyl ethyl ketone were reacted at 90 ° C. for about 10 hours to obtain a carboxyl group-containing polyurethane polyol solution having an acid value of 3 (solid content conversion) and a hydroxyl value of 13 (solid content conversion). This was used as the polyol component (A-5).

[Production of Polyisocyanate Component (B)] Production Example 4 136.5 parts of MDI and a propylene oxide adduct of propylene glycol (number average molecular weight = 95) in a flask.
1) 376.0 parts of ethyl acetate and 237.5 parts of ethyl acetate were charged and reacted at 80 to 100 ° C. for 5 hours under a nitrogen stream, and then 0.04 parts of dibutyltin dilaurate was added and further reacted for 3 hours, NCO content (solid content conversion) is 2.5
% Urethane prepolymer was obtained. Then, after cooling the content to 50 ° C. or lower, 250 parts of polyisocyanate ethyl acetate solution [NCO content (solid content conversion); 17.7%, solid content 75%] in which 3 mol of TDI was added to 1 mol of trimethylolpropane. Was charged and mixed at 40 to 50 ° C. for 1 hour. Thus, NCO content (solid content conversion) 6.5
%, Solid content 70%, viscosity 1,200 mPa · s / 25 ° C.
The polyisocyanate component (B-1) of was obtained.

Example 1 Polyol component (A-1), polyisocyanate component (B-1) and ethyl acetate were mixed in the compounding amounts shown in Table 1 to obtain an adhesive composition 1 of the present invention. This adhesive composition 1 was applied to the first substrate shown in Table 2 with a solvent type dry laminator so as to have a concentration of 2.7 to 3.3 g / m ² (solid content), and a hot air dryer at 70 to 90 ° C. After being dried for about 1 minute in the above and the solvent was volatilized, the coated surface was bonded to the second base material shown in Table 2 to prepare laminated samples X-1 and X-2. The sample X-1 was used to evaluate the curing rate, the finished appearance of the laminate film, the initial adhesive strength and the adhesive strength with time,
Sample X-2 was used to evaluate the adhesion to metal (to aluminum). In addition, the stability of the compounding liquid was evaluated using the adhesive composition 1. The results are shown in Table 3.

Example 2 Example 1 except that the polyol component (A-2) was used in place of the polyol component (A-1).
Adhesive composition 2 of the invention was obtained in the same manner as described above, and laminate samples X-3 and X-4 were prepared. The sample X-3 was used to evaluate the curing rate, the finished appearance of the laminate film, the initial adhesive strength and the adhesive strength with time, and the sample X-4 was used.
Was used to evaluate the adhesion to metal. Further, the adhesive composition 2 was used to evaluate the stability of the compounded liquid. The results are shown in Table 3.

Example 3 Example 1 was repeated except that the polyol component (A-3) was used in place of the polyol component (A-1).
Adhesive composition 3 of the present invention was obtained in the same manner as in, and laminate samples X-5 and X-6 were prepared. The sample X-5 was used to evaluate the curing rate, the finished appearance of the laminated film, the initial adhesive strength and the adhesive strength with time, and the sample X-6 was used.
Was used to evaluate the adhesion to metal. In addition, the stability of the compounding liquid was evaluated using the adhesive composition 3. The results are shown in Table 3.

Comparative Example 1 Example 1 except that the polyol component (A-4) was used in place of the polyol component (A-1) in Example 1.
Comparative Adhesive Composition 4 was obtained in the same manner as in, and Laminate Samples X-7 and X-8 were prepared. Using the sample X-7, the curing speed, the finished appearance of the laminated film,
The initial adhesive strength and the adhesive strength with time were evaluated, and the adhesion to metal was evaluated using Sample X-8. Also, the adhesive composition 4
Was used to evaluate the stability of the formulation liquid. The results are shown in Table 3.

Comparative Example 2 In Example 1, a polyol component (A-5) was used in place of the polyol component (A-1), and a polyisocyanate component (B-1) was used in JP-A-3-281589. Seika Bond C-90 described in [[Dainichi Seika, N
Comparative adhesive composition 5 was obtained in the same manner as in Example 1 except that CO content (solid content conversion): 5.0%, solid content 80%] was used, and laminate samples X-9 and X-10 were obtained. Created. The sample X-9 was used to evaluate the curing rate, the finished appearance of the laminate film, the initial adhesive strength and the adhesive strength with time, and the sample X-10 was used to evaluate the adhesion to metal. Further, the adhesive composition 5 was used to evaluate the stability of the compounding liquid. The results are shown in Table 3.

[0044]

[Table 1]

[0045]

[Table 2]

[0046]

[Table 3]

The evaluation method is as follows.

[Curing speed] The sample was placed in a curing bath at 40 ° C., and the absorption intensity (2300 cm ⁻¹ ) of the isocyanate group immediately after preparation, 3, 5, 7, 24, and 72 hours later was measured by an infrared spectrometer. Then, the reaction rate was obtained from the following calculation formula. The higher the reaction rate in a shorter time, the faster the curing rate. Reaction rate (%) = (1-N / N ₀ ) × 100 N ₀ : IR absorption intensity (height) based on isocyanate groups immediately after the films are bonded N: IR absorption based on isocyanate groups at each elapsed time Strength (height)

[Finishing Appearance of Film] The finishing appearance immediately after the sample was prepared and after 5 hours of winding and curing (40 ° C.) were visually evaluated according to the following criteria. ⊚: The laminated film is excellent in transparency and has no coating unevenness, cracks, or blows (tunneling). ○: The laminated film is excellent in transparency, coating unevenness,
No cracks, blows (tunneling), etc. △; The transparency of the bonded film is good, but some coating unevenness, cracks, blows (tunneling), etc. are seen. Those that can be seen or have coating unevenness, cracks, blows (tunneling), etc.

[Initial adhesive strength] The sample was cut into a size of 200 mm × 15 mm within 30 minutes after preparation, and the T-type peel strength (g / 15 mm) was measured under the following conditions. The larger the value, the better the initial adhesive strength. T-type peel test condition; using an Instron type tensile tester,
The T-type peel strength was measured at 20 ° C. Load speed 300mm
/ Min, unit is g / 15 mm. The measurement was performed on 10 samples, and the average value was used as the test result.

[Adhesion with time] After the sample was prepared, it was placed in a curing bath at 40 ° C., and the T-type peel strength (g / 15 mm) after 3, 5, 7, 24 and 72 hours was measured. It is indicated that the faster the development of the peeling strength indicating the film material destruction (material destruction), the shorter the curing time. The conditions for the T-type peel test are:
The same as in the case of the initial adhesive strength measurement described above.

[Adhesion property to metal] After curing the sample at 40 ° C for 24 hours, the T-type peel strength (g / 15 mm) was measured. The larger the value, the better the adhesion to metal. The T-type peel test conditions are the same as in the case of the above-described initial adhesive force measurement.

[Stability of compounded liquid] Each adhesive composition was placed in a tightly closed container, placed in a constant temperature bath at 40 ° C., taken out after a lapse of time shown in Table 3, and viscosity (second / 4) in Zahn cup # 3.
0 ° C.) was measured. The smaller the difference in viscosity compared to the value after 40 ° C. × 1 hour, the better the stability of the compounding liquid.

[0054]

The adhesive composition for dry lamination of the present invention has the following effects as compared with the conventional adhesive composition. Since the curing speed is fast, the curing time can be shortened and the productivity is greatly improved. The stability of the two-part formulation is excellent. Since the wettability to various plastics, metal vapor deposition films, etc. is good, the finished appearance of the composite film after lamination is excellent. The initial adhesion and adhesion to (deposited) metal are particularly good. The composite film after lamination has excellent acid resistance and heat resistance. From the above effect, the adhesive composition of the present invention is a film composite packaging material for packaging medicines, foods, etc. (for example, polyethylene, polypropylene, polyethylene terephthalate, nylon, cellophane, polystyrene,
It is suitable as an adhesive by a dry lamination method of a resin film such as polyvinyl chloride or polyvinylidene chloride; paper, synthetic paper such as polystyrene or polyethylene; metal vapor deposition film or metal foil such as aluminum or copper). Further, by using the adhesive composition of the present invention, it is possible to obtain a laminated product having improved productivity and stable quality. In addition to the above composite packaging material, it is also useful as an adhesive for laminating a plastic building material such as polyvinyl chloride, ABS, melamine resin or the like and a metal building material such as iron or aluminum and the above-mentioned film.

Continuation of the front page (56) Reference JP-A-8-81671 (JP, A) JP-A-6-228524 (JP, A) JP-A-8-183829 (JP, A) JP-A-7-97557 (JP , A) JP-A-8-60131 (JP, A) JP-A-58-109528 (JP, A) JP-A-8-104861 (JP, A) JP-A-9-255751 (JP, A) JP-A 3-281589 (JP, A) JP-A-8-183943 (JP, A) JP-A-8-27243 (JP, A) JP-A-63-235383 (JP, A) JP-A-3-234783 (JP, A) A) JP-A-4-25589 (JP, A) JP-A-6-313161 (JP, A) JP-A-6-329902 (JP, A) JP-A-7-206965 (JP, A) JP-A-8 -3258 (JP, A) JP-A-8-12959 (JP, A) JP-A-8-92540 (JP, A) JP-A-8-225780 (JP, A) JP-A-8-253550 (JP, A) ) JP-A-60-243182 (JP, A) JP-A-54-90239 (JP, A) JP-A-49-339 (JP, A) A) JP-A-7-207246 (JP, A) JP-A-7-97557 (JP, A) JP-A-5-311146 (JP, A) JP-A-3-182584 (JP, A) JP-A-8 -333431 (JP, A) JP-A-6-172639 (JP, A) JP-A-57-205469 (JP, A) JP-A-9-675556 (JP, A) JP-A-6-25636 (JP, A) ) JP-A-2-274788 (JP, A) JP-A-62-181376 (JP, A) JP-A-57-8274 (JP, A) JP-A-58-129078 (JP, A) JP-A-6- 506007 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C09J 175/04 C08G 18/40 C08L 75/04

Claims (7)

(57) [Claims] 1. A dry laminating adhesive comprising a polyol component (A) and a polyisocyanate component (B), wherein (A) comprises a carboxyl group-containing organic polymer polyol (A1), and 3 to 3 of the carboxyl groups are used.
A solvent-free or solvent-type two-component dry laminate adhesive composition, wherein 80 equivalent% is neutralized with a base. 2. The adhesive composition according to claim 1, wherein (A1) has an acid value of 1 to 20 and a hydroxyl value of 10 to 80. 3. The adhesive composition according to claim 1, wherein the base for neutralizing the carboxyl group in (A1) is a tertiary amine. 4. The adhesive composition according to claim 1, wherein (A1) is a carboxyl group-containing polyurethane polyol. 5. The carboxyl group-containing polyurethane polyol is an organic polyisocyanate having a number average molecular weight of 500.
5. The adhesive composition according to claim 4, which is a polyether polyol of 4,000 to 4,000, a low molecular weight polyol having a number average molecular weight of less than 500, and a carboxyl group-containing polyurethane polyol derived from dihydroxycarboxylic acid. 6. A phosphoric acid triester (C) is further added,
The adhesive composition according to claim 1, which is contained in an amount of 1 to 30% by weight based on the weight of (A). 7. An adhesive body obtained by adhering a composite packaging material selected from a resin film, paper, synthetic paper, metal vapor deposition film, and metal foil using the adhesive composition according to any one of claims 1 to 6.