JP2001152127A - Polyurethane adhesive composition and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an adhesive composition for dry laminating that has improved properties in heat-resistant adhesion, hot water-resistant adhesion, acid- resistant adhesion, and oil-resistant adhesion and is applicable for various kinds of contents including all foods; and to provide a manufacturing method therefor. SOLUTION: An organic polyisocyanate is reacted with a polymer polyol, and further with an epoxy resin if desired, to produce a polyurethane polyol, which is then reacted with a copolymer of styrene with maleic anhydride to obtain a modified polyurethane resin. An organic polyisocyanate as a hardener is added to the above resin as a base resin to prepare the object polyurethane adhesive composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention is used in the production of a composite laminate film made by laminating various plastic films, metal foils, metallized films and the like.
The present invention relates to an adhesive composition for a composite laminate film having excellent heat resistance, water resistance, acid resistance, and oil resistance.

[0002]

2. Description of the Related Art As a material for food packaging, pharmaceutical packaging and cosmetics packaging, a composite laminate film obtained by laminating various plastics, for example, a film of polyethylene, polypropylene, nylon, polyethylene terephthalate, polyvinylidene chloride and a metal foil such as an aluminum foil. Also, composite laminate films obtained by laminating the above plastic films are already widely used.

[0003] As a method for bonding these plastic films or metal foils, various techniques have been developed based on a combination of, for example, polyester polyurethane polyol, organic polyisocyanate and epoxy resin. On the other hand, especially in the field of food packaging, along with the trend of improving the eating habits and simplifying the era, as the packed foods become more diverse and sophisticated, the content composition becomes more complicated, and various sources, The diversification of combinations of soy sauce, vinegar, animal and vegetable fats and oils, various spices, alcohol-containing substances, etc., has never stopped. At the same time, the sterilization temperature of the food is 100 ° C (boil), 120 ° C (retort) and 135 ° C.
℃ (high retort), water resistance at high temperature,
Strict performances such as oil resistance and acid resistance are required for laminate films, but this tendency is expected to continue to increase with the complexity of the contents.

[0004] In recent years, urethane-based adhesive compositions with improved adhesive performance have been used for packaging foods containing vinegar, free fatty acids, and the like. For example,
There have been proposed urethane adhesives composed of a polymer polyol and a polyisocyanate, to which pyromellitic anhydride is added, and those obtained by grafting maleic acid and its anhydride to a polyol component. These have been found to improve the adhesive strength when acidic foods are used as contents, but they still have many insufficient points. For example, when a vinegar component or a mixture containing animal fats and oils is packed and stored for a long period of time to observe the state of delamination between aluminum foil and CPP (unstretched polypropylene), there are still weak points. Understand.

[0005]

As a result of various studies to solve the technical problems of the conventional adhesive,
An adhesive composition for dry lamination that can improve various properties such as heat-resistant adhesiveness, hot-water adhesiveness, acid-resistant adhesiveness, and oil-resistant adhesiveness, and is practical for all kinds of contents including foods and the like. It does not provide a manufacturing method.

[0006]

Means for Solving the Problems The first invention of the present application is:
A polyurethane adhesive composition for a composite laminate film comprising (a) an organic polyisocyanate, (b) a polymer polyol, and (c) a copolymer of styrene and maleic anhydride, wherein (a) an organic polyisocyanate and A polyurethane adhesive composition comprising, as a main component, a modified polyurethane resin obtained by reacting b) a polymer polyol with (c) a copolymer of styrene and maleic anhydride, and (a) a curing agent containing an organic polyisocyanate. The second invention of the present application is a process for producing a polyurethane adhesive composition for a composite laminate film, comprising (a) an organic polyisocyanate, (b) a polymer polyol, and (c) a copolymer of styrene and maleic anhydride. In the method, (a) an organic polyisocyanate is reacted with (b) a polymer polyol to produce a polyurethane polyol, and (c) a copolymer of styrene and maleic anhydride is reacted with the polyurethane polyol to form a modified polyurethane resin. The present invention provides a method for producing a polyurethane adhesive composition, characterized in that this modified polyurethane resin is used as a main component and (a) an organic polyisocyanate is added as a curing agent. The third invention of the present application provides (a)
Organic polyisocyanate, (b) polymer polyol,
Provided is a polyurethane adhesive composition for a composite laminate film, comprising (c) a copolymer of styrene and maleic anhydride, and (d) an epoxy resin. The fourth invention of the present application relates to (a) an organic polyisocyanate, (b)
A method for producing a polyurethane adhesive composition for a composite laminate film comprising a polymer polyol, (c) a copolymer of styrene and maleic anhydride, and (d) an epoxy resin, wherein (a) an organic polyisocyanate and (b) A) producing a polyester polyurethane resin in which a polymer polyol and (d) an epoxy resin are blended; and (c) reacting a copolymer of styrene and maleic anhydride with the polyester polyurethane resin to produce a modified polyester polyurethane resin. Provided is a method for producing a polyurethane adhesive composition comprising a modified polyester polyurethane resin as a main component and (a) an organic polyisocyanate as a curing agent.

The organic polyisocyanate used in the present invention includes, for example, hexamethylene diisocyanate, phenylene diisocyanate, 2,4 or 2,
6-tolylene diisocyanate, diphenylmethane-
4,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, ω, ω'-diisocyanate-1,3 dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, tetramethyl Xylylene diisocyanate, ω, ω'-diisocyanate-1,3-dimethylcyclohexane, ω, ω'-diisocyanate 1,4-
Polyisocyanate monomers such as dimethylcyclohexane, and mixtures thereof, dimers, trimers, burette compounds, allophanate compounds derived from the above polyisocyanate monomers and low molecular weights of less than 200 such as trimethylolpropane and glycerin. An adduct with a polyol, or a polyester polyol having a molecular weight of about 200 to 30,000,
Adducts of polyether polyol, polyester polyether polyol and the like can be mentioned.

The polymer polyol used in the present invention has a functional group number of about 2 to 6, preferably about 2 to 4, and a molecular weight of about 500 to 100,000, preferably 3,000.
20,000 compounds.

More specifically, a polyester polyol,
Polyether polyols, polyether ester polyols, acrylic polyols, polyurethane polyols or mixtures thereof are mentioned.

Examples of such polyester polyols include, for example, dibasic acids such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, and dialkyl esters thereof, or mixtures thereof;
For example, ethylene glycol, propylene glycol,
Examples include polyester polyols obtained by reacting glycols such as diethylene glycol, butylene glycol, neopentyl glycol, 1,6-hexanediol, or a mixture thereof.

Examples of polyether polyols include oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran, and low molecular weight polyols such as water, ethylene glycol, propylene glycol, trimethylolpropane and glycerin as initiators. And polyether polyols obtained by polymerization.

The polyether ester polyol is obtained by reacting a dibasic acid such as terephthalic acid, isophthalic acid, adipic acid, azelaic acid, sebacic acid, or a dialkyl ester thereof or a mixture thereof with the above polyether polyol. Polyetherester polyols are included.

As the acrylic polyol, one in one molecule is used.
It can be obtained by copolymerizing a polymerizable monomer having at least two hydroxyl groups, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., or their corresponding methacrylic acid or its ester.

The polyurethane polyol is a polyol having a urethane bond in one molecule, for example, a polyester polyol, a polyether polyol, a polyether ester polyol, an acryl polyol having a molecular weight of about 500 to 20,000, and the above-mentioned organic polyether. Obtained by reacting with isocyanate.

The copolymer of styrene and maleic anhydride used in the present invention is, for example, one known under the trade names such as SMA Resin (trademark) of Arco Chemical Company and Scripset (trademark) of Monsanto Company. Having a molecular weight of about 1,000 to 350,000, preferably about 1,000.
0 to 120,000. The copolymerization ratio of styrene to maleic anhydride is from 1: 1 to 5: 1, preferably about 1: 1.
~ 2: 1 is used. The amount of the copolymer of styrene and maleic anhydride is 1 to the total adhesive composition.
-30% by weight, preferably 2-15% by weight.

The copolymer of styrene and maleic anhydride is not compatible with an organic polyisocyanate such as an adduct of 3 moles of isophorone diisocyanate and 1 mole of trimethylolpropane, and the two polymers are not soluble in ethyl acetate. When mixed, it was thought that a precipitate immediately formed and was unusable. However, it has been discovered that by partially reacting a copolymer of styrene and maleic anhydride with, for example, a polyester polyurethane polyol in advance, the copolymer is completely compatible with the polyisocyanate compound at a free ratio. . Further, the polyurethane resin modified with the copolymer of styrene and maleic anhydride does not cause a change such as an increase in viscosity even after storage at 50 ° C. for 5 months or more. It is not clear why polyurethane resins modified with this copolymer of styrene and maleic anhydride exhibit excellent performance in hot water adhesion, heat resistance, oil resistance, and acid resistance. And a maleic anhydride copolymer were specifically effective. For example, a copolymer of isobutylene and maleic anhydride showed no such effect. Also, when a maleic anhydride monomer was used, the effect was not recognized.

In the present invention, the present invention can be carried out by adding an epoxy resin or the like. The epoxy resin is, for example, a reaction product of a polyhydric phenol such as bisphenol A and tetrahydroxydiphenylethane with a polyfunctional halohydrin such as epichlorohydrin, and is a trade name such as Epicoat (trademark) of Yuka Shell Co., Ltd. With a known molecular weight of about 330 to 10,000,
Preferably about 330-4,000 are used.
The amount of the epoxy resin is 1 to 20 with respect to the total adhesive composition.
% By weight, preferably 1 to 10% by weight. The addition may be performed at a high temperature during the resin synthesis reaction or at a cold time after the completion of the reaction. Further, in the present invention, the present invention can be carried out by adding other components widely used in this kind of polyurethane adhesive composition for dry lamination.

[0018]

Next, the present invention will be described in more detail with reference to examples. However, the present invention should not be construed as being limited to these examples.

Example 1 194 g of dimethyl phthalate, ethylene glycol 12
4 g, 104 g of neopentyl glycol and 0.1 g of tetrabutyl titanate under a N ₂ gas flow from 160 to 220.
A transesterification reaction was performed at ° C.

After distilling a predetermined amount of methanol, sebacic acid 2
02g and adipic acid 73g, 220-230 ° C
And gradually reduce the pressure to 230-26.
The polycondensation reaction was carried out at 0 ° C. under 1 mmHg for 3 hours. A polyester polyol having a number average molecular weight of about 6,000 was obtained.
This was dissolved and diluted in ethyl acetate to give a 50% NV solution.

In addition, dibutyltin dilaurate 0.15
g, isophorone diisocyanate (100 g) and ethyl acetate (100 g) were added, and the mixture was reacted at 70 ° C. for 7 hours in an N ₂ gas stream. OH number 10 with number average molecular weight of about 10,000
Of polyurethane polyol was obtained.

SMA resin (trademark) 1,000A
(Styrene / maleic anhydride = 1/1 copolymer, molecular weight 1,600, product of Arco Chemical Co.)
After adding 2 g and 102 g of ethyl acetate, the mixture was reacted at 70 ° C. for 60 minutes to obtain a viscosity U (bubble viscometer, 25 ° C., NV50
%) Of a modified polyester polyurethane resin.

To 100 g of the above resin solution (base agent), as a curing agent, a polyisocyanate compound Takenate (trademark) D-140N (3 mol of isophorone diisocyanate / 1 mol of trimethylolpropane, 75% ethyl acetate solution, Takeda Chemical Co., Ltd. 10 g), diluted with ethyl acetate to 25%, and PET was applied using a laminator so that the solid content was 3.5 g / m ^2.
(12μ thickness) / Al (40μ thickness) / CPP (50μ thickness)
Were bonded to three layers, and an adhesion test described later was performed.

Example 2 According to the method of Example 1, isophthalic acid / sebacic acid =
1 / 1.5 (molar ratio), ethylene glycol / neopentyl glycol / 1.6 hexanediol / epicoat 828 (epoxy resin manufactured by Yuka Shell Co., Ltd.) = 1 /
The reaction was carried out at a ratio of 0.65 / 1 / 0.1 (molar ratio) to obtain a polyester polyol having a number average molecular weight of about 5,000.

This was reacted with isophorone diisocyanate in an ethyl acetate solution to give a number-average molecular weight of about 9,000.
A polyester polyurethane resin solution having an OH value of 0 and an OH value of 15 was obtained. To this, SMA Resin (trademark) 1,000A was added so as to be 5% of the total adhesive composition, and reacted in the same manner as in Example 1 to obtain a modified polyester polyurethane resin. The above-mentioned Takenate (trademark), which is a polyisocyanate compound as a curing agent, is added to 100 g of the resin solution (base resin).
10 g of D-140N was blended and bonded under the same conditions as in Example 1.

Example 3 A similar polyester polyol was synthesized from the same raw materials according to the production method shown in Example 1, and then ω, ω'-diisocyanate-1,3 dimethylbenzene was used as a crosslinking agent. The same reaction was performed to obtain a polyester polyurethane solution having an OH value of 5.

[0027] Epicoat (trademark) 1001, SM
A Resin (trademark) 1,000 A was added to each so as to be 5% of the total adhesive composition, and reacted in the same manner as in Example 1.
Modified polyester polyurethane resin solution (NV50%)
I got 10 g of Takenate (trademark) D-110N was blended as a curing agent with 100 g of this resin solution (main agent), and they were adhered under the same conditions as in Example 1. In addition, this Takenate (trademark) D-110N is ω, ω′-diisocyanate-
An adduct of 1,3 dimethylbenzene / TMP = 3/1 (molar ratio), NV 75% ethyl acetate solution, a product of Takeda Pharmaceutical Co., Ltd.

Comparative Example A A similar polyester polyurethane resin was synthesized from the same raw materials according to the production method shown in Example 1, and 100 g of an ethyl acetate solution (50% NV) was used as a curing agent for the above Takenate (trademark) D. After blending 10 g of -140N, the mixture was diluted to 25% NV with ethyl acetate, bonded under the same conditions as in Example 1, and subjected to an adhesion test.

Comparative Example B A similar polyester polyol was synthesized from the same raw materials according to the production method described in Example 1, and 3 g of pyromellitic dianhydride was added to 100 g of an ethyl acetate solution (NV 50%). Was mixed with 10 g of the above Takenate (trademark) D-140N as a curing agent, diluted with ethyl acetate to 25% NV, bonded together under the same conditions as in Example 1, and subjected to an adhesion test.

Comparative Example C A similar polyester polyol was synthesized from the same raw materials according to the production method described in Example 1, and this was mixed with an ethyl acetate solution (N
(V50%) to 100 g, 3 g of maleic anhydride was added.
While warming to ° C, 10 g of a 10% solution of benzoyl peroxide in ethyl acetate was added dropwise with stirring. After completion, the reaction was maintained at 80 ° C. for 60 minutes. After cooling, 10 g of the above-mentioned Takenate (trademark) D-140N was mixed as a curing agent, diluted with ethyl acetate to 25%, and adhered under the same conditions as in Example 1.
An adhesion test was performed.

Adhesion Test For the above Examples 1, 2, 3 and Comparative Examples A, B, and C, a test piece having a size of 200 mm × 15 mm was cut from each of the laminated films, and an Instron type tensile tester was used. , T-type peeling, crosshead speed 50mm /
The adhesive strength was measured in minutes. The measured value is the adhesive strength (g / g) between the Al foil and the unstretched polypropylene film (CPP).
(15 mm width) was shown by the average value of five test pieces. Table 1
2 shows the results of a turpentine oil test (a test piece was immersed in turpentine oil for 24 hours and the state of delamination between Al / CPP was observed).

[0032]

[Table 1]

Table 2 shows the heat-resistant creep test (Al / CP
A load of 100 g was applied to the CPP side between P, and it was left in an oven at 100 ° C. for 40 seconds, and the peeled distance was measured.

[0034]

[Table 2]

Table 3 shows the content resistance test (the laminate film was aged at 40 ° C. for 72 hours, then 15 cm × 20 cm).
cm flat bag, vinegar / water / salad oil = 1/1
/ 1 mixture is injected. 2. 135 ° C for 20 minutes;
After sterilization by heating with hot water under a pressure of 8 kg / cm ² , 30
After storage for a day, the results of measuring the adhesion strength between Al / CPP, observing the state of delamination, and observing the corrosion state of the Al foil surface) are shown.

[0036]

[Table 3]

[0037]

As described above, the present invention improves various properties such as heat resistance, water resistance, acid resistance, oil resistance, etc., and is applicable to various contents including foods. A possible adhesive composition for dry lamination and a method for producing the same have been provided.

Claims (4)

[Claims] (A) an organic polyisocyanate, (b)
A polyurethane adhesive composition for a composite laminate film comprising a polymer polyol and (c) a copolymer of styrene and maleic anhydride, wherein (a) an organic polyisocyanate, (b) a polymer polyol, (c) styrene, A polyurethane adhesive composition comprising, as a main component, a modified polyurethane resin obtained by reacting a copolymer of maleic anhydride and (a) an organic polyisocyanate as a curing agent. 2. (a) an organic polyisocyanate, (b)
A method for producing a polyurethane adhesive composition for a composite laminate film comprising a polymer polyol and (c) a copolymer of styrene and maleic anhydride, wherein (a) an organic polyisocyanate is reacted with (b) a polymer polyol. To produce a polyurethane polyol,
The modified polyurethane resin is produced by reacting (c) a copolymer of styrene and maleic anhydride with the polyurethane polyol, and the modified polyurethane resin is used as a main component, and (a) an organic polyisocyanate is added as a curing agent. Of producing a polyurethane adhesive composition. (3) (a) an organic polyisocyanate, (b)
A polyurethane adhesive composition for a composite laminate film, comprising a polymer polyol, (c) a copolymer of styrene and maleic anhydride, and (d) an epoxy resin. (4) an organic polyisocyanate, (b)
A method for producing a polyurethane adhesive composition for a composite laminate film comprising a polymer polyol, (c) a copolymer of styrene and maleic anhydride, and (d) an epoxy resin, wherein (a) an organic polyisocyanate and (b) A) producing a polyester polyurethane resin in which a polymer polyol and (d) an epoxy resin are blended; and (c) reacting a copolymer of styrene and maleic anhydride with the polyester polyurethane resin to produce a modified polyester polyurethane resin. A method for producing a polyurethane adhesive composition, comprising a modified polyester polyurethane resin as a main component and (a) an organic polyisocyanate as a curing agent.