JPH1067976A - Polyurethane resin adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyurethane resin adhesive excellent in heat resistance, weather resistance, hydrolysis resistance, mechanical properties, adhesivity to all substrates including polyolefin substrates, etc. SOLUTION: This adhesive comprises a polyurethane resin obtained by reacting an organic diisocyanate with an active hydrogen groupcontaining compound containing 1-50mol.% of a hydroxyl groupcontaining poly(ethylene- butylene) copolymer having an ethylene group/butylene group molar ratio of 30/70 to 70/30. The adhesive also comprises the polyurethane resin and a polyisocyanate compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane resin adhesive, and more particularly, to adhesion to all substrates including hydrolysis resistance, heat resistance, weather resistance, mechanical properties, and polyolefin. The present invention relates to a polyurethane resin adhesive excellent in properties and the like.

[0002]

2. Description of the Related Art Conventionally, polyurethane-based adhesives are characterized by excellent adhesiveness to various adherends, high durability, etc., so that film laminates, plywood, furniture, automobiles, railways, electric appliances, and nonwoven fabrics are used. Are widely used in various fields such as shoes, bags and the like. However, in general, polyurethane-based adhesives have insufficient adhesion to polyolefins. In order to improve the adhesion to the polyolefin, a polyurethane-based adhesive having a polyolefin-based compound introduced into a molecular structure has been developed. For example, JP-A-3-20
No. 7782 discloses a reactive hot melt adhesive into which a hydroxyl group-containing polyisoprene is mainly introduced.
Japanese Patent Application Laid-Open No. 7-41751 discloses a thermoplastic elastomer adhesive using chlorinated polyolefin.

[0003]

However, the adhesive having a polyisoprene structure has 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 and hydrogenated products thereof have more than two functional groups, so there are restrictions on the molecular design of the polyurethane-based resin. That is, when the amount of the introduced active hydrogen group-containing polyolefin in the molecule is increased,
Since the molecular weight of the polyurethane must be reduced, the durability is poor. Conversely, if the durability is to be improved by increasing the molecular weight, the amount of the introduction must be reduced, so that the adhesion to the polyolefin becomes poor. Further, those using a chlorinated polyolefin have problems such as deterioration of the adhesive and corrosion of the adhesive container due to a dehydrochlorination reaction over time. An object of the present invention is to solve these problems of the prior art and to provide an adhesive which simultaneously satisfies the adhesiveness to polyolefin and the durability at the same time.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve such problems of the prior art, and as a result,
The present inventors have found that an adhesive using a polyurethane resin into which a specific hydroxyl group-containing polyolefin has been introduced and an adhesive obtained by adding a polyisocyanate compound to the adhesive can achieve the above object, and have completed the present invention.

That is, the present invention relates to an active hydrogen group containing 1 to 50 mol% of a hydroxyl group-containing poly (ethylene-butylene) copolymer having a molar ratio of ethylene group to butylene group in the range of 30/70 to 70/30. An adhesive comprising a polyurethane resin obtained by reacting a contained compound with an organic diisocyanate.

Further, the present invention provides an active hydrogen group-containing poly (ethylene-butylene) copolymer containing 1 to 50 mol% of a hydroxyl group-containing poly (ethylene-butylene) copolymer having a molar ratio of ethylene groups to butylene groups in the range of 30/70 to 70/30. An adhesive comprising a polyurethane resin obtained by reacting a compound with an organic diisocyanate, and a polyisocyanate compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The hydroxyl group-containing poly (ethylene-butylene) copolymer used in the present invention is a compound having a molar ratio of ethylene groups to butylene groups in the range of 30/70 to 70/30. It can be obtained by grafting a vinyl alcohol compound to a poly (ethylene-butylene) copolymer obtained by living polymerization such as radical polymerization or anionic polymerization of ethylene and butylene, or by treating a terminal polymerization initiator component. Random copolymers are preferred because they have the lowest crystallinity and the highest adhesive strength. When the molar ratio between the ethylene group and the butylene group of the hydroxyl group-containing poly (ethylene-butylene) copolymer is out of the range of 30/70 to 70/30, the crystallinity becomes large and the melting temperature becomes high. Is difficult to obtain.

The number average molecular weight of the hydroxyl group-containing poly (ethylene-butylene) copolymer is preferably from 500 to 10,000, more preferably from 1,000 to 9,000. When the number average molecular weight of the hydroxyl group-containing poly (ethylene-butylene) copolymer is less than 500, the result is almost the same as when a mere aliphatic chain extender is introduced into the polyurethane resin,
Although the Tg and softening point of the obtained polyurethane resin are high, the adhesiveness to polyolefin is insufficient. Also,
When the number average molecular weight exceeds 10,000, the compatibility with other polyols and isocyanates is originally low, and the viscosity of the hydroxyl group-containing poly (ethylene-butylene) copolymer becomes high. It is difficult to obtain a polyurethane resin adhesive.

The hydroxyl group content of the hydroxyl group-containing poly (ethylene-butylene) copolymer is 1.5 to 2.5 per molecule.
Is preferable, and 1.8 to 2.0 are more preferable.
Zero is most preferred. 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 molecule, and as a result, the stability with time is poor. When the number of hydroxyl groups exceeds 2.5, gelation occurs during the synthesis of the polyurethane resin depending on the amount of the hydroxyl group-containing poly (ethylene-butylene) copolymer introduced, and it is difficult to obtain the polyurethane resin itself.

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

In the present invention, the amount of the hydroxyl group-containing poly (ethylene-butylene) copolymer introduced into the polyurethane resin molecule is 1 to 5 with respect to the total amount of the active hydrogen group-containing compound.
0 mol%, preferably 5 to 30 mol%. If the amount of the hydroxyl group-containing poly (ethylene-butylene) copolymer is less than 1 mol%, the adhesion to the polyolefin will be poor. On the other hand, if it exceeds 50 mol%, the adhesion to other than polyolefin such as polyethylene terephthalate and nylon becomes poor.

In the present invention, the active hydrogen group-containing compound used in combination with the hydroxyl group-containing poly (ethylene-butylene) copolymer is, for example, a polyester polyol, polyether polyol, polycarbonate polyol, acrylic polyol, polyether polyamine or the like having a molecular weight of 500. A high molecular polyol, a high molecular polyamine or a low molecular polyol having a molecular weight of 18 to 500, a low molecular polyamine,
A chain extender such as a low molecular weight amino alcohol or water may be used. Other active hydrogen group-containing compounds include monoalcohols and monoamines, and these and the aforementioned low-molecular-weight amino alcohols are also used as reaction terminators. Preferred polymer polyols are polyester polyols having good adhesion, heat resistance and durability. These active hydrogen group-containing compounds may be a single product or may be composed of a plurality of compounds having an average number of functional groups of 2 to 3. Is most preferable because it is easy to control the molecular weight. In addition, these active hydrogen group-containing compounds may include a carboxyl group, a tertiary amino group, a sulfonic acid group, a phosphoric acid group, and the like, and salts thereof in the molecule.

Among the above-mentioned high molecular polyols, specific examples of polyester polyols 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,
So-called low molecular glycols such as 2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A Or a mixture thereof and a dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid, naphthylene dicarboxylic acid, and these acids Examples thereof include polyesters having hydroxyl groups at both terminals obtained by a dehydration condensation reaction with an ester or an acid anhydride, and polycaprolactone diol obtained by ring-opening polymerization of ε-caprolactone.

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

Specific examples of the polycarbonate polyol include those obtained by a dephenol reaction between diphenyl carbonate and low molecular weight glycols used in the synthesis of the polyester polyol.

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

Examples of the low molecular polyol include low molecular glycols used in the synthesis of the polyester polyol.

Examples of the low-molecular polyamine include aliphatic diamines such as ethylenediamine and hexamethylenediamine, alicyclic diamines such as isophoronediamine (hereinafter abbreviated as IPDA) and cyclohexyldiamine, and the like.
And aromatic diamines such as diaminodiphenylmethane and diaminodiphenylsulfone.

Examples of the low molecular weight amino alcohol include monoethanolamine and diethanolamine.

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

The organic diisocyanate used in the present invention includes hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate (hereinafter abbreviated as IPDI), cyclohexyl diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene diisocyanate, Hydrogenated trimethylxylylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, 2,2,4-trimethylhexamethylene-1,6-diisocyanate, 2,4,4
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 abbreviated as 2,4-TDI), tolylene-2,6-diisocyanate, ortho-xylylene diisocyanate, meta-xylylene diisocyanate, para-xylylene diisocyanate, tetramethyl xylylene diisocyanate, etc. And mixtures of two or more of the above.

The isocyanate group / active hydrogen group (molar ratio) of the active hydrogen group-containing compound and the organic diisocyanate is preferably 0.5 / 1.% in order to avoid gelation in the production of the polyurethane resin and to make the terminal active hydrogen group. 0-1.0
/1.0 is preferable.

For synthesizing the polyurethane resin in the present invention, a known so-called urethane-forming catalyst can be used. Specific examples include organic metal compounds such as dibutyltin dilaurate (hereinafter abbreviated as DBTDL), organic amines such as triethylenediamine, and salts thereof.

The method for producing a polyurethane resin according to the present invention is a method for reacting all the active hydrogen group-containing compounds including a hydroxyl group-containing poly (ethylene-butylene) copolymer with an organic diisocyanate at a time to form a terminal active hydrogen group. The shot method, or first, hydroxyl group-containing poly (ethylene-
An isocyanate-terminated prepolymer is synthesized by reacting a butylene) copolymer and / or an active hydrogen group-containing compound with an organic diisocyanate sequentially or all at once, followed by chain extension with a chain extender or reaction with a reaction terminator to activate the terminal. A prepolymer method using a hydrogen group may be used. In these methods, it can be produced by a solid reaction method using no solvent or a solution reaction method using a solvent. When synthesizing a polyurethane resin by a solution reaction method, as a solvent that can be used,
Aliphatic hydrocarbon solvents such as pentane and hexane, aromatic hydrocarbon solvents such as toluene and xylene, acetone and methyl ethyl ketone (hereinafter abbreviated as MEK)
Ketone solvents such as methanol, alcohol solvents such as methanol and ethanol, ester solvents such as ethyl acetate and butyl acetate, ether solvents such as diethyl ether, and chlorine solvents such as methylene chloride and ethylene dichloride. Can be used singly or as a mixture, and may be appropriately selected according to the bonding conditions and the like.

The number average molecular weight of the polyurethane resin in the present invention is preferably from 5,000 to 1,000,000, and more preferably from 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 the melting temperature become too high, resulting in poor workability.

The polyurethane resin adhesive of the present invention can be used as a so-called one-pack, but it may be used by adding a polyisocyanate compound thereto in order to further improve heat resistance and durability. .

The amount of the polyisocyanate compound is preferably 1 to 50 parts by weight, and more preferably 3 to 50 parts by weight, based on 100 parts by weight of the polyurethane resin from the viewpoint of adhesive strength.
More preferably, it is 20 parts by weight.

Examples of the polyisocyanate compound that can be used in the present invention include, in addition to polymeric MDI and crude TDI, so-called prepolymers having a terminal isocyanate group. Adduct modified types such as Coronate L and Coronate HL manufactured by Co., Ltd .; Coronate HX and Coronate 2030 manufactured by Nippon Polyurethane Industry Co., Ltd.
And Hustans Japan Co., Ltd. VESTANATE T-1
890 and the like, and buret modified types such as Duranate 24A-100 manufactured by Asahi Kasei Corporation and Sumidur N manufactured by Sumitomo Bayer Urethane Co., Ltd.

Further, in the present invention, other resins such as vinyl chloride resin, nylon resin and acrylic resin may be added. Further, a wax, a plasticizer, an elastomer, a stabilizer and the like may be added.

In the bonding method using the polyurethane resin adhesive of the present invention, an adhesive is applied to an ordinary adherend, and if necessary, an open time is applied for several seconds to several minutes, and bonding is performed. In addition to the heating reaction method, the polyurethane resin adhesive of the present invention has good blocking resistance, so that the adhesive is applied to the adherend in advance, and a few days later, it is bonded by heat sealing. Can be glued.

In particular, when bonding is performed by a heat sealing method, the heat sealing condition is preferably a temperature of 100 to 20.
0 ° C., more preferably 120-180 ° C., the sealing pressure is preferably 0.1-10 kgf / cm ² , more preferably 1-5 kgf / cm ² , and the sealing time is preferably 0.1-0.
It is 1 to 10 seconds, more preferably 0.5 to 5 seconds.
Temperature is less than 100 ° C, sealing pressure is 0.1kgf / cm ²
When the sealing time is less than 0.1 second, the adhesive strength hardly appears. When the bonding temperature exceeds 200 ° C., the adhesive and the adherend are damaged. Seal pressure is 10
When it exceeds kgf / cm ² or when the sealing time exceeds 10 seconds, there is no problem in adhesive strength or durability, but it is not economical.

The polyurethane resin adhesive of the present invention has a P
It can be bonded to polar substrates such as ET and nylon, non-polar substrates such as polyethylene and polypropylene, rubbers such as SBR and NBR, metals such as iron and aluminum, glass, wood, and paper. It is particularly effective as a polyolefin-based adhesive, which did not provide sufficient adhesive strength with a conventional polyurethane-based resin adhesive.

[0033]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Unless otherwise specified, parts and% in Synthesis Examples, Comparative Synthesis Examples, Examples and Comparative Examples mean “parts by weight” and “% by weight”, respectively.

[Synthesis of Polyurethane-Based Resin] Synthesis Example 1 3-Methyl-1,5-methyl was added to a four-necked flask equipped with a stirrer, thermometer, Aline cooling tube, and nitrogen gas inlet tube.
Hydroxyl-terminated polyester obtained from dehydration condensation of pentanediol and adipic acid (trade name: Kuraray polyol P-2010, manufactured by Kuraray Co., Ltd., number average molecular weight 20)
00), 30.0 parts of a hydroxyl group-containing poly (ethylene-butylene) copolymer (trade name: HPVM-2202, manufactured by Shell, number average molecular weight 3600), NPG
And 1300 parts of toluene and 300 parts of toluene were charged and heated to 40 ° C. To this, 38.0 parts of 2,4-TDI (isocyanate group / hydroxyl group (molar ratio) = 0.96), DBTDL
0.03 parts, 2270 cm by infrared spectroscopy
Until the peak of the isocyanate group of ^-1 disappears.
For urethanization reaction. Then, toluene was added to 200
And MEK were added to obtain a polyurethane resin solution PU-1. The solid content of PU-1 was 29.8%, the viscosity was 2700 cP / 25 ° C., and the number average molecular weight was 33,000.

Synthesis Example 2 In the same apparatus as in Synthesis Example 1, a number average molecular weight of 1000 obtained by dehydration condensation of diethylene glycol and sebacic acid was used.
Of both ends hydroxyl-containing polyester (hereinafter, DEG / Se)
A-1000), 146.3 parts of a hydroxyl group-containing poly (ethylene-butylene) copolymer HPVM-220
20.0 parts and toluene 200 parts were charged and heated to 40 ° C. Then, 68.6 parts of IPDI (isocyanate group / hydroxyl group (molar ratio) = 1.90) and 0.03 part of DBTDL were charged and urethanization reaction was carried out at 80 ° C. for 4 hours. Thereafter, 200 parts of toluene and 200 parts of MEK were added. Was charged to obtain a urethane prepolymer solution having isocyanate groups at both terminals. To this urethane prepolymer solution, a solution prepared by previously dissolving 23.6 parts of IPDA and 1.5 parts of diethanolamine in 100 parts of isopropanol was added, and reacted until infrared spectroscopic analysis revealed that the peak of the isocyanate group at 2270 cm ^-1 had disappeared. A polyurethane resin solution PU-2 was obtained. PU-2 had a solid content of 30.0%, a viscosity of 4000 cP / 25 ° C., and a number average molecular weight of 23,000.

Synthesis Example 3 In the same apparatus as in Synthesis Example 1, a number average molecular weight of 300 obtained by dehydration condensation of 1,6-hexanediol and adipic acid was used.
0 of both ends hydroxyl-containing polyester (hereinafter HG / AA)
-3000), and a hydroxyl group-containing poly (ethylene-butylene) copolymer HPVM-2202
Was added and 90.0 parts of toluene were charged, and the mixture was heated to 40 ° C. To this, 19.7 parts of 4,4'-MDI (isocyanate group / hydroxyl group (molar ratio) = 0.90), DBTD
L was added in an amount of 0.03 part, and 2270c obtained by infrared spectroscopy
Until the peak of the isocyanate group at m ^-1 disappears, 80
The urethanization reaction was carried out at ℃. Then, toluene was added to 200
And 200 parts of MEK, to obtain a polyurethane resin solution PU-3. PU-3 had a solid content of 29.8%, a viscosity of 3500 cP / 25 ° C., and a number average molecular weight of 34,000.

Synthesis Example 4 In a device similar to Synthesis Example 1, a dicarboxylic acid mixture of phthalic anhydride / azelaic acid = 1/1 (molar ratio) and EG / N
PG = 1/1 (molar ratio) A diol mixture obtained by dehydration condensation of a diol mixture having a number-average molecular weight of 2,000 and having both terminal hydroxyl groups (hereinafter referred to as (EG / NPG) / (PA / Az)
A) -2000), 203.3 parts of a hydroxyl group-containing poly (ethylene-butylene) copolymer HPVM-22
20.0, 3.2 parts of ethylene glycol and 300 parts of toluene were charged and uniformly stirred. 17.7 parts of IPDI and 13.8 parts of 2,4-TDI (isocyanate group / hydroxyl group (molar ratio) = 0.94) were added to this solution.
0.03 parts of DBTDL was charged, and 2
The urethanization reaction was carried out at 80 ° C. until the peak of the isocyanate group at 270 cm ⁻¹ disappeared. Thereafter, 200 parts of toluene and 200 parts of MEK were added to obtain a polyurethane resin solution PU-4. The solid content of PU-4 is 30.0
%, Viscosity is 2000 cP / 25 ° C., number average molecular weight is 29
000.

Comparative Synthesis Example 1 In the same apparatus as in Synthesis Example 1, 219.6 parts of a polyester Kuraray polyol P-2010 containing hydroxyl groups at both ends, a toluene solution of chlorinated polypropylene containing an active hydrogen group (solid content = 50%, commercial product) Name: Supercron 813A, 60.0 parts of Nippon Paper Industries Co., Ltd., 11.4 parts of NPG, bisphenol A type epoxy resin (trade name: Epicoat 828, manufactured by Yuka Shell Epoxy) 1.5 parts and 270 parts of toluene were charged and heated to 40 ° C. To this,
37.4 parts of 4-TDI (isocyanate group / hydroxyl group (molar ratio) = 0.96) and 0.03 part of DBTDL were charged, and 80 parts were measured until the peak of the isocyanate group at 2270 cm ^-1 by infrared spectroscopy disappeared. The urethanization reaction was carried out at ℃. Then, 200 parts of toluene and 200 parts of MEK
In addition, a polyurethane resin solution PU-5 was obtained. P
U-5 has a solid content of 30.0% and a viscosity of 1700 cP / 2.
At 5 ° C., the number average molecular weight was 30,000.

Comparative Synthesis Example 2 Hydroxyl-Containing Poly (ethylene-butylene) Copolymer HPV
M-2202 is a hydroxyl group-containing polybutadiene (trade name: R
The reaction solution was gelled when synthesized in the same manner as in Synthesis Example 2 except that -45HT was replaced by Idemitsu Petrochemical Co., Ltd.).

The raw materials and synthesis results of Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 and 2 are summarized in Table 1.

[Table 1]

Examples 1 to 12 and Comparative Examples 1 to 3 [Preparation of adhesive] Synthetic polyurethane resin solution PU
Using -1 to 5, an adhesive was prepared by blending as follows. <Composition> Polyurethane-based resin solution 50 parts MEK 25 parts Toluene 25 parts Coronate L or Coronate HL 0 parts or 3 parts Table 2 summarizes this composition.

[0042]

[Table 2]

[Adhesion Test 1] Each of the adhesives prepared as described above was used as a bar coater No. At 6, coating was performed using the following film combinations so that the coating amount was 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 applying each adhesive on the treated surface of
The sample was allowed to stand at + 40 ° C. × 24 hours for 5 seconds. Then, with the combination of the films (1) to (4), the adhesive-applied surfaces are overlapped with each other, and 130 ° C. × 3 kgf / cm ² × 2
Heat sealed for seconds. The heat-sealed test piece was cut to a width of 15 mm, and a tensile speed: 50 mm /
A T-peel test was performed at 25 ° C. × 50% RH.

[Adhesion Test 2] Each adhesive was treated with a bar coater No. At 6, coating was performed using the following film combinations so that the coating amount was 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 Adhesive Was applied to the treated surface of each film, and after taking an open time of 80 ° C. × 5 seconds, the films were immediately bonded, and after the bonding, they were allowed to stand at 50 ° C. × 24 hours. Then, it is cut to a width of 15 mm, and a tensile speed: 50 mm / min.
Measurement atmosphere: T-type peel test was performed at 25 ° C. × 50% RH.

Table 3 shows the results of the adhesion test 1 and Table 4 shows the results of the adhesion test 2.

[Table 3]

[0046]

[Table 4]

[Weather Resistance and Water Resistance Tests] Each of the prepared adhesives was coated with a bar coater No. In 6, the coating amount is 2 g / dry
It was applied to each treated surface of the corona-treated CPP film and the corona-treated CPP film so as to obtain m ² , and allowed to stand at 80 ° C. × 5 seconds + 40 ° C. × 24 hours. Thereafter, the adhesive-coated surfaces are overlapped with each other, and 130 ° C. × 3 kgf / cm ²
Heat sealing was performed for 2 seconds. The heat-sealed test piece was cut into a width of 15 mm, and the test piece was subjected to a cycle of UV: 70 ° C. × 8 hours + condensation: 50 ° C. × 4 hours by QUV manufactured by Q Panel, USA for 4 weeks. Thereafter, the tensile speed: 50 mm / min, measuring conditions: 25 ° C. × 5
A T-type peel test was performed at 0% RH.

[Blocking Resistance Test] Each of the prepared adhesives was applied to a bar coater No. 6、2g dry amount
/ M ² on a corona-treated CPP film. After applying the adhesive to the film, the solvent was volatilized at 80 ° C. × 5 seconds. After that, the film coated with the adhesive was layered on the surface-back, and 3 kg was measured with a blocking tester.
An anti-blocking property was evaluated under a condition of 50 ° C. × 24 hours under a load of f / cm ² . Evaluation criteria: good ◎> ○ ＞ △ ＞ × poor The results of the weather resistance, water resistance test and blocking resistance test are summarized in Table 5.

[0049]

[Table 5]

[0050]

As described above, the polyurethane resin adhesive of the present invention is excellent in heat resistance, weather resistance, water resistance, mechanical properties, adhesion to any base material including polyolefin, and the like. is there. Also, using the adhesive of the present invention,
In addition to the conventional dry lamination method, it is possible to produce a laminated film by bonding a film by a heat sealing method because of its excellent blocking resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08G 18/65 NES C08G 18/65 NES

Claims (2)

[Claims] 1. The method according to claim 1, wherein the molar ratio of ethylene groups to butylene groups is 30.
Comprising a polyurethane resin obtained by reacting an active hydrogen group-containing compound containing 1 to 50 mol% of a hydroxyl group-containing poly (ethylene-butylene) copolymer in the range of / 70 to 70/30 with an organic diisocyanate, An adhesive characterized by the following. 2. The method according to claim 1, wherein the molar ratio of ethylene groups to butylene groups is 30.
Polyurethane resin obtained by reacting an organic diisocyanate with an active hydrogen group-containing compound containing 1 to 50 mol% of a hydroxyl group-containing poly (ethylene-butylene) copolymer in the range of / 70 to 70/30, and polyisocyanate An adhesive comprising a compound.