JP3057366B2 - Adhesive for two-component dry lamination - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an adhesive for two-component dry lamination. More specifically, polyolefin film, polyester film, polyacryl film, polyvinyl chloride film, polystyrene film,
Especially for dry laminating of plastic film such as nylon film, ethylene vinyl alcohol copolymer film, polyvinyl alcohol film or plastic film whose surface is vapor-deposited with aluminum or silica or coated with polyvinylidene chloride, and polyolefin film The present invention relates to a two-part adhesive for dry lamination that can be suitably used.

[0002]

2. Description of the Related Art Polyurethane adhesives conventionally used for laminating plastic films or sheets include isocyanate group-terminated urethane prepolymers composed of trihydric alcohols and polyether polyols and polyester polyols and polyisocyanates, and polyether polyols. And / or adhesive composition for laminate film comprising polyester polyol (for example, JP-A-63-196678), two-pack curing type comprising a polyol or polyurethane polyol and an aromatic polyisocyanate group-terminated urethane prepolymer Adhesive composition (for example, JP-A-3-182584)
Etc. are known.

[0003]

However, the above-mentioned materials have insufficient adhesion to polyolefin films, and the above-mentioned materials have insufficient adhesion, weather resistance and heat resistance to polyolefin films. was there.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a combination of an isocyanate component having a specific composition and a polyol component having a specific composition of a polyol or a modified product thereof is used. It has been found that by using this, an adhesive for two-component dry lamination having excellent adhesion, flexibility, transparency, weather resistance and heat resistance to a polyolefin film or the like can be obtained, and the present invention has been achieved.

That is, the present invention relates to an isocyanate group-terminated urethane prepolymer (A1) comprising a polyol (a1) and an excess of an aliphatic polyisocyanate (b1), or (A1) and an aliphatic polyisocyanate (A2). An isocyanate component (A) consisting of
1) and / or a two-component dry laminating adhesive comprising a polyol component (B) comprising a hydroxyl-terminated urethane prepolymer (B2) from a polyol (a2) and an aliphatic polyisocyanate (b2); a
1) Polyester polyol (a11) having a hydroxyl equivalent of 300 to 1500, polyether polyol (a12) having a hydroxyl equivalent of 300 to 1500, and a hydroxyl equivalent of 300
Less than 3 to 8 functional polyol (a13) and polydiene polyol (a14) having a hydroxyl equivalent of 300 to 2000
An adhesive characterized by using a 4- to 8-functional polyol (a21) having a hydroxyl equivalent of 50 to 300 as (B1) and / or (a2); and a polyolefin film, a polyester film, a polyacryl film, A plastic film selected from a polyvinyl chloride film, a polystyrene film, a nylon film, an ethylene vinyl alcohol copolymer film, a polyvinyl alcohol film, and a film obtained by vapor-depositing the surface of these with aluminum or silica or coating with polyvinylidene chloride; A film is a laminated film bonded by dry lamination bonding or extrusion lamination bonding using the adhesive.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The isocyanate component (A) in the present invention comprises an isocyanate group-terminated urethane prepolymer (A1) or (A1) and an aliphatic polyisocyanate (A2).

The isocyanate group-terminated urethane prepolymer (A1) has a hydroxyl equivalent of 300 to 1500.
Examples of the polyester polyol (a11) include dicarboxylic acids [aliphatic dicarboxylic acids having 4 to 20 carbon atoms (for example, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, dimer acid, and the like); And at least one aromatic dicarboxylic acid (e.g., terephthalic acid, isophthalic acid, etc.) and their ester-forming derivatives (lower alkyl esters, acid anhydrides, acid halides, etc.) and a low molecular polyol [2 to 3] Functional low molecular polyols (dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butane Diol, 2,3-butanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, 2-methyl-2-propyl -
1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-
Pentanediol, 2,2,4-trimethyl-1,3-
Pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol,
1,8-octanediol, 1,9-nonanediol and the like; trihydric alcohols such as glycerin and trimethylolpropane, and alkylene oxides thereof (the above and below, having 2 to 12 carbon atoms, preferably 2 to 2 carbon atoms)
Ethylene oxide, propylene oxide, 1,
2-, 1,3- or 2,3-butylene oxide,
Examples include tetrahydrofuran, styrene oxide and epichlorohydrin. ) Low molar adduct (molecular weight 5)
Condensed polyester polyol obtained by polycondensation with at least one of the following low-molecular-weight polyols:
A polylactone polyol obtained by ring-opening polymerization of a lactone having 4 to 12 carbon atoms (e.g., γ-butyrolactone, ε-caprolactone, γ-valerolactone, 3-methyl-γ-valerolactone, etc.) using at least one species as a starting material ( For example, polycaprolactone diol or triol, polyvalerolactone diol and the like); polycarbonate polyols (for example, polyhexamethylene carbonate diol and the like) derived from one or more of the above low-molecular polyols and a carbonate ester (ethylene carbonate, dimethyl carbonate and the like) and A mixture of two or more of these may be mentioned. Among these, preferred are condensed polyester polyols, and particularly preferred are polyalkylene adipate diols obtained by polycondensing adipic acid with ethylene glycol and / or propylene glycol. The hydroxyl equivalent of (a11) is usually 300
１1500, preferably 350２〜1200, and the number of functional groups is usually 2３3, preferably 2. If the hydroxyl equivalent is less than 300, the flexibility of the cured film of the adhesive is poor, and if it exceeds 1500, the adhesion to the polyolefin film is reduced.

The hydroxyl equivalent constituting (A1) is from 300 to
As the polyether polyol (a12) of 1500, one or more alkylene oxides (co) of the dihydric alcohol or trihydric alcohol exemplified as the starting material of the polyester polyol and the tetra- to octahydric alcohol exemplified in (a13) below Additives (addition form in case of co-addition may be either block or random)
Is mentioned. Of these, preferred is polyoxytetramethylene glycol obtained by ring-opening addition polymerization of tetrahydrofuran starting from 1,4-butanediol. The hydroxyl equivalent of (a12) is usually 30
The number is from 0 to 1500, preferably from 350 to 1200, and the number of functional groups is usually from 2 to 8, preferably from 2 to 4. If the hydroxyl equivalent is less than 300, the flexibility of the cured film of the adhesive is poor, and if it exceeds 1500, the adhesion to the polyolefin film is reduced.

The 3- to 8-functional polyol (a13) having a hydroxyl equivalent of less than 300 constituting (A1) is preferably 3 to 8
Octahydric alcohols (trihydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, 1,2,6-hexanetriol; 4- to 8hydric alcohols such as pentaerythritol, diglycerin, dipentaerythritol, trihydric alcohol Glycerin, tripetaerythritol, xylose, arabinose, ribulose, glucose, fructose, mannose, galactose, erythritol, trait, arabbit, rebit, xylit, sorbit, mannitol, sucrose, etc.), and alkylene oxide (co) adducts thereof ( The form of addition in the case of co-addition may be either block or random.) And polylactone polio obtained by ring-opening addition polymerization of lactones starting from tri- to hexafunctional polyhydric alcohols. Le, and the like. These (a1
Two or more of those exemplified as 3) can be used in combination. Of these, preferred are trimethylolpropane, propylene oxide adduct of trimethylolpropane, propylene oxide adduct of glycerin, and polycaprolactone triol, and particularly preferred are trimethylolpropane, polycaprolactone triol and combinations thereof. The hydroxyl equivalent of (a13) is usually less than 300, preferably 250 or less, and the number of functional groups is usually 3 to 8, preferably 3 to 4. When the hydroxyl equivalent is 300 or more, the adhesiveness to the polyolefin film is reduced.

The hydroxyl equivalent of the component (A1) is from 250 to
As the polydiene polyol (a14) of 2000,
Examples thereof include polybutadiene polyol, polyisoprene polyol, a partially or completely hydrogenated product thereof. Of these, preferred is polybutadiene diol, and particularly preferred is polybutadiene diol having 1,2-bonds in the molecule in the microstructure of 80% by weight or more. The hydroxyl equivalent of (a14) is usually 250
2,000, preferably 300-1800, and the average number of functional groups is usually 1.5-3, preferably 1.7-.
2.5. If the hydroxyl group equivalent is less than 250, the cured film of the adhesive becomes hard and there is a problem in terms of flexibility. If it exceeds 2,000, the adhesion to the polyolefin film is reduced.

The aliphatic polyisocyanate (b1) constituting (A1) includes, for example, hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate (TMDI) and lysine diisocyanate (LDI). 2-18 aliphatic diisocyanates; dicyclohexylmethane diisocyanate (HMDI),
An alicyclic diisocyanate having 4 to 15 carbon atoms such as isophorone diisocyanate (IPDI), 1,4-cyclohexane diisocyanate (CHDI), hydrogenated xylene diisocyanate (HXDI), hydrogenated tolylene diisocyanate (HTDI); xylylene diisocyanate (X
DI), 8 to 15 carbon atoms such as α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI)
Araliphatic diisocyanates; modified products of these diisocyanates [for example, isocyanurate modified product, buret modified product, uretdione modified product, carbodiimide modified product, diisocyanate adduct of polyhydric alcohol (for example, trimethylolpropane and diisocyanate 1:
And a mixture of two or more of these. Preferred of these are IP
DI and HMDI, with IPD being particularly preferred.
I. In the present invention, the term "aliphatic polyisocyanate", as generally used, refers to aliphatic,
The alicyclic (formula) and araliphatic polyisocyanates are used in a meaning that includes them.

The polyol (a1) in (A1)
Are (a11), (a12), (a13) and (a1)
The equivalent ratio when (4) is composed of (a11) is 0.01 to 1 equivalent, preferably 0.1 equivalent, per 1 equivalent of (a11).
02 to 0.8, (a13) is 0.01 to 2 equivalents, preferably 0.02 to 1.5, and (a14) is 0.01 to 1 equivalent, preferably 0.02 to 0.8 equivalent. . (A1
If 2) is less than 0.01 equivalent, the appearance of the adhesive becomes cloudy and 1
If the amount exceeds the equivalent, the adhesiveness to the polyolefin film decreases. If (a13) is less than 0.01 equivalent, the adhesion to the polyolefin film will be reduced, and if it exceeds 2 equivalents, the flexibility of the cured film of the adhesive will be poor. (A1
If 4) is less than 0.01 equivalent or more than 1 equivalent, the adhesiveness to the polyolefin film is reduced. Also,
The content of (a11) in the total of (a11), (a12) and (a13) is 20 to 95 mol%, preferably 30 to 95 mol%.
85 mol%, the content of (a12) is 1 to 20 mol%, preferably 2 to 15 mol%, and the content of (a13) is 4 to 60 mol%.
Mol%, preferably 5 to 50 mol%, and (a
The total of (a11), (a12) and (a13) in 1) is 80 to 99 mol%, preferably 90 to 98 mol%, and (a14) is 1 to 20 mol%, preferably 2 to 10 mol%.
Mol%.

The polyol (a1) in the above (A1)
Is (a11), (a12) and (a13), the equivalent ratio is (a11) per equivalent, (a1)
2) is 0.01 to 1 equivalent, preferably 0.02 to 0.8
Equivalent, (a13) is 0.01 to 2 equivalents, preferably 0.1 equivalent.
02 to 1.5 equivalents. When (a12) is less than 0.01 equivalent, the appearance of the adhesive becomes cloudy, and when it exceeds 1 equivalent, the adhesiveness to the polyolefin film is reduced. (A1
If 3) is less than 0.01 equivalent, the adhesiveness to the polyolefin film is lowered, and if it exceeds 2 equivalent, the flexibility of the cured film of the adhesive becomes poor. Also, (a11), (a1
The content of (a11) in the total of (2) and (a13) is 2
0 to 95 mol%, preferably 30 to 85 mol%, (a1
The content of 2) is 1 to 20 mol%, preferably 2 to 15 mol%, and the content of (a13) is 4 to 60 mol%, preferably 5 to 5 mol%.
~ 50 mol%.

The (A1) is composed of (a1) and an excess (b1)
By a conventional method (one-shot method or multi-stage method) to obtain a urethanization reaction. The equivalent ratio of the isocyanate group of (b1) to the hydroxyl group of (a1) (NCO /
OH) is usually (1.1-2.5): 1, preferably (1.2-2.2): 1. If (b1) is less than 1.1 equivalents, the viscosity of the obtained component (A) becomes high, so that the coating workability of the adhesive becomes poor. If it exceeds 2.5 equivalents, the adhesiveness to the polyolefin film tends to decrease. Becomes The reaction temperature for urethanization is usually 50 to 100 ° C. An organic solvent (eg, cyclohexane, toluene, xylene, methyl ethyl ketone, methyl acetate, ethyl acetate, N, N-dimethylformamide, etc.) can be used for the urethanization reaction, if necessary. Further, a catalyst usually used for polyurethane to promote the reaction [for example, an organometallic compound (dibutyltin dilaurate,
Stannous octoate, stannas octoate, tetrabutoxytitanium, tetrapropoxytitanium, isopropoxy / trisdioctylphosphonyltitanium, etc.); amine compounds (triethylamine, triethylenediamine, N
-Pentamethyldiethylenetriamine and the like)]. The amount of the catalyst used is not particularly limited, but is usually 0.0001 to 0.5% by weight based on the total weight of (a1) and (b1).

The aliphatic polyisocyanate (A2) constituting the component (A) in the present invention is preferably one having 3 to 6 functional groups or more, more preferably 3 to 4 functional groups, such as aliphatic diisocyanate and / or alicyclic ring. Modified products of the formula diisocyanate [modified isocyanurates, modified burettes, diisocyanate adducts of polyhydric alcohols (for example, a 1: 3 mol adduct of trimethylolpropane and diisocyanate), and the like]; Mixtures of more than one species. Of these, particularly preferred are modified isocyanurate and modified burette of hexamethylene diisocyanate.

In the component (A), (A1) and (A2)
When (A1) :( A2) is used in combination, the equivalent ratio is usually 1: (0 to 5), preferably 1: (0.01 to 5), and more preferably 1: (0.02 to 3). It is. When (A2) exceeds 5 equivalents, the adhesiveness to the polyolefin film decreases.

The content of free isocyanate groups (per solid) in the component (A) is usually 1 to 15% by weight, preferably 2 to 10% by weight. The viscosity (25 ° C.) is usually 50 to 3000 m at a solid content concentration of 50 to 70% by weight.
Pa · s, preferably 100 to 2500 mPa · s.

The polyol component (B) in the present invention comprises a hydroxyl-terminated urethane prepolymer (B2) comprising a polyol (B1) and / or a polyol (a2) and an aliphatic polyisocyanate (b2).

The polyols (B1) and (a2) constituting the component (B) in the present invention have a hydroxyl equivalent of 50.
And a combination of (a21) and a polydiene polyol (a22) having a hydroxyl equivalent of 250 to 2,000.

As the above (a21), alkylene oxide (co) adducts of 4- to octahydric alcohols among those exemplified as (a13) can be mentioned. Of these, preferred are propylene oxide adducts of one or more polyhydric alcohols selected from pentaerythritol, dipentaerythritol and sorbitol, and block or random coadducts of ethylene oxide and propylene oxide. The hydroxyl group equivalent of (a21) is usually from 50 to 300, preferably from 70 to 250, and the number of functional groups is usually from 4 to 8, preferably from 5 to 6. If the hydroxyl group equivalent is less than 50, the flexibility of the cured film of the adhesive becomes poor, and if it exceeds 300, the adhesiveness to the polyolefin film decreases.

Further, (a2) used in combination with (a21)
Examples of 2) include polybutadiene polyol, polyisoprene polyol, and partially or completely hydrogenated products thereof. Of these, preferred are polybutadiene polyols, and particularly preferred are polybutadiene polyols having 1,2-bonds in the molecule in the microstructure of 80% by weight or more. The hydroxyl group equivalent of (a22) is usually from 250 to 2,000, preferably from 300 to 180.
0, and the average number of functional groups is usually 1.5 to 3, preferably 1.7 to 2.5. When the hydroxyl equivalent is less than 250, the cured film of the adhesive becomes hard, so that the flexibility of the composite film becomes insufficient. When it exceeds 2,000, the adhesiveness to the polyolefin film decreases. (A21) and (a
The equivalent ratio of (a21) :( a22) when used together with 22) is usually 1: (0.05 to 1), preferably 1:
(0.08 to 0.9). Within this range, the adhesion to the polyolefin film will be better.

Hydroxyl terminated urethane prepolymer (B2)
As the aliphatic polyisocyanate (b2) constituting the above, the aliphatic polyisocyanate exemplified as (b1) in the component (A) can be mentioned. Of these, preferred are modified aliphatic diisocyanates and / or alicyclic diisocyanates (modified isocyanurates, modified burettes, modified uretdione, modified carbodiimides, modified diisocyanate adducts of polyhydric alcohols, and the like). And particularly preferred are isocyanurate-modified and burette-modified hexamethylene diisocyanate.

The equivalent ratio (OH / NCO) of the hydroxyl group of (a2) and the isocyanate group of (b2) in (B2)
Is usually (3 to 25 or more): 1, preferably (5 to 20): 1. When (a2) is less than 3 equivalents,
(B2) is not preferred because the viscosity of (B2) may be too high or gelation may occur. The reaction temperature for obtaining the compound (B2) is usually 50 to 100 ° C, and if necessary, an organic solvent (for example, cyclohexane, toluene, xylene, methyl ethyl ketone, methyl acetate, ethyl acetate, N, N-
Dimethylformamide, etc.). Further, the catalyst exemplified in the section of the component (A) can be used to promote the reaction. The amount of the catalyst is not particularly limited, but is usually 0.0001 to 0.5% by weight based on the total weight of (a2) and (b2).

The hydroxyl value of the component (B) (per solid)
Is usually 100 to 1200, preferably 150 to 100
0, more preferably 200 to 800. The viscosity (25 ° C.) is usually 3 to 150 mPa · s, preferably 5 to 130 mPa at a solid concentration of 50 to 60% by weight.
-It is s.

In the adhesive of the present invention, the equivalent ratio of the isocyanate group of the component (A) to the hydroxyl group of the component (B) (NC
(O / OH) is usually (0.7-1.3): 1, preferably (0.8-1.2): 1, and more preferably (0.9-1.3).
-1.1): 1. When the component (A) is less than 0.7 equivalent or more than 1.3 equivalent, the adhesiveness to the polyolefin film is reduced.

The adhesive of the present invention may contain a curing acceleration catalyst for the purpose of accelerating the curing reaction between the components (A) and (B). Examples of the curing-promoting catalyst include metal salts of alkyl (2 to 20 carbon atoms) phosphonic acid (salts such as potassium and sodium); metal salts of fatty acids having 8 to 20 carbon atoms (sodium, potassium, nickel, cobalt and cadmium). , Barium, calcium, zinc, etc.); dibutyltin dilaurate, dioctyltin maleate, dibutyldibutoxytin, bis (2-ethylhexyl) tin oxide, 1,1,3,3-tetrabutyl-
Organotin compounds such as 1,3-diacetoxydistannoxane; amine compounds (triethylamine, triethylenediamine, N-pentamethyldiethylenetriamine, etc.); tetrabutoxytitanium, tetrapropoxytitanium, isopropoxy / trisdioctylphosphonyltitanium, iso Organic titanium compounds such as propoxy triisostearate titanium; and mixtures of two or more thereof. Among these, preferred are organotin compounds, amine compounds and organotitanium compounds, and more preferred are dibutyltin dilaurate, dioctyltin maleate and titanium isopropoxy triisostearate. The amount of the curing accelerating catalyst to be added is usually 0.1 to the total solid weight of the components (A) and (B).
It is from 0.01 to 4% by weight, preferably from 0.1 to 3% by weight.
If necessary, known additives such as an antioxidant and an ultraviolet absorber can be added. The amount of the additive is usually 0.1 to 4% by weight, preferably 0.5 to 3% by weight based on the total weight of the solid components (A) and (B). There is no particular limitation on the method of adding these curing accelerating catalysts and additives, but it is desirable to incorporate them in the component (B) in advance.

The stability (pot life) of the two-part mixture comprising the component (A) and the component (B) is very good,
For example, when the solid content concentration of the two-part liquid mixture is 50% by weight,
The viscosity change rate [(viscosity after storage−initial blending viscosity) × 100 / initial blending viscosity] after storage at a temperature of 20 ° C. for 12 hours is less than 10%.

The two-component dry laminating adhesive of the present invention is useful for dry lamination bonding and / or extrusion lamination bonding between various plastic films or sheets and a polyolefin film. Plastic films such as polyolefin films, polyester films, polyacrylic films and polyvinyl chloride films, polystyrene films, nylon films, ethylene vinyl alcohol copolymer films, and polyvinyl alcohol films used for unit bath interiors and marking films Alternatively, a laminate film of a plastic film whose surface has been vapor-deposited with aluminum or silica or coated with polyvinylidene chloride and a polyolefin film. It can be particularly preferably used in the Lum manufacturing.

For coating the adhesive, a gravure coater, a reverse coater or the like is used. The coating amount (solid content) of the adhesive is usually ² to ²⁰ g / m ² . An ordinary dry laminator or extrusion laminator is used for lamination. The adhesive is completely cured when the laminated film is usually cured at 20 to 50 ° C. for 20 to 120 hours.

[0030]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto. In the following, "parts" indicates parts by weight and "%" indicates% by weight.

Example 1 1 L equipped with a stirrer, thermometer, cooling pipe and nitrogen inlet pipe
In a four-neck flask having a capacity of 150 parts, 150 parts of polyethylene adipate diol (“San Ester 2610”, manufactured by Sanyo Chemical Industries, number average molecular weight 1000, hydroxyl equivalent 500), polyoxypropylene diol (“San Nix Diol PP-1000”, Sanyo) Chemical average, number average molecular weight 10
00, hydroxyl equivalent 500) 37 parts, polybutadiene polyol ("NISSO-PB G-2000", manufactured by Nippon Soda, number average molecular weight 2000, hydroxyl equivalent 1120) 3
7 parts, trimethylolpropane 5 parts, polyoxypropylene triol (“Sannicks Triol GP-60”).
0 ", manufactured by Sanyo Chemical Industries, Ltd., 30 parts of number average molecular weight 600, hydroxyl equivalent 200), 280 parts of ethyl acetate and 70 parts of cyclohexane were uniformly mixed at a liquid temperature of 50 ° C. for 30 minutes. The water content of this mixture was 0.03%. Subsequently, 121 parts of dicyclohexylmethane diisocyanate and 0.06 parts of dibutyltin dilaurate were charged with stirring, and reacted at 70 ° C. for 5 hours under a nitrogen stream to obtain a free isocyanate group (NCO) content of 2.2% and a viscosity of 500 mPa.
An isocyanate-terminated urethane prepolymer solution (A-1) having a solid content of 52% at s (25 ° C.) was obtained. In a similar reaction vessel, a propylene oxide adduct of sorbitol (“Sanix hexaol SP-750”, manufactured by Sanyo Chemical Industries, number average molecular weight 750, hydroxyl equivalent 125) 3
50 parts, ethyl acetate 350 parts, dibutyltin dilaurate 2 parts, "Irganox 1135" (manufactured by Ciba Geigy,
0.5 parts of antioxidant, 1 part of "Tinuvin 571" (manufactured by Ciba Geigy, ultraviolet absorber) and 1 part of "Tinuvin 765"
(Ciba Geigy, light stabilizer) 1 part, 50 ℃
For 1 hour, hydroxyl value 244, viscosity 8 mPa · s
(25 ° C.), 50% solids polyol solution (B-1)
I got 100 parts of the above (A-1) and (B-1) 12
Parts (NCO / OH equivalent ratio = 1/1) were uniformly mixed to obtain the adhesive of the present invention. This adhesive was applied to the surface of a 50 μm-thick corona-treated polypropylene film (hereinafter abbreviated as surface-treated PP), and dried with warm air at 50 to 70 ° C. for 5 minutes. The adhesive application amount after drying was 9 g / m ² . A surface-treated PP having a thickness of 50 μm was bonded thereon and cured at 45 ° C. for 48 hours. Table 1 shows the performance evaluation results.

Example 2 In the same reaction vessel as in Example 1, (A-1) 5 of Example 1 was added.
In 00 parts, a biuret-modified hexamethylene diisocyanate (HDI) (“Duranate 24A-10”) was added.
0 ", manufactured by Asahi Kasei Kogyo Co., Ltd., NCO content: 23%), and stirred and mixed at room temperature to obtain an NCO content of 2.8%, a viscosity of 300 mPa · s (25 ° C), and a solid content of 53%.
A terminal urethane prepolymer solution (A-2) was obtained. 100 parts of the above (A-2) and 15 parts of the polyol solution (B-1) obtained in Example 1 (NCO / OH equivalent ratio = 1/1) were uniformly mixed to prepare an adhesive of the present invention. Using this adhesive, laminating 2 using the same film as in Example 1
Curing was performed at 5 ° C. for 72 hours. Table 1 shows the performance evaluation results.

Example 3 In the same reaction vessel as in Example 1, polyethylene adipate diol ("San Ester 2620", manufactured by Sanyo Chemical Industries, number average molecular weight 2000, hydroxyl equivalent 1000) 18
8 parts, polyoxypropylene diol (“Sannix Diol PP-1000”) 46 parts, polybutadiene polyol (“NISSO-PB G-1000”, manufactured by Nippon Soda, number average molecular weight 1350, hydroxyl equivalent 780) 3
2 parts, polycaprolactone triol (Placcel P
CL-303 ", manufactured by Daicel Chemical Industries, number average molecular weight 3
7 parts of 00, hydroxyl equivalent 100), 280 parts of ethyl acetate and 70 parts of cyclohexane were charged and uniformly mixed at a liquid temperature of 50 ° C. The water content of this mixture was 0.04%. Subsequently, 77 parts of isophorone diisocyanate and 0.06 parts of dibutyltin dilaurate were charged with stirring, and reacted at 70 ° C. for 5 hours under a nitrogen stream to obtain an NCO content of 2.1.
%, A viscosity of 150 mPa · s (25 ° C.) and a solid content of 50% isocyanate-terminated urethane prepolymer solution (A-
3) was obtained. In a similar reaction vessel, a propylene oxide adduct of sorbitol (“Sanix Hexaol S”
P-750 ") 305 parts and ethyl acetate 350 parts were charged and uniformly mixed at a liquid temperature of 50 ° C for 30 minutes. The water content of this mixture was 0.05%. Subsequently, a HDU-modified violet (“Duranate 24A-
100 ") 45 parts and 2 parts of dibutyltin dilaurate were charged and reacted at 70 ° C. for 2 hours to obtain an NCO content of 0.0
After confirming that the content was 5% or less, the same stabilizers (three types) as in Example 1 were added, and mixed at 50 ° C. for 1 hour.
A hydroxyl-terminated urethane prepolymer solution having a hydroxyl value of 176, a viscosity of 20 mPa · s / 25 ° C., and a solid content of 50% (B-
2) was obtained. 100 parts of the above (A-3) and (B-2)
16 parts (NCO / OH equivalent ratio = 1/1) were uniformly mixed to prepare an adhesive of the present invention. Apply this adhesive to a thickness of 50μ.
m of the surface-treated PP and dried with warm air at 50 to 70 ° C. for 5 minutes. The adhesive application amount (solid content) after drying is 9 g /
m ² . A 50 μm thick untreated surface polyethylene terephthalate film is stuck on it and
For 48 hours. Table 1 shows the performance evaluation results of this product.
Shown in

Example 4 In the same reaction vessel as in Example 1, (A-3) 5 of Example 2 was added.
In 00 parts, an isocyanurate-modified HDI (“Duranate TPA-100”, manufactured by Asahi Kasei Corporation, NCO content 2)
3%), 20 parts were stirred and mixed at room temperature, and an NCO content of 2.9%, a viscosity of 100 mPa · s (25 ° C.) and a solid content of 52% was used as an NCO-terminated urethane prepolymer solution (A-
4) was obtained. 100 parts of the above (A-4) and 22 parts of the polyol solution (B-2) obtained in Example 3 (NCO / OH equivalent ratio = 1/1) were uniformly mixed to prepare an adhesive of the present invention. Using this adhesive, the same film as in Example 3 was bonded and cured at 25 ° C. for 72 hours. Table 1 shows the performance evaluation results.

Example 5 Polycaprolactone diol ("Placcel PLC210", manufactured by Daicel Chemical Industries, number average molecular weight 1000, hydroxyl equivalent 500) was placed in a reaction vessel similar to that of Example 1 in an amount of 177.
Part, polyoxytetramethylene glycol ("PTMG
-1000 ", manufactured by Sanyo Chemical Industries, number average molecular weight 100
0, hydroxyl equivalent 500) 35 parts, polyoxypropylene triol (“Sannicks Triol GP-60”).
0 ") 21 parts, polycaprolactone triol (" Placcel PCL-303 ") 11 parts and ethyl acetate 35
0 parts were charged and uniformly mixed at a liquid temperature of 50 ° C. The water content of this mixture was 0.02%. Subsequently, 106 parts of isophorone diisocyanate and 0.06 part of dibutyltin dilaurate were charged with stirring, and the mixture was heated at 70 ° C. under a nitrogen stream at 70 ° C.
After reacting for an hour, the mixture was cooled to 40 ° C., and subsequently, a burette modified form of HDI (“Duranate 24A-10
0 ") 46 parts were mixed uniformly at a liquid temperature of 40 ° C. for 30 minutes, the NCO content was 3.2%, and the viscosity was 200 mPa · s.
(25 ° C.), an isocyanate-terminated urethane prepolymer solution (A-5) having a solid content of 53% was obtained. In a similar reaction vessel, 125 parts of a propylene oxide adduct of sorbitol (“Sanix hexaol SP-750”) and polybutadiene polyol (“NISSO-PB G-1”)
000 ") and 180 parts of ethyl acetate were charged and uniformly mixed at a liquid temperature of 50 ° C. for 30 minutes. The water content of this mixture was 0.04%. Then H under stirring
DI isocyanurate modified product (“Duranate TPA”)
-100 ") and 46 parts of dibutyltin dilaurate were charged and reacted at 70 ° C. for 2 hours to give an NCO content of 0.1 part.
After confirming that the content was not more than 05%, the same stabilizer (three kinds) as in Example 1 was added thereto and mixed at 50 ° C. for 1 hour to obtain a hydroxyl value of 79, a viscosity of 100 mPa · s (25 ° C.),
A hydroxyl-terminated urethane prepolymer having a solid content of 50% (B-
3) was obtained. 100 parts of the above (A-5) and (B-3)
54 parts (NCO / OH equivalent ratio = 1/1) were uniformly mixed to prepare an adhesive of the present invention. Apply this adhesive to a thickness of 50μ.
m of the surface-treated PP and dried with warm air at 50 to 70 ° C. for 5 minutes. The adhesive application amount (solid content) after drying is 7 g /
m ² . An untreated polyacryl film ("Acryprene", manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 50 [mu] m was laminated thereon and cured at 25 [deg.] C. for 72 hours. Table 1 shows the performance evaluation results.

Comparative Example 1 In the same reaction vessel as in Example 1, polyoxypropylene triol (“Sannicks Triol TP-400”,
Sanyo Chemical Industries, number average molecular weight 430, hydroxyl equivalent 14
3) 311 parts and 350 parts of ethyl acetate were charged and uniformly mixed at a liquid temperature of 50 ° C. for 30 minutes. The water content of this mixture was 0.03%. Subsequently, the isocyanurate-modified HDI (“Duranate TPA-10”) was stirred under stirring.
0 ") 39 parts and dibutyltin dilaurate 2 parts were charged and reacted at 70 ° C. for 2 hours, and the NCO content was 0.05%.
After confirming the following, the same stabilizers (three types) as in Example 1 were added in the same amount and mixed at 50 ° C. for 1 hour, and the hydroxyl value was 156, the viscosity was 15 mPa · s (25 ° C.), and the solid content was 5
0% hydroxyl-terminated urethane prepolymer solution (B-4)
I got 100 parts of the isocyanate group-terminated urethane prepolymer solution (A-5) obtained in Example 5 and the above (B-
4) 27 parts (NCO / OH equivalent ratio = 1/1) were uniformly mixed to prepare a comparative adhesive. A laminate film was prepared using this adhesive in the same manner as in Example 2, and the performance was evaluated. Table 2 shows the results.

Comparative Example 2 The procedure of Example 5 was repeated except that 177 parts of polyoxytetramethylene glycol ("PTMG-1000") was used instead of 177 parts of the polycaprolactone diol used in (A-5) of Example 5. In the same manner as in A-5), a comparative isocyanate group-terminated urethane prepolymer solution (A-6) was obtained. The (A-6) has an NCO content of 3.2% and a viscosity of 2
00 mPa · s (25 ° C.), solid content was 53%.
100 parts of this (A-6) and 24 parts of the polyol solution (B-2) obtained in Example 3 (NCO / OH equivalent ratio = 1/1) were uniformly mixed to prepare a comparative adhesive. A laminate film was prepared using this adhesive in the same manner as in Example 2, and the performance was evaluated. Table 2 shows the results.

Comparative Example 3 In a reaction vessel similar to that in Example 1, polyethylene adipate diol (“Sunester 2610”, 167 parts) and polyoxytetramethylene glycol (“PTMG-100”) were added.
0 "), 41 parts of polycaprolactone triol (" Placcel PCL-303 "), 25 parts of trimethylolpropane, 280 parts of ethyl acetate and 70 parts of cyclohexane were charged and uniformly mixed at a liquid temperature of 50C for 30 minutes. . The water content of this mixture was 0.05%. Subsequently, 114 parts of tolylene diisocyanate were charged under stirring and reacted at 70 ° C. for 5 hours under a nitrogen stream, NCO content: 3.5%, viscosity: 200 mPa · s (25 ° C.), solid content: 5
A 0% isocyanate-terminated urethane prepolymer solution (A-7) was obtained. 100 parts of this (A-7) and Example 3
27 parts of the polyol solution (B-2) used in (NCO / O
(H equivalent ratio = 1/1) was uniformly mixed to prepare a comparative adhesive. This adhesive was applied to a surface-treated PP having a thickness of 50 μm and dried with warm air at 50 to 70 ° C. for 5 minutes. The adhesive application amount (solid content) after drying was 9 g / m ² . An untreated surface polyethylene terephthalate film having a thickness of 50 μm was laminated thereon and cured at 45 ° C. for 48 hours. Table 2 shows the performance evaluation results.

The performance evaluation items and evaluation methods in Tables 1 and 2 are as follows. Transparency: Visual evaluation of the appearance of the laminated film. Flexibility: Visual evaluation to determine whether cracks, cracks, whitening, peeling, etc. occur when the laminated film is bent in an atmosphere at a temperature of 0 ° C. Normal adhesiveness: Peel strength (180 ° peel peel strength, tensile speed 100 mm / min, unit: K)
gf / 25 mm). Hot water adhesion: Peel strength (180 ° peel peel strength, pulling speed 100 mm / min, unit: Kgf / 25) after immersing the bonded film in hot water at 60 ° C. for 24 hours
mm). Heat resistance: Peel strength (180 ° peel strength, tensile speed 100 mm / min, unit: Kgf) after storing the laminated film in an oven at 80 ° C. for 100 hours
/ 25 mm). Weather resistance: 1000 hours of xenon weather meter irradiation [irradiation conditions; 63 ° C (black panel temperature) x 60RH]
%, Irradiation 102 minutes / rainfall + irradiation 18 minutes], the presence or absence of yellowing of the bonded films was evaluated.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

The adhesive for two-component dry lamination of the present invention has an extremely excellent adhesiveness between a polyolefin film and various plastic films as compared with a conventional adhesive for the same application, and also has a hot water resistance, Excellent heat resistance and weather resistance. In addition, room temperature curability is also excellent. Due to the above effects, the two-component dry laminating adhesive of the present invention is extremely useful in the production of laminated films used in applications such as packaging films, building material decorative films, unit bath interior films, and marking films. Useful.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-49-339 (JP, A) JP-A-50-123141 (JP, A) JP-A-3-182584 (JP, A) JP-A-3-182584 281589 (JP, A) JP-A-7-207246 (JP, A) JP-A-10-176159 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09J 1/00-201 / 10 B32B 7/00-35/00 CA (STN) REGISTRY (STN)

Claims (9)

(57) [Claims] 1. An isocyanate group-terminated urethane prepolymer (A1) comprising a polyol (a1) and an excess of an aliphatic polyisocyanate (b1) or an isocyanate comprising said (A1) and an aliphatic polyisocyanate (A2). Hydroxyl-terminated urethane prepolymer (B) from component (A), polyol (B1) and / or polyol (a2) and aliphatic polyisocyanate (b2)
In the two-component dry laminating adhesive comprising the polyol component (B) comprising 2), the polyester polyol (a) having a hydroxyl equivalent of 300 to 1500 as (a1)
11), a polyether polyol (a12) having a hydroxyl equivalent of 300 to 1500, a 3 to 8 functional polyol (a13) having a hydroxyl equivalent of less than 300, and a hydroxyl equivalent of 250 to 20.
Using the polydiene polyol (a14)
1) and / or (a2) a hydroxyl equivalent of 50 to 3
An adhesive characterized by using the 4- to 8-functional polyol (a21) of No. 00. 2. (a11): (a12): (a13):
The equivalent ratio of (a14) is 1: (0.01 to 1) :( 0.0
1-2): (0.01-1), and the equivalent ratio of the isocyanate group of (b1) to the total hydroxyl group of (a11), (a12), (a13) and (a14) is (1. 1 to
2.5) The adhesive according to claim 1, wherein the ratio is 1: 1. 3. (A2) is a trifunctional or higher aliphatic polyisocyanate, and the equivalent ratio of (A1) to (A2) is 1:
The adhesive according to claim 1, which is (0.01 to 5). 4. The method according to claim 1, wherein (a13) is polycaprolactone triol and / or alkanetriol.
4. The adhesive according to any one of items 3 to 3. 5. The adhesive according to claim 1, wherein (b2) is an aliphatic or alicyclic polyisocyanate and / or a modified product of the polyisocyanate. 6. An equivalent ratio of the hydroxyl group of (a2) to the isocyanate group of (b2) is (3 to 25): 1.
6. The adhesive according to any one of the above items 5. 7. The adhesive according to claim 1, wherein the equivalent ratio of the isocyanate component (A) to the polyol component (B) is (0.7 to 1.3): 1. 8. A polyolefin film, a polyester film, a polyacryl film, a polyvinyl chloride film, a polystyrene film, a nylon film, an ethylene vinyl alcohol copolymer film, a polyvinyl alcohol film and their surfaces are subjected to a vapor deposition treatment with aluminum or silica, The adhesive according to any one of claims 1 to 7, which is used for dry lamination adhesion and / or extrusion lamination adhesion between a plastic film selected from a film coated with vinylidene chloride and a polyolefin film. 9. A polyolefin film, a polyester film, a polyacryl film, a polyvinyl chloride film, a polystyrene film, a nylon film, an ethylene vinyl alcohol copolymer film, a polyvinyl alcohol film. A laminate film formed by bonding a plastic film selected from a film coated with vinylidene chloride and a polyolefin film by dry lamination or extrusion lamination using the adhesive according to any one of claims 1 to 7.