KR100297074B1 - Polyurethane Resin Adhesive - Google Patents

Abstract

In particular, it provides an adhesive that satisfies the adhesiveness and durability to polyolefin at the same time. It is a polyurethane resin or the adhesive agent which consists of this resin and a polyisocyanate compound. This polyurethane resin reacts an organic diisocyanate with an active hydrogen group-containing compound containing 1 to 50 mol% of a hydroxyl-containing poly (ethylene-butylene) copolymer having a molar ratio of ethylene and butylene groups of 30/70 to 70/30. To obtain.

Description

Polyurethane Resin Adhesive

The present invention relates to a polyurethane resin adhesive, and more particularly, to a polyurethane resin adhesive having excellent hydrolysis resistance, heat resistance, weather resistance, mechanical properties, adhesion to all substrates including polyolefin, and the like.

Conventional polyurethane-based adhesives have been widely used in various fields such as film laminates, plywood, furniture, automobiles, railways, electrical appliances, nonwoven fabrics, shoes, bags, etc., due to characteristics such as excellent adhesion to various adherends and high durability. Generally, however, polyurethane adhesives have insufficient adhesion to polyolefins. In order to improve the adhesiveness to this polyolefin, the polyurethane adhesive which introduce | transduced the polyolefin type compound in the molecular structure was developed. For example, Japanese Patent Laid-Open No. 91-207782 discloses a reactive hot melt adhesive mainly containing hydroxyl group-containing polyisoprene. In addition, Japanese Patent Laid-Open No. 95-41751 discloses a thermoplastic elastomer adhesive using chlorinated polyolefin.

However, adhesives incorporating a polyisoprene structure have poor weather resistance because double bonds remain in the molecule. In addition, conventional active hydrogen group-containing polyolefin-based compounds such as hydroxyl-containing polybutadiene and polyisoprene or hydrogenated products thereof have limitations on the molecular design of the polyurethane-based resin because the number of functional groups exceeds two. In other words, increasing the amount of polyolefin containing an active hydrogen group in the molecule decreases the molecular weight of the polyurethane, resulting in insufficient durability. On the contrary, when the molecular weight is increased and the durability is improved, the amount of introduction thereof decreases, so that the adhesion to polyolefin is insufficient. In addition, the use of chlorinated polyolefins has a problem of deterioration of the adhesive and corrosion of the adhesive container because of dehydrochlorination reaction over time.

The present invention aims to solve these problems of the prior art, and in particular to provide an adhesive which satisfies the adhesion and durability to polyolefins at the same time.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve this problem of the prior art, the adhesive agent using the polyurethane-type resin which introduce | transduced specific hydroxyl-containing polyolefin, and the adhesive agent which added the polyisocyanate compound to this can achieve the said objective. It has been found that the present invention has been completed.

That is, the present invention reacts an organic diisocyanate with an active hydrogen group-containing compound containing 1 to 50 mol% of a hydroxyl group-containing poly (ethylene-butylene) copolymer having a molar ratio of ethylene and butylene groups of 30/70 to 70/30. The adhesive is characterized by consisting of a polyurethane-based resin obtained by.

The present invention also reacts an organic diisocyanate with an active hydrogen group-containing compound containing 1 to 50 mol% of a hydroxyl group-containing poly (ethylene-butylene) copolymer having a molar ratio of ethylene and butylene groups of 30/70 to 70/30. It is an adhesive characterized by consisting of a polyurethane-based resin and a polyisocyanate compound obtained by.

The hydroxyl group-containing poly (ethylene-butylene) copolymer used in the present invention is a compound having a molar ratio of ethylene group and butylene group of 30/70 to 70/30, for example, living such as radical polymerization and anionic polymerization of ethylene and butylene ( It is obtained by grafting a vinyl alcohol compound to a poly (ethylene-butylene) copolymer obtained by living) polymerization and treating the terminal polymerization initiator component, but the random copolymer has the lowest crystallinity and also has high adhesion. Do.

When the molar ratio of the ethylene group and the butylene group of the hydroxyl group-containing poly (ethylene-butylene) copolymer is other than 30/70 to 70/30, the crystallinity is increased and the melting temperature is high, so that the desired polyurethane resin adhesive is difficult to be obtained. .

500-10,000 are preferable and, as for the number average molecular weight of a hydroxyl-containing poly (ethylene-butylene) copolymer, 1,000-9,000 are more preferable.

When the number-average molecular weight of the hydroxyl-containing poly (ethylene-butylene) copolymer is less than 500, the Tg and softening point of the resulting polyurethane-based resin are high, which is almost the same as the introduction of a simple aliphatic chain extender into the polyurethane-based resin. Adhesion to polyolefins is insufficient. In addition, when the number average molecular weight is more than 10,000, not only the compatibility with other polyols and isocyanates is low, but also the viscosity of the hydroxyl-containing poly (ethylene-butylene) copolymer becomes high. Is difficult to obtain.

The hydroxyl group content of the hydroxyl-containing poly (ethylene-butylene) copolymer is preferably 1.5 to 2.5 per molecule, more preferably 1.8 to 2.0, and most preferably 2.0.

When the number of hydroxyl groups is less than 1.5, the hydroxyl group-containing poly (ethylene-butylene) copolymer is less likely to be introduced into the polyurethane resin molecules, and as a result, the stability with time becomes insufficient. When the number of hydroxyl groups exceeds 2.5, gelation occurs depending on the amount of the hydroxyl group-containing poly (ethylene-butylene) copolymer when synthesizing the polyurethane-based resin, making it difficult to obtain the polyurethane-based resin.

Specific examples of the hydroxyl group-containing poly (ethylene-butylene) copolymer include the Clayton Liquid series HPVM-2202 manufactured by Shell Corporation.

The amount of hydroxyl group-containing poly (ethylene-butylene) copolymer introduced into the polyurethane resin molecule according to the present invention is 1 to 50 mol%, preferably 5 to 30 mol%, based on the total of the active hydrogen group-containing compounds.

When the amount of the hydroxyl group-containing poly (ethylene-butylene) copolymer is less than 1 mol%, the adhesion to the polyolefin is insufficient. Moreover, when it exceeds 50 mol%, adhesiveness to things other than polyolefin, such as polyethylene terephthalate and nylon, will become inadequate.

In the present invention, as an active hydrogen group-containing compound used in combination with a hydroxyl group-containing poly (ethylene-butylene) copolymer, molecular weights such as polyester polyols, polyether polyols, polycarbonate polyols, acrylic polyols, polyether polyamines and the like exceed 500, for example. And a chain extender such as a high molecular polyol, a high molecular polyamine, and a low molecular polyol having a molecular weight of 18 to 500, a low molecular polyamine, a low molecular amino alcohol, or water. Other active hydrogen group-containing compounds may also include monoalcohols, monoamines, and the like, and these low molecular weight aminoalcohols are also used as reaction terminators. Preferred polymeric polyols are polyester polyols with good adhesion, heat resistance and durability. These active hydrogen group-containing compounds may be used alone or may be constituted in plural so as to have an average number of functional groups of 2 to 3, but the bifunctional active hydrogen group-containing compound is most preferred because it is easy to control the molecular weight of the resulting polyurethane-based resin. .

Specific examples of the polyester polyol in the polymer polyol include ethylene glycol (hereinafter, abbreviated as EG), diethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1 , 3-butanediol, 1,4-butanediol, neopentyl glycol (hereinafter abbreviated as NPG), 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol , 2-methyl-1.5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3 -Hexanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A So-called low molecular glycols and mixtures thereof and dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid, naphthylenedicarboxylic acid, and acid esters thereof , And the like obtained by the dehydration condensation reaction of the anhydride, the hydroxyl group at both terminals polylactone ester, or obtained by ring-opening polymerization of ε- caprolactone polycaprolactone diol having a.

Specific examples of the polyether polyol include polyether polyols obtained by ring-opening polymerization of epoxides such as ethylene oxide and propylene oxide alone or a mixture thereof, or polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran.

As a specific example of a polycarbonate polyol, there may be obtained by a dephenol reaction of low molecular glycols and diethyl carbonate used in the synthesis of the polyester polyol.

The number average molecular weight of such a polymer polyol is preferably 500 to 10,000, more preferably 1,000 to 5,000.

As said low molecular polyol, the low molecular glycols used for the synthesis | combination of the said polyester polyol can also be illustrated.

As a low molecular polyamine, For example, Aliphatic diamines, such as ethylenediamine and hexamethylenediamine; Alicyclic diamines such as isophorone diamine (hereinafter abbreviated as IPDA) and cyclohexyldiamine; And aromatic diamines such as diaminodiphenylmethane and diaminodiphenylsulfone.

Low molecular amino alcohols include monoethanol amine and diethanol amine.

Monoalcohols include methanol, ethanol, propanol, isopropanol and the like. Examples of the monoamine include primary monoamines such as ethylamine and butylamine, secondary monoamines such as diethylamine and dibutylamine.

Organic diisocyanates used in the present invention include hexamethylene diisocyanate, lycidine diisocyanate, isophorone diisocyanate (hereinafter abbreviated as IPDI), cyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, water Added xylene diisocyanate, hydrogenated trimethylxylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexamethylene-1, 6-diisocyanate, 2,4,4-trimethylhexamethylene-1,6-diisocyanate, 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as 4,4'-MDI), 2,4 ' -Diphenylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, paraphenylene diisocyanate, tolylene-2,4-diisocyanate (hereinafter as 2,4-TDI) Abbreviated), tolylene-2,6-diisocyanane , Orthoxylylene diisocyanate, methaxylylene diisocyanate, paraxylylene diisocyanate, tetramethylxylylene diisocyanate and the like and mixtures of two or more thereof.

The isocyanate group / active hydrogen group (molar ratio) of the active hydrogen group-containing compound and the organic diisocyanate should be in the range of 0.5 / 1.0 to 1.0 / 1.0 in order to avoid gelation due to the preparation of the polyurethane-based resin and to make the terminal an active hydrogen group. desirable.

Known so-called urethanization catalysts can be used to synthesize the polyurethane-based resins according to the present invention.

Specific examples include organic metal compounds such as dibutyltin dilaurate (hereinafter abbreviated as DBTDL), organic amines such as triethylene diamine, and salts thereof.

The method for producing a polyurethane-based resin according to the present invention is a one-shot method in which all active hydrogen group-containing compounds, including hydroxyl group-containing poly (ethylene-butylene) copolymers, and organic diisocyanate are reacted together at one time, or the terminal is an active hydrogen terminal. A hydroxyl group-containing poly (ethylene-butylene) copolymer and / or an active hydrogen group-containing compound and an organic diisocyanate are reacted sequentially or together to synthesize an isocyanate terminal prepolymer, followed by chain extension with a chain extender and reaction stopper There is a prepolymer method in which the terminal is an active hydrogen group.

In these methods, it can manufacture by the solid reaction method which does not use a solvent, and the solution reaction method which uses a solvent.

When synthesizing a polyurethane resin by a solution reaction method, examples of the solvent that can be used include aliphatic hydrocarbon solvents such as pentane and hexane; Aromatic hydrocarbon solvents such as toluene and xylene; Ketone solvents such as acetone and methyl ethyl ketone (hereinafter abbreviated as MEK); Alcohol solvents such as methanol and ethanol; Ester solvents such as ethyl acetate, butyl acetate; Ether solvents such as diethyl ether; Chlorine solvents such as methyl chloride and ethylene dichloride may be used alone or as a mixture, and may be appropriately selected depending on the adhesion conditions and the like.

The number average molecular weight of the polyurethane-based resin according to the present invention is preferably 5,000 to 1,000,000, more preferably 10,000 to 100,000.

When the number average molecular weight of the polyurethane resin is less than 5,000, the adhesive strength becomes insufficient. If it exceeds 1,000,000, the viscosity and melting temperature may be high, resulting in poor workability.

Although the polyurethane resin adhesive of the present invention can be used as a so-called single liquid, in particular, since the heat resistance and durability are improved, a polyisocyanate compound may be added thereto.

It is preferable that it is 1-50 weight part with respect to 100 weight part of polyurethane-type resins from a viewpoint of adhesive force, and, as for this polyisocyanate compound, it is more preferable that it is 3-20 weight part.

Examples of the polyisocyanate compound which can be used in the present invention include, for example, a polymer of so-called terminal isocyanate groups in addition to the polymeric MDI and the crude TDI, but examples thereof include adduct modifications such as Chronate HL manufactured by Nippon Polyurethane Co., Ltd. Molding; Isocyanurate-modified forms such as Kronate HX or Kronate 2030 from Nippon Polyurethane Co., Ltd. and Kukstanate T-1890 from Hose Japan Japan; There are burette modified types such as Duranate 24A-100, manufactured by Asahi Kasei Kogyo Co., Ltd., and Sumule N, manufactured by Sumitomo Bayer Urethane.

In the present invention, other resins such as vinyl chloride resin, nylon resin and acrylic resin may be added. Moreover, you may add a wax, a plasticizer, an elastomer, a stabilizer, etc.

The adhesive method using the polyurethane-based resin adhesive of the present invention is a polyurethane-based adhesive of the present invention, in addition to a method of applying the adhesive to a conventional adherend, and then, after standing for a few hours from a few seconds if necessary, followed by heat reaction. Since the resin adhesive has good adhesion resistance, it can be adhered by applying the adhesive to the adherend in advance and bonding it by heat sealing several days later.

In particular, in the case of bonding by heat sealing, the temperature is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, and the sealing pressure is preferably 0.1 to 10 kgf / cm 2, more preferably as the heat sealing condition. 1 to 5 kgf / cm 2, and the sealing time is preferably 0.1 to 10 seconds, more preferably 0.5 to 5 seconds. When the temperature is less than 100 ° C., the sealing pressure is less than 0.1 kgf / cm 2, and the sealing time is less than 0.1 second, the adhesive strength is hardly found. If the adhesion temperature exceeds 200 ° C., damage occurs to the adhesive and the adherend. When the sealing pressure is more than 10kgf / ㎠ or the sealing time is more than 10 seconds, there is no problem in the adhesive strength and durability, but lacks in economic efficiency.

The polyurethane resin adhesive of the present invention can be attached to all substrates such as polar substrates such as PET and nylon, nonpolar substrates such as polyethylene and polypropylene, rubber such as SBR and NBR, metal such as iron and aluminum, glass, wood and paper. In particular, a conventional polyurethane resin adhesive is particularly effective as a polyolefin adhesive which does not have sufficient adhesive strength.

EXAMPLES

Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. Unless otherwise specified, parts and% in the synthesis examples, comparative synthesis examples, examples and comparative examples mean "parts by weight" and "% by weight", respectively.

Synthesis of Polyurethane Resin

Synthesis Example 1

A two-terminal hydroxyl-containing polyester obtained from the dehydration of 3-methyl-1,5-pentanediol and adipic acid in a four-necked flask equipped with a stirrer, a thermometer, an arin cooling tube, and a nitrogen gas introduction tube. 219.0 parts for Les Polyol P-2010, Clare Corporation, number average molecular weight 2000), and 30.0 for a hydroxyl group-containing poly (ethylene-butylene) copolymer (trade name: HPVM-2202, manufactured by Shell), number average molecular weight 3600) 11.4 parts of NPG and 300 parts of toluene were added and it heated at 40 degreeC. 38.0 parts (isocyanate group / hydroxy group (molar ratio) = 0.96) of 2,4-TDI and 0.03 part of DBTDL were put therein, and urethanized at 80 degreeC until the peak of 2270 cm <^-1> isocyanate groups by an infrared spectroscopy disappeared. Reacted. Thereafter, 200 parts of toluene and 200 parts of MEK were added to obtain a polyurethane resin solution PU-1.

Solid content of PU-1 was 29.8%, the viscosity was 2700 cP / 25 degreeC, and the number average molecular weight was 33000.

Synthesis Example 2

146.3 parts of a hydroxyl group-containing polyester (hereinafter abbreviated to DEG / SeA-1000) with a number-average molecular weight of 1000 obtained by dehydration of diethylene glycol and sebacic acid in the same apparatus as Synthesis Example 1 60.0 parts of (ethylene-butylene) copolymer HPVM-2202 and 200 parts of toluene were put, and it heated up at 40 degreeC. Here, 68.6 parts of IPDI (isocyanate group / hydroxyl group (molar ratio) = 1.90) and 0.03 part of DBTDL were put in a urethane reaction at 80 ° C. for 4 hours, followed by 200 parts of toluene and 200 parts of MEL. The urethane prepolymer solution which is an isocyanate group was obtained. A solution obtained by dissolving 23.6 parts of IPDA and 1.5 parts of diethanolamine in 100 parts of isopropanol was previously added to the urethane prepolymer solution, and reacted until the 2270 cm ^-1 isocyanate group peak disappeared by infrared spectroscopy. -2 was obtained.

Solid content of PU-2 was 30.0%, the viscosity was 4000 cP / 25 degreeC, and the number average molecular weight was 23000.

Synthesis Example 3

188.1 parts of a number-average molecular weight 3000 terminal-containing polyester (hereinafter abbreviated as HG / AA-3000) obtained from the dehydration condensation of 1,6-hexanediol and adipic acid in the same apparatus as Synthesis Example 1 90.0 parts of hydroxyl group-containing poly (ethylene-butylene) copolymer HPVM-2202 and 300 parts of toluene were added and heated to 40 ° C. Here, 19.7 parts of 4,4'-MDI (isocyanate group / hydroxy group (molar ratio) = 0.90) and 0.03 part of DBTDL were put, and the urethane at 80 ° C was removed until the peak of 2270 cm ^-1 isocyanate group by infrared spectroscopy disappeared. Reacted. Thereafter, 200 parts of toluene and 200 parts of MEK were added to obtain a polyurethane resin solution PU-3.

Solid content of PU-3 was 29.8%, the viscosity was 3500 cP / 25 degreeC, and the number average molecular weight was 34000.

Synthesis Example 4

The amount of the number average molecular weight 2000 obtained from the dehydration condensation of the dicarboxylic acid mixture of phthalic anhydride / azelaic acid = 1/1 (molar ratio) and the diol mixture of EG / NPG = 1/1 (molar ratio) in the same apparatus as Synthesis Example 1 203.3 parts of terminal hydroxyl group-containing polyester (hereinafter abbreviated as (EG / NPG) / (PA / AzA) -200), 60.0 parts of hydroxyl group-containing poly (ethylene-butylene) copolymer HPVM-2202, and ethylene glycol 3.2 parts and 300 parts of toluene were added and stirred uniformly. In this solution, 17.7 parts of IPDI, 13.8 parts of 2,4-TDI (isocyanate group / hydroxy group (molar ratio) = 0.94) and 0.03 part of DBTDL were removed, and the peak of 2270 cm ^-1 isocyanate group disappeared by infrared spectroscopy. The urethanation reaction was carried out at 80 degreeC until. Thereafter, 200 parts of toluene and 200 parts of MEK were added to obtain a polyurethane resin solution PU-4.

Solid content of PU-4 was 30.0%, the viscosity was 2000 cP / 25 degreeC, and the number average molecular weight was 29000.

Comparative Synthesis Example 1

219.6 parts of both terminal hydroxyl group containing polyester claret polyol P-2010, the toluene solution of active hydrogen group containing chlorinated polypropylene in the same apparatus as the synthesis example 1 (solid content = 50%, brand name: Sparklon 813A, Japan Paper Co., Ltd.) 60.0 parts) of NPG, 11.4 parts of NPG, and 1.5 parts of bisphenol A type epoxy resins (trade name: Epicoat 828, manufactured by Emulsified Shell Epoxy Co., Ltd.) and 270 parts of toluene were heated to 40 ° C. 37.4 parts (2 isocyanate group / hydroxyl group (molar ratio) = 0.96) of 2, 4-TDI and 0.03 part of DBTDL were put therein, and urethanized at 80 degreeC until the 2270 cm <^-1> isocyanate group peak disappeared by infrared spectroscopy. Reacted. Thereafter, 200 parts of toluene and 200 parts of MEK were added to obtain a polyurethane-based resin solution PU-5.

Solid content of PU-5 was 30.0%, the viscosity was 1700 cP / 25 degreeC, and the number average molecular weight was 30000.

Comparative Synthesis Example 2

When synthesized in the same manner as in Synthesis Example 2, except that the hydroxyl group-containing poly (ethylene-butylene) copolymer HPVM-2202 was replaced with a hydroxyl group-containing polybutadiene (trade name: R-45HT, manufactured by Kwangkwang Petrochemical Co., Ltd.), The reaction solution was gelled.

Table 1 shows all the raw materials and the synthesis results of Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2.

TABLE 1

Examples 1 to 12, Comparative Examples 1 to 3

[Preparation of Adhesive]

The adhesive was prepared by mix | blending as follows using the synthesized polyurethane-type resin solution PU-1-5.

<Composition>

50 parts of polyurethane resin solution

MEK Part 25

Toluene 25 parts

Cronate L or Cronate HL 0 or 3 parts

Table 2 shows all of these formulations.

TABLE 2

Adhesion Test 1

Each adhesive prepared as described above was bar coater No. It applied to the film assembly shown below so that application amount by 6 might be set to 2 g / m <2> in a dry state.

(1) Corona Treated CPP Film / Corona Treated CPP Film

(2) corona treated PET film / corona treated PET film

(3) corona treated PET film / corona treated CPP film

(4) Corona Treated CPP Film / Corona Treated Nylon Film

After apply | coating each adhesive agent to the process surface of each film, it left still on the conditions of 5 second at 80 degreeC, and 24 hours at 40 degreeC. Then, in the combination of the films of (1)-(4), adhesive application surfaces were piled up and heat-sealed on condition of 130 degreeC, 3 kgf / cm <2>, and 2 second. The heat-sealed specimens were cut to a width of 15 mm and subjected to a T-type peeling test at a tensile rate of 50 mm / min, a measurement atmosphere of 25 ° C. and 50 ° C. RH.

Adhesion Test 2

Each adhesive with a bar coater No. It applied to the film assembly shown below so that application amount by 6 might be set to 2 g / m <2> in a dry state.

(1) Corona Treated CPP Film / Corona Treated CPP Film

(2) corona treated PET film / corona treated PET film

(3) corona treated PET film / corona treated CPP film

(4) Corona Treated CPP Film / Corona Treated Nylon Film

An adhesive was applied to the treated surface of each film, allowed to stand at 80 ° C. for 5 seconds and immediately adhered, and left to stand at 50 ° C. for 24 hours after adhesion. Then, it cut | disconnected to 15 mm width, and performed the T-type peeling test by 50 mm / min of tensile velocity, 25 degreeC of measurement atmosphere, and 50% RH.

The result of the adhesion test 1 is shown in Table 3, and the result of the adhesion test 2 is shown in Table 4.

TABLE 3

Note) Film breakdown occurs on all CPP films.

TABLE 4

Note) Film breakdown occurs on all CPP films.

[Weathering resistance and water resistance test]

Each prepared adhesive is a bar coater No. By 6, it apply | coated to each process surface of a corona treatment CPP film and a corona treatment CPP film so that application amount might be set to 2 g / m <2> in a dry state, and it left still on the conditions of 5 second at 80 degreeC, and 24 hours at 40 degreeC. Thereafter, the adhesive coated surfaces were overlapped and heat sealed under the conditions of 130 ° C., 3 kgf / cm 2, and 2 seconds. The heat-sealed specimen was cut to a width of 15 mm, and the specimen was subjected to a cycle of UV (70 ° C. for 8 hours) and dew condensation (50 ° C. for 4 hours) by QUV manufactured by US Q Panel. Thereafter, a T-type peeling test was conducted at a tensile rate of 50 mm / min, a measurement atmosphere of 25 ° C., and 50% RH.

[Adhesion Resistance Test]

Each prepared adhesive is a bar coater No. By 6, it apply | coated to the corona treatment CPP film so that application amount might be 2 g / m <2> in a dry state. After the adhesive was applied to the film, the solvent was volatilized at 80 ° C. for 5 seconds. Thereafter, the film coated with the adhesive was surface-backed and subjected to a load of 3 kgf / cm 2 by an adhesion tester, and then the adhesion resistance was evaluated under the conditions of 24 hours at 50 ° C.

Evaluation criteria: Good ◎> ○> △> × Poor

The results of the weather resistance, water resistance test, and adhesion test are summarized in Table 5.

TABLE 5

As described above, the polyurethane resin adhesive of the present invention is excellent in heat resistance, weather resistance, water resistance, mechanical properties, adhesion to all substrates including polyolefin, and the like. Moreover, since adhesiveness of this invention is excellent in adhesiveness other than the conventional dry lamination method, it is also possible to adhere | attach a film by a heat sealing method, and to manufacture a contact film.

Claims (2)

A laminating adhesive comprising a polyurethane resin obtained by reacting an active hydrogen group-containing compound with an organic diisocyanate, wherein the active hydrogen group-containing compound has a hydroxyl group-containing poly with a molar ratio of ethylene and butylene groups of 30/70 to 70/30. The adhesive for lamination | stacking containing 1-50 mol% of (ethylene-butylene) copolymers. In a laminating adhesive comprising a polyurethane-based resin obtained by reacting an active hydrogen group-containing compound with an organic diisocyanate, and a polyisocyanate compound, the molar ratio of the active hydrogen group-containing compound is 30/70 to 70 / A laminating adhesive, comprising 1 to 50 mol% of a hydroxyl group-containing poly (ethylene-butylene) copolymer of 30.