JP6481321B2 - Urethane catalyst, polyol mixture, adhesive, and laminated film - Google Patents

Description

  The present invention relates to a polyol mixture, an adhesive, and a laminated film obtained by laminating various films using the adhesive. More specifically, the present invention relates to an adhesive for laminating used in the production of composite films mainly used for packaging materials such as foods, pharmaceuticals, and detergents by laminating various plastic films, metal vapor deposited films, aluminum foils and the like.

  For food packaging materials, pharmaceuticals, and soft packaging materials for daily necessities, after applying a laminating adhesive to the surface of the film substrate, if necessary, the solvent is evaporated to dryness, and other layers are laminated by heating and pressure bonding. Films are widely used because arbitrary films can be selectively combined according to the required characteristics of each application.

  Such a flexible packaging material laminate adhesive is mainly a two-component polyurethane adhesive in which a polyol component having a hydroxyl group at a polymer terminal and a polyisocyanate are combined. Although this two-component polyurethane adhesive undergoes a curing reaction even at room temperature, it takes a long time to be completely cured. Therefore, a so-called aging process for accelerating the reaction in an aging room at about 40 to 50 ° C. is essential for the curing reaction after lamination.

  In order to improve productivity by shortening this aging process, the polyol component of the laminate adhesive contains a catalyst for urethanization reaction. As typical catalysts, organotin catalysts exhibiting excellent activity, mainly dibutyltin dilaurate (DBTDL) or octyltin maleate are widely used. However, when these catalysts are contained to accelerate the curing reaction, there is a problem of so-called pot life deterioration that causes a significant increase in the viscosity of the adhesive itself on the laminating machine.

  In addition, organotin catalysts have been pointed out to be toxic, and tributyltin contained as impurities in DBTDL is particularly problematic as an environmental hormone that is toxic to the human body. Already there has been a movement to regulate organotin catalysts in polyurethane production, mainly in Europe, and there is a strong demand for alternative catalysts for organotin catalysts.

Therefore, a technique using a photolatent chelate catalyst is known as a non-tin-based catalyst that has both an excellent curing acceleration effect and a good pot life (see Patent Documents 1 and 2).
When such a photolatent chelate catalyst is used, there is a merit that curing can be started at the timing of light irradiation, but in actuality, the viscosity of the mixed liquid immediately after blending the polyol component and the polyisocyanate component is increased. Was inevitable and sufficient pot life performance could not be obtained. In addition, the curing accelerating effect was not at a sufficient level, and the sealing strength with time after lamination was weak.

Special table 2013-504671 Special table 2013-504673 gazette

  Therefore, the problem to be solved by the present invention is a urethanization catalyst having both excellent pot life performance and excellent curing acceleration performance after ultraviolet irradiation, a mixture of the catalyst and a polyol component, and curing performance thereof. It is in providing the adhesive agent which has, and the laminated | multilayer film using this adhesive agent.

  As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have used an aliphatic cyclic amide compound (A) and a titanium chelate complex (B) as a curing catalyst in a polyol / polyisocyanate curable adhesive. By using in combination, it was found that the viscosity increase after blending the polyol component and the polyisocyanate component is small and the pot life performance is excellent, and the curing promoting effect after ultraviolet irradiation is dramatically increased, and the present invention has been completed. .

  That is, the present invention relates to a urethanization catalyst comprising an aliphatic cyclic amide compound (A) and a titanium chelate complex (B) as essential components.

  The present invention further relates to a polyol mixture comprising an aliphatic cyclic amide compound (A), a titanium chelate complex (B) and a polyol (C) as essential components.

  The present invention further relates to an adhesive comprising a polyol (C), an aliphatic cyclic amide compound (A), a titanium chelate complex (B), and a polyisocyanate (D) as essential components.

The present invention further provides a laminated film obtained by applying the adhesive to a first film substrate, then laminating a second film substrate on the coated surface, and curing the adhesive layer.
About.

  According to the present invention, a urethanization catalyst having both excellent pot life performance and excellent curing acceleration performance after ultraviolet irradiation, a mixture of the catalyst and a polyol component, an adhesive having these curing performance, and the A laminated film using an adhesive can be provided.

  The urethanization catalyst of the present invention is a curing catalyst useful for a two-component adhesive mainly composed of a polyol component and a polyisocyanate component. As described above, the aliphatic cyclic amide compound (A) and a titanium chelate complex ( And B) as essential components.

  Examples of the aliphatic cyclic amide compound (A) used here include δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, β-propiolactam, and the like. Among these, ε-caprolactam is preferable from the viewpoint of excellent curing acceleration effect.

  Next, the titanium chelate complex (B) is a compound whose catalytic activity is enhanced by ultraviolet irradiation, and is preferably a titanium chelate complex having an aliphatic or aromatic diketone as a ligand from the viewpoint of excellent curing acceleration effect. Further, in the present invention, those having an alcohol having 2 to 10 carbon atoms in addition to an aromatic or aliphatic diketone as a ligand are preferable because the effects of the present invention become more remarkable.

  Here, specific examples of the aliphatic diketone used as the ligand include the following structural formulas L-1 to L-3, and the aromatic diketone includes the following structural formulas L-4 to L-8. Is mentioned.

上記した各種の脂肪族又は芳香族ジケトンは、通常、エノラートアニオンとしてチタン原子に配位するが、そのままチタン原子に配位していてもよい。これらのなかでも本発明では、硬化促進効果が良好である点から構造式Ｌ−２、Ｌ−５、Ｌ−６のものが好ましく、特に構造式Ｌ−２のものが好ましい。

The above-mentioned various aliphatic or aromatic diketones are usually coordinated to a titanium atom as an enolate anion, but may be coordinated to a titanium atom as they are. Among these, in the present invention, those having the structural formulas L-2, L-5, and L-6 are preferable from the viewpoint of good curing acceleration effects, and those having the structural formula L-2 are particularly preferable.

  Examples of the alcohol having 1 to 20 carbon atoms include methanol, ethanol, isopropyl alcohol, t-butyl alcohol, lauryl alcohol (C12), myristyl alcohol (C14) and stearyl alcohol (C18). t-Butyl alcohol is preferred. An alcohol having 1 to 20 carbon atoms is also coordinated to a titanium atom as an alkoxy anion, but may be coordinated to a titanium atom as it is.

  When an aromatic or aliphatic diketone and an alcohol having 2 to 10 carbon atoms coexist as a ligand, the abundance ratio [diketone / alcohol] is in a range of 70/30 to 30/70 on a mass basis. It is preferable from the point which is excellent in the promotion effect.

  In the present invention, the use ratio [(A) / (B)] when combining the aliphatic cyclic amide compound (A) and the titanium chelate complex (B) is in the range of 1/9 to 9/1 on a mass basis. It is preferable from the viewpoint of excellent balance between pot life performance and curing acceleration effect.

  The urethanization catalyst of the present invention described in detail above, when blending the polyol (C) and the polyisocyanate (D), blends the aliphatic cyclic amide compound (A) and the titanium chelate complex (B) on the spot. However, the polyol mixture (X) containing the aliphatic cyclic amide compound (A), the titanium chelate complex (B), and the polyol (C) as essential components from the viewpoint of excellent workability during adhesive coating. It is preferable to use as the coating workability.

  The polyol (C) used here is, for example, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, , 6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutanediol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1,4- Glycols such as cyclohexanediol, 1,4-cyclohexanedimethanol, triethylene glycol; bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol Bisphenol such as F; dimer diol; polyether polyol obtained by addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene in the presence of a polymerization initiator such as glycol, or Urethane bond-containing polyether polyol obtained by further polymerizing the polyether polyol with the aromatic or aliphatic polyisocyanate; propiolactone, butyrolactone, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, etc. Between the polyester obtained by the ring-opening polymerization reaction of the cyclic ester compound and a polyhydric alcohol such as glycol, glycerin, trimethylolpropane and pentaerythritol. Polyester polyol as a reaction product; polyester polyol obtained by reacting a bifunctional polyol such as the glycol, dimer diol, or the bisphenol with a polyvalent carboxylic acid: the polyester polyol and the polyether polyol and aromatic or Urethane bond-containing polyester polyether polyol obtained by reacting with an aliphatic polyisocyanate; polyester polyurethane polyol obtained by polymerizing the polyester polyol with an aromatic or aliphatic polyisocyanate; a mixture of a polyester polyol and a polyether polyol Bisphenol A type epoxy resin having an epoxy equivalent of 200 to 500 g / eq, bisphenol F type epoxy resin having an epoxy equivalent of 200 to 500 g / eq, etc. Hydroxyl group-containing epoxy resin.

  Here, examples of the polyvalent carboxylic acid used as a raw material for polyester polyol, urethane bond-containing polyester polyether polyol, and polyester polyurethane polyol include succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, and maleic anhydride. , Fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6- Naphthalenedicarboxylic acid, naphthalic acid, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids; p-hydroxybenzoic acid, p- ( 2-hydro Shietokishi) benzoic acid and ester-forming derivatives of these dihydroxy carboxylic acids include polybasic acids such as dimer acid.

  In addition, the polyester polyol obtained by reacting a bifunctional polyol and a polyvalent carboxylic acid is used in combination with a trifunctional or higher polyhydric alcohol such as glycerin, trimethylolpropane, pentaerythritol as an alcohol component. Also good.

  For these flexible packaging, polyether polyols, urethane bond-containing polyester polyether polyols, and mixtures of polyester polyols and polyether polyols are preferred from the viewpoint of imparting appropriate flexibility to the cured product. In this case, the hydroxyl value is 3 A range of ˜50 mg KOH / g is preferable from the viewpoint of excellent wettability to the substrate.

  For rigid substrates, polyester polyol or polyester polyurethane polyol is preferred from the viewpoint of excellent adhesive strength. For such a hard base material, the polyester polyol or the polyester polyurethane polyol specifically has a hydroxyl value in the range of 3 to 50 mgKOH / g because the balance between wettability to the base material and adhesive strength is excellent. preferable.

  Next, the polyisocyanate (D) used in the present invention is, for example, an aromatic polyisocyanate such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate; Aliphatic polyisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane; aromatic or aliphatic polyisocyanate And polyether polyurethane polyisocyanate which is a reaction product of the polyether polyol exemplified as the polyol (C) Polyester polyurethane polyisocyanate, which is a reaction product of the polyester polyol exemplified as the polyol (C), aromatic or aliphatic polyisocyanate, and the polyol (C). Polyether polyester polyurethane polyisocyanate which is a reaction product of polyester polyol and polyether polyol, biuret of these aromatic or aliphatic polyisocyanates, nurate of these aromatic or aliphatic polyisocyanates, and fragrances thereof And adducts obtained by modifying an aliphatic or aliphatic polyisocyanate with trimethylolpropane.

  Among these polyisocyanates (D), an adduct body obtained by modifying an aromatic polyisocyanate with trimethylolpropane and an adduct body obtained by modifying an aliphatic polyisocyanate with trimethylolpropane are preferable because of excellent chemical resistance after adhesion. The biuret form of aliphatic polyisocyanate and the nurate form of aliphatic polyisocyanate are preferred from the viewpoint of avoiding toxicity and imparting appropriate flexibility of the cured product. From the standpoint of avoiding toxicity, a compound having a low risk of releasing aromatic amines is preferred. From this viewpoint, trimethylolpropane adduct of xylylene diisocyanate, trimethylolpropane adduct of aliphatic polyisocyanate, aliphatic polyisocyanate Biuret bodies and nurate bodies of aliphatic polyisocyanates are preferred. These adduct bodies, biuret bodies, and nurate bodies preferably have an isocyanate content of 4 to 30% by mass by titration (using di-n-butylamine) from the viewpoint of curability.

  On the other hand, polyether polyurethane polyisocyanate which is a reaction product of aromatic polyisocyanate and polyether polyol, aromatic or aliphatic polyisocyanate, polyester polyol and polyether because the reaction rate with polyol (C) is increased. Aromatic polyisocyanates such as polyether polyester polyurethane polyisocyanate, which is a reaction product with polyol, are preferred from the viewpoint of non-food packaging applications. Although such aromatic polyisocyanate is concerned about the elution of aromatic amine (PAA), which is a toxic substance, into food contents, in the present invention, such elution of PAA can be effectively suppressed.

  Next, in the polyol mixture (X), the aliphatic cyclic amide compound (A) is in the range of 0.1 to 5 parts by mass and the titanium chelate complex (B) is 0.05 to 100 parts by mass of the polyol (C). Mixing in the range of 5 parts by mass is preferable because the pot life is stable, the coating workability is excellent, and the curing acceleration effect is excellent. Moreover, it is preferable from the point of productivity that mixing of a polyol (C) and an aliphatic cyclic amide compound (A) is performed on the temperature conditions of 40-60 degreeC.

  Moreover, the adhesive strength of the adhesive of the present invention is such that the equivalent ratio [isocyanate group / hydroxyl group] of the isocyanate group in the polyisocyanate (D) and the hydroxyl group in the polyol resin (B) is 1.0 to 5.0. In view of excellent heat resistance during heat sealing, a range of 1.5 to 4.5 is particularly preferable because these properties become remarkable.

  Therefore, the use ratio of the polyol mixture (X) and the polyisocyanate (D) is the equivalent ratio of the hydroxyl group in the polyol mixture (X) to the isocyanate group in the polyol resin (A) [isocyanate group / hydroxyl group. ] Is a ratio of 1.0 to 5.0, particularly preferably a ratio of 1.5 to 4.5.

  The adhesive of the present invention can be used as a solvent type adhesive or a solventless type adhesive, but it is particularly preferable to use it as a solvent type adhesive because it can exhibit excellent pot life stability. Examples of the solvent that can be used as the solvent-type adhesive include methanol, ethanol, isopropyl alcohol, methyl acetate, ethyl acetate, n-butyl acetate, acetone, methyl ethyl ketone (MEK), cyclohexanone, toluol, xylol, n-hexane, cyclohexane, and the like. Is mentioned. Among these, ethyl acetate and methyl ethyl ketone (MEK) are preferable from the viewpoint of solubility, and ethyl acetate is particularly preferable. The amount of the organic solvent used is preferably in the range of 20 to 50% by mass from the viewpoint of viscosity.

  The adhesive of the present invention may be used in combination with a pigment as necessary. In this case, usable pigments are not particularly limited. For example, extender pigments, white pigments, black pigments, gray pigments, red pigments described in the Paint Material Handbook 1970 edition (edited by the Japan Paint Industry Association) Examples thereof include organic pigments and inorganic pigments such as pigments, brown pigments, green pigments, blue pigments, metal powder pigments, luminescent pigments, and pearl pigments, and plastic pigments. Specific examples of these colorants include various types, and examples of organic pigments include various insoluble azo pigments such as Bench Gin Yellow, Hansa Yellow, Raked 4R, etc .; Soluble properties such as Raked C, Carmine 6B, Bordeaux 10 and the like. Azo pigments;

  Various (copper) phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green; various chlorine dyeing lakes such as rhodamine lake and methyl violet lake; various mordant dye pigments such as quinoline lake and fast sky blue; anthraquinone pigment; Various vat dyes such as thioindigo pigments and perinone pigments; various quinacridone pigments such as Cincacia Red B; various dioxazine pigments such as dioxazine violet; various condensed azo pigments such as chromoftal; aniline Black etc. are mentioned.

  Examples of inorganic pigments include various chromates such as chrome lead, zinc chromate, and molybdate orange; various ferrocyan compounds such as bitumen; titanium oxide, zinc white, mapico yellow, iron oxide, bengara, chrome oxide Various metal oxides such as green and zirconium oxide; various sulfides or selenides such as cadmium yellow, cadmium red and mercury sulfide;

  Various sulfates such as barium sulfate and lead sulfate; Various silicates such as calcium silicate and ultramarine blue; Various carbonates such as calcium carbonate and magnesium carbonate; Various phosphates such as cobalt violet and manganese purple; Aluminum Various metal powder pigments such as powder, gold powder, silver powder, copper powder, bronze powder and brass powder; flake pigments of these metals, mica flake pigments; mica flake pigments coated with metal oxides, mica-like iron oxide Examples thereof include metallic pigments such as pigments and pearl pigments; graphite and carbon black.

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

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

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

  The mass ratio of the pigment used in the present invention is preferably 1 to 400 parts by mass, more preferably 10 to 300 parts by mass, with respect to 100 parts by mass of the resin component, because it is excellent in adhesiveness and blocking resistance.

  If necessary, the adhesive composition of the present invention may contain other additives other than those described above. Examples of the additive include additives generally used in resin compositions that form films and coating films. Examples of additives include leveling agents; inorganic fine particles such as colloidal silica and alumina sol; organic fine particles based on polymethyl methacrylate; antifoaming agents; anti-sagging agents; wetting and dispersing agents; silane coupling agents; Ultraviolet absorber; Metal deactivator; Peroxide decomposing agent; Flame retardant; Reinforcing agent; Plasticizer; Lubricant; Rust inhibitor; Fluorescent brightener; Inorganic heat absorber; Agents; dehydrating agents and the like.

  When the adhesive of this invention uses the polyol mixture which uses a polyol (C), an aliphatic cyclic amide compound (A), and a titanium chelate complex (B) as an essential component, for example, each other than polyisocyanate (D) A premix containing components in advance can be prepared as the polyol mixture, and this can be mixed with polyisocyanate (D).

  The method for producing a laminated film using the adhesive of the invention described in detail above includes, for example, applying an adhesive to a first film substrate, then laminating a second film substrate on the coated surface, and then applying the adhesive. The method of hardening a layer is mentioned. Here, in the present invention, the curing reaction can be accelerated by ultraviolet irradiation, and the viscosity change of the adhesive coating layer until the ultraviolet irradiation is extremely small. Therefore, the timing of ultraviolet irradiation can be adjusted. It is easy and the workability and productivity can be dramatically improved. Further, in the present invention, the urethanization catalyst is activated by ultraviolet irradiation, and is different from an acrylic polymer that is instantly cured by ultraviolet irradiation. Therefore, it is possible to irradiate ultraviolet rays before lamination, so a layer that shields ultraviolet rays, such as a metal layer on the film base or a full-face printed layer, is applied to both the base film and sealant film. Even if it is provided, it is possible to laminate. In addition, when manufacturing a multilayer film of three or more layers, after laminating the second film substrate, an adhesive may be applied, and the second film substrate may be further laminated and cured in the same manner.

  Here, the method of apply | coating the adhesive agent of this invention to a 1st film base material includes the method of apply | coating this adhesive agent to a plastic film base material with a gravure coater, a die coater, or a lip coater. In the die coater and the lip coater, the coating width can be freely adjusted by deckles attached to both ends of the die or the lip portion. When using a volatile acidic compound, the adhesive gels when the acidic compound volatilizes, so it is preferable to always maintain the pH at 1 to 8, preferably 3 to 7.

The application amount of the adhesive is preferably in the range of about 0.5 to 6.0 g / m ² , particularly 1.0 to 4.0 g / m ^{2 based on} the solid content.

In the case of a solvent-type adhesive, after drying in a dryer, ultraviolet rays can be irradiated to bond other films such as a sealant film. Here, the ultraviolet light source can be cured by irradiation with a mercury lamp such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp or a low-pressure mercury lamp, a xenon lamp, a carbon arc, a metal height lamp or the like. In this case, the ultraviolet light exposure is preferably in the range of 0.1 to 3000 mJ / cm ² .

  Moreover, as a 1st film base material used here, for example, polyethylene terephthalate (PET), aluminum vapor deposition PET, silica vapor deposition PET, alumina vapor deposition PET, biaxially stretched polypropylene (OPP), nylon (NY), polyvinylidene chloride Examples thereof include coated nylon, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride coated OPP (KOP), biaxially oriented polystyrene (OPS), and paper. These film base materials may be printed.

  When the second film substrate is a two-layer film, a sealant film such as polyethylene (PE), unstretched polypropylene (CPP), aluminum vapor-deposited CPP, or linear low density polyethylene (LLDPE) is used. Can be mentioned. In the case of a multilayer film of three or more layers, the second film substrate is polyethylene terephthalate (PET), aluminum vapor deposited PET, silica vapor deposited PET, alumina vapor deposited PET, biaxially oriented polypropylene (OPP), nylon (NY), In addition to plastic films such as polyvinylidene chloride coated nylon, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride coated OPP (KOP), biaxially oriented polystyrene (OPS), metal foil films such as aluminum foil can also be used. Furthermore, after laminating | stacking these film base materials as needed, the said sealant film can be finally laminated | stacked and the target laminated | multilayer film can be obtained.

  In addition, as described above, in the present invention, even when a metal foil is used as an intermediate film substrate or when a film having a metal vapor deposition layer or a printing layer is laminated, ultraviolet irradiation can be performed before lamination. It can be cured by ultraviolet irradiation.

  When the adhesive composition of the present invention is used, the adhesive is cured in 6 to 24 hours after being irradiated with ultraviolet rays after lamination, and expresses practical physical properties.

  Hereinafter, the contents and effects of the present invention will be described in more detail with reference to examples.

Synthesis example 1 (Preparation example of polyester polyurethane resin solution)
In a polyester reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, a rectification tube, a water separator, etc., 41.2 parts by mass of isophthalic acid, 18.0 parts by mass of adipic acid, 9.8 of sebacic acid The rectifying tube upper temperature was charged with 1 part by mass, 17.3 parts by mass of ethylene glycol, 14.9 parts by mass of neopentyl glycol, 16.7 parts by mass of 1,6-hexanediol and 0.006 parts by mass of titanium catalyst. Was gradually heated so as not to exceed 100 ° C., and the internal temperature was maintained at 240 ° C. When the acid value reached 5 mgKOH / g, xylene was added and xylene was refluxed at the same temperature using a water separator, and the reaction was further continued until the acid value became 2 mgKOH / g or less. The pressure was reduced to 10 mmHg or less, and the esterification reaction was terminated by holding for 1.5 hours to obtain an intermediate polyester polyol having a hydroxyl value of 28 mgKOH / g.
70 parts by mass of ethyl acetate, 3.1 parts by mass of isophorone diisocyanate, 0.05 parts by mass of dibutyltin laurate are added to 100 parts by mass of the obtained intermediate polyester polyol, and the mixture is heated and stirred at 80 ° C. for 30 minutes. A polyester polyurethane resin solution (hydroxyl value 9 mgKOH / g) having a solid content of 59.6% by mass was obtained.

Examples 1-5
The polyester polyurethane resin solution obtained in Synthesis Example 1 has ε-caprolactam and a titanium chelate complex (“SOLYFAST0010” manufactured by BASF, dipivaloylmethane / isopropyl alcohol = 50/50 (mass basis) as a ligand. Titanium chelate complex) was added in the amounts shown in Table 1 and held at 50 ° C. for about 1 hour to obtain a polyol mixture.
Then, the obtained polyol mixture and an ethyl acetate solution (solid content: 75% by mass) of aromatic polyisocyanate (trimethylolpropane adduct of tolylene diisocyanate) were mixed with an excess of isocyanate (equivalent ratio (NCO / OH)). An adhesive was obtained by blending at a ratio of 3.8 and adding ethyl acetate so that the final solid content was 30% by mass.
[Pot life evaluation]
After standing for 30 minutes at 25 ° C. immediately after the adhesive preparation, the viscosity was measured with Zahn cup # 3.
The mixture was placed in a constant temperature bath at 40 ° C. and the reaction was promoted for 6 hours. After standing at 25 ° C. for 30 minutes, the viscosity was measured again.
Further, the mixture was allowed to stand at room temperature, and the viscosity was measured 18 hours later (24 hours after the blending). The results are shown in Table 1.
Evaluation ◎: The viscosity of the liquid mixture after 24 hours is less than 20 seconds Evaluation ○: The viscosity of the liquid mixture after 24 hours is less than 25 seconds Evaluation Δ: The viscosity of the liquid mixture after 24 hours is less than 30 seconds Evaluation x: 24 hours The viscosity of the later compounding liquid is 30 seconds or more

[Coloring evaluation of main resin solution]
The polyester urethane polyisocyanate was diluted with 111.9 parts by mass of ethyl acetate and then promoted for 1 month at 50 ° C., and then the colored state was visually evaluated. The results are shown in Table 1.
Evaluation ◎: colorless and transparent evaluation ○: slightly yellow transparent evaluation ×: yellow transparent

[Manufacture of laminated film and evaluation of damping rate]
The adhesive was applied to a film so that the coating amount was about 2.5 to 3.5 g / m ² , dried with a dryer, and then irradiated with ultraviolet rays.
(UV irradiation conditions)
Uses 80W metal halide lamp
Line speed 10m / min Irradiation amount 50mJ / cm ² (actual measurement with integrated light meter made by Iwasaki Electric Co., Ltd.)
5 irradiations (total 250 mJ / cm ² )
A calender roll was used to closely adhere the coated surface of this film, another sealant film, and the coated surface to produce a laminate film.
The laminate film was prepared in two configurations: OPP / CPP (for NCO attenuation rate measurement) and NY / LLDPE (for time-dependent seal strength measurement).
This laminate film was placed in a constant temperature bath at 40 ° C., and measured according to the evaluation test method shown below every time.
In addition, the used film is as follows.
NY: “Emblem ON” manufactured by Unitika (15μm)
LLDPE: “TUX HC” (60 μm) manufactured by Mitsui Chemicals Tosero
OPP: “FOR” manufactured by Futamura Chemical Co., Ltd. (15μm)
CPP: “Pyrene Film-CTP-1128” manufactured by Toyobo Co., Ltd. (30 μm)
(Measurement of seal strength over time)
The ONY / LLDPE laminate film was bent so that the sealant was inside, and the bent portion was heat-sealed at 1 atm, 180 ° C. for 1 second. This was cut into a strip shape so as to have a width of 15 mm, and the strength of the heat seal part was measured at n = 5 at a peeling rate of 300 mm / min using a peeling tester. The results are shown in Table 1.
Evaluation 5: Film breakage occurs. Evaluation 4: Film breakage and edge breakage occur. Evaluation 3: Edge breakage occurs. Evaluation 2: Edge breakage and triangular peeling occur.
Evaluation 1: Triangular peeling occurs (Isocyanate decay rate measurement)
The OPP / CPP laminate film was subjected to infrared absorption spectrum measurement by a transmission method, and an isocyanate-derived absorption spectrum (near 2270 cm ⁻¹ ) was measured. The results are shown in Table 1.
Evaluation 5: Isocyanate reaction rate is 90% or more Evaluation 4: Isocyanate reaction rate is 80% or more Evaluation 3: Isocyanate reaction rate is 70% or more Evaluation 2: Isocyanate reaction rate is 50% or more Evaluation 1: Isocyanate reaction rate is less than 50%

Comparative Examples 1-5
Each of the catalyst components shown in Table 1 was blended with the polyester polyurethane resin solution obtained in Synthesis Example 1 and held at 50 ° C. for about 1 hour to obtain a polyol mixture.
Then, the obtained polyol mixture and an ethyl acetate solution (solid content: 75% by mass) of aromatic polyisocyanate (trimethylolpropane adduct of tolylene diisocyanate) were mixed with an excess of isocyanate (equivalent ratio (NCO / OH)). It mix | blended in the ratio used as 3.8, ethyl acetate was added and prepared so that it might finally become a solid content 30 mass%, the adhesive agent was obtained, and various evaluation was performed similarly to Examples 1-5. The results are shown in Table 1.

Comparative Example 6
The polyester polyurethane resin solution obtained in Synthesis Example 1 and the ethyl acetate solution (solid content 75% by mass) of aromatic polyisocyanate (trimethylolpropane adduct of tolylene diisocyanate) were mixed with an excess of isocyanate [equivalent ratio (NCO / OH)] is blended at a ratio of 3.8, and finally an ethyl acetate is added so that the solid content is 30% by mass to obtain an adhesive. Various evaluations are performed in the same manner as in Examples 1 to 5. went. The results are shown in Table 1.

Claims (11)

A urethanization catalyst comprising an aliphatic cyclic amide compound (A) and a titanium chelate complex (B) as essential components. The urethane according to claim 1, wherein the abundance ratio [(A) / (B)] of the aliphatic cyclic amide compound (A) and the titanium chelate complex (B) is a ratio of 1/9 to 9/1 on a mass basis. Catalyst. A polyol mixture comprising an aliphatic cyclic amide compound (A), a titanium chelate complex (B), and a polyol (C) as essential components. The cyclic amide compound (A) is one or more compounds selected from the group consisting of δ-valerolactam, ε-caprolactam, ω-enanthollactam, η-capryllactam, and β-propiolactam. 3. The polyol mixture according to 3. The polyol (C) comprises a polyether polyol, a urethane bond-containing polyether polyol, a polyester polyol, a urethane bond-containing polyester polyether polyol, a mixture of a polyester polyol and a polyether polyol, a polyester polyurethane polyol, and a hydroxyl group-containing epoxy resin. The polyol mixture according to claim 4, which is selected from the group. The aliphatic cyclic amide compound (A) is contained in a range of 0.05 to 5 parts by mass and the titanium chelate complex (B) in a range of 0.05 to 5 parts by mass per 100 parts by mass of the polyol (C). The polyol mixture according to claim 3. An adhesive comprising a polyol (C), an aliphatic cyclic amide compound (A), a titanium chelate complex (B), and a polyisocyanate (D) as essential components. The adhesion according to claim 7 , wherein the polyol mixture (X) in which the polyol (C), the aliphatic cyclic amide compound (A), and the titanium chelate complex (B) are mixed in advance and the polyisocyanate (D) are used. Agent. The adhesive according to claim 8, wherein the polyol mixture (X) is the polyol mixture according to any one of claims 3 to 6. The polyol mixture and (X), a hydroxyl group of the proportion of the polyisocyanate (D) is the polyol mixture (X), an equivalent ratio [isocyanate group / hydroxyl group] with the isocyanate groups in the polyisocyanate (D) The adhesive according to claim 8 or 9, which has a ratio of 1.0 to 5.0. The laminated film formed by apply | coating the adhesive agent in any one of Claims 7-10 to a 1st film base material, then laminating | stacking a 2nd film base material on an application surface, and hardening this adhesive bond layer.