JP2001172600A - Two-part adhesive for dry laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-part adhesive composition for dry laminates which retains good adhesive properties between various plastic films and an inorganic board or a plastic board and at the same time is excellent in clarity, pigment dispersibility and boiling water resistance, compared with the conventional adhesives. SOLUTION: The two-part adhesive composition comprises (A) an isocyanate component comprising at least 50 wt.% of (A1) an isocyanate group-terminated urethane prepolymer derived from (a1) a polydiene polyol having a hydroxyl equivalent of 300-2,000 and (a2) an excess of an organic polyisocyanate and (B) a polyol component comprising at least 50 wt.% polyol mixture of (B1) a polyfunctional polyol having a functionality of 4-8 and a hydroxyl equivalent of 50-300 and (B2) a polyurethane polyol having at least one organic acid (salt) group selected from the group consisting of a carboxylic acid (salt) group, a sulfamic acid (salt) group, a sulfonic acid (salt) group and a phosphoric acid ester (salt) group and having an organic acid (salt) equivalent of 1,000-30,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an adhesive for two-component dry lamination. More specifically, the present invention relates to a two-pack type dry laminating adhesive which can be particularly suitably used for dry lamination bonding between a plastic film and an inorganic plate or a plastic resin molded plate.

[0002]

2. Description of the Related Art Conventionally, as a polyurethane adhesive used for bonding plastic films, a polyurethane adhesive composition obtained by blending an organic polyisocyanate, an organic polyol, an oxygen acid of phosphorus or a derivative thereof, an amine compound and an epoxy resin is used. Product (for example, JP-A-7-
No. 11225), an organic polymer polyol component such as polyester polyol and polyurethane polyol, and an organic polyisocyanate component composed of a bifunctional polyisocyanate compound and a trifunctional or higher polyfunctional polyisocyanate compound. Compositions (for example, JP-A-8-60131) are known.

[0003]

However, in the above-mentioned materials, the adhesiveness of the bonded body obtained by laminating the plastic film and the inorganic plate is insufficient in the sharpness and dispersibility with respect to the pigment.
Further, the above-mentioned ones have a problem that the image clarity, the pigment dispersibility and the boiling water resistance are insufficient.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an isocyanate component having a specific composition, a polyfunctional polyol having 4 to 8 valences, and a polyurethane polyol having a specific composition. By using in combination with a polyol component, it is found that an adhesive for two-component dry lamination with excellent adhesion to plastic films and inorganic plates, sharpness, pigment dispersibility, and hot water resistance can be obtained. The present invention has been reached.

That is, according to the present invention, the hydroxyl equivalent is 300 to
An isocyanate component (A) containing at least 50% by weight of an isocyanate group-terminated urethane prepolymer (A1) derived from 2,000 polydiene polyol (a1) and excess organic polyisocyanate (a2); 8, and at least one selected from a polyfunctional polyol (B1) having a hydroxyl equivalent of 30 to 300 and a carboxylic acid (salt) group, a sulfamic acid (salt) group, a sulfonic acid (salt) group, and a phosphate ester (salt) group. Organic acid (salt) groups having an equivalent of 1,000 to 3 organic acid (salt) groups.
A two-component dry laminating adhesive comprising a polyol component (B) containing at least 50% by weight of a polyol mixture consisting of a polyurethane polyol (B2) having a molecular weight of 000.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The isocyanate component (A) in the present invention is an isocyanate group-terminated urethane prepolymer (A1) derived from a polydiene polyol (a1) and an organic polyisocyanate (a2), or (A).
1) and a polyol (a3) other than the above (a1) [eg, polyester polyol, polyether polyol, etc.]
And isocyanate group-terminated urethane prepolymer (A2) derived from (a2). When (A1) and (A2) are used in combination in component (A), the content of (A1) is at least 50% by weight, preferably at least 60% by weight, based on the total weight of (A1) and (A2). It is more preferably at least 70% by weight. If the content of (A1) is less than 50% by weight, the hot water resistance is undesirably reduced.

The polydiene polyol (a1) constituting (A1) includes polybutadiene polyol, polyisoprene polyol, partially or completely hydrogenated products thereof. Of these, preferred is polybutadiene diol, and particularly preferred is polybutadiene diol having 1,4-bonds in the molecule in a microstructure of 70 mol% or more. The hydroxyl group equivalent of (a1) is usually 300 to 2,000, preferably 300 to 2,000.
1,800, and the average number of functional groups is usually 1.5 to
3, preferably 1.7 to 2.5. 3 hydroxyl equivalents
If it is less than 00, the cured film of the adhesive becomes hard and there is a problem in terms of flexibility, and if it exceeds 2,000, the adhesion to the plastic film is reduced.

The polyol (a3) other than (a1) constituting the above (A2) includes polyester polyol (a31) and polyether polyol (a3).
2).

Examples of the polyester polyol (a31) include dicarboxylic acids [aliphatic dicarboxylic acids having 4 to 20 carbon atoms (eg, succinic acid, glutaric acid, adipic acid, azelaic acid, etc.), and aromatic compounds having 8 to 18 carbon atoms. Group dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, etc.), and their ester-forming derivatives [lower alkyl (1 to carbon atoms)
4) one or more of esters, acid anhydrides, acid halides, etc.] and low molecular polyols [bifunctional trifunctional low molecular polyols (dihydric alcohols having 2 to 12 carbon atoms such as ethylene glycol, propylene glycol, 4-butanediol, neopentyl glycol, etc .;
Condensed polyester polyols obtained by polycondensation with at least one of trihydric alcohols (e.g., glycerin, trimethylolpropane, etc.), alkylene oxide adducts (with a molecular weight of less than 500), etc.); A polylactone polyol (eg, polycaprolactone diol or triol) obtained by ring-opening polymerization of a lactone having 4 to 12 carbon atoms (eg, ε-caprolactone, γ-butyrolactone, etc.) starting from at least one species; Examples thereof include polycarbonate polyols (for example, polyhexamethylene carbonate diol and the like) derived from one or more and a carbonate (ethylene carbonate, dimethyl carbonate, and the like), and a mixture of two or more thereof. Preferred among these are condensation polyester polyols,
Particularly preferred are polyalkylene adipate diols obtained by polycondensing adipic acid with ethylene glycol and / or propylene glycol. The hydroxyl group equivalent of (a31) is usually from 300 to 2,000, preferably from 350 to 1,500, and the number of functional groups is usually from 2 to 3, preferably from 2. When the hydroxyl group equivalent is less than 300, the cured film of the adhesive becomes hard and there is a problem in flexibility, and when it exceeds 2,000, the adhesion to the plastic film is reduced.

Examples of the polyether polyol (a32) include the alkylene oxide (co) adducts of the dihydric alcohol and the trihydric alcohol exemplified as the starting materials for the polyester polyol. Above and below, as the alkylene oxide, ethylene oxide (EO), propylene oxide (PO),
1,2-, 1,3-, 2,2- and 1,4-butylene oxide, α-olefin oxides having 5 to 12 carbon atoms, styrene oxide and a combination of two or more of these (block and / or random Addition). Preferred as (a32) is polyoxytetramethylene glycol obtained by ring-opening addition polymerization of 1,4-butylene oxide (tetrahydrofuran) starting from 1,4-butanediol. The (a3
The hydroxyl equivalent of 2) is usually from 300 to 2,000, preferably from 350 to 1,500, and the number of functional groups is usually from 2 to
3, preferably 2. When the hydroxyl equivalent is less than 300, the flexibility of the cured film of the adhesive becomes poor, and when it exceeds 2,000, the adhesion to the plastic film is reduced.

As the organic polyisocyanate (a2) constituting (A1) and, if necessary, (A2) used in the present invention, those conventionally used in polyurethane production can be used. Such polyisocyanates include aromatic polyisocyanates having 6 to 20 carbon atoms (excluding carbon in NCO groups, the same applies hereinafter), and 2 to 2 carbon atoms.
18 aliphatic polyisocyanate, alicyclic polyisocyanate having 4 to 15 carbon atoms, araliphatic polyisocyanate having 8 to 15 carbon atoms and modified products of these polyisocyanates (urethane group, carbodiimide group, allophanate group, urea group , Burette group, uretdione group,
Uretoimine group, isocyanurate group, oxazolidone group-containing modified product) and mixtures of two or more of these.

Specific examples of the aromatic polyisocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), and 2,4 '. -And / or
Or 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-diisocyanatobiphenyl,
3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane and the like can be mentioned. Specific examples of the aliphatic polyisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, And lysine diisocyanate.
Specific examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MD).
I), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-
Examples thereof include 1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate. Specific examples of the araliphatic polyisocyanate include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI). Examples of the modified polyisocyanate include modified MDI (carbodiimide-modified MDI), biuret-modified HDI, isocyanurate-modified HDI, isocyanurate-modified IPDI, and a mixture of two or more of these. Of these, preferred are those having 2 to 3 functional groups.
belongs to. The free isocyanate group content of the modified polyisocyanate and prepolymer is usually from 8 to 33.
%, Preferably 10 to 30%, particularly preferably 12 to
29%. Of these, preferred are alicyclic diisocyanates, and particularly preferred are IPDs.
I and HMDI.

The above (A1) and (A2) correspond to (a1)
Alternatively, it can be obtained by subjecting (a3) and an excess of (a2) to a urethanation reaction by an ordinary method (one-shot method or multi-stage method). (A2) an isocyanate group and (a)
1) or the equivalent ratio to the hydroxyl group of (a3) (NCO / O
H) is usually (1.1 to 8): 1, preferably (1.5 to 8).
5): 1. When (a2) is less than 1.1 equivalents, the viscosity of the obtained component (A1) or (A2) becomes high, so that the workability of applying the adhesive becomes poor, and when it exceeds 8 equivalents, the adhesiveness to a plastic film decreases. Tend to be.

The reaction temperature for urethane formation 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. Also,
Catalysts usually used for polyurethane to promote the reaction [for example, organometallic compounds (dibutyltin dilaurate, stannous octoate, stannas octoate, tetrabutoxytitanium, tetrapropoxytitanium, isopropoxy / trisdioctylphosphonyltitanium, etc.) ); Amine compounds (such as triethylamine, triethylenediamine, and N-pentamethyldiethylenetriamine)]. There are no particular restrictions on the amount of catalyst used, but (a1) and (a2) or (a3) and (a2)
Is usually 0.0001 to 0.5% by weight based on the total weight of

The content of free isocyanate (NCO) groups (per solid) in the isocyanate component (A) [(A1) or a mixture of (A1) and (A2)] is usually 1-2.
0% by weight, preferably 2 to 15% by weight. The viscosity (25 ° C.) is usually 50 to 20,000 mPa · s at a solid concentration of 60 to 80% by weight, preferably 100 to 20,000 mPa · s.
It is 15,000 mPa · s.

The polyol component (B) in the present invention comprises:
A polyfunctional polyol (B1) having 4 to 8 functional groups and a hydroxyl equivalent of 30 to 300, a carboxylic acid (salt) group, a sulfamic acid (salt) group, a sulfonic acid (salt) group, and a phosphate ester (salt) group Having at least one organic acid (salt) group selected from the group consisting of
It is composed of 30,000 polyurethane polyol (B2).

As the polyol (B1) constituting the component (B) in the present invention, polyhydric alcohols having 4 to 8 valences (for example, pentaerythritol, diglycerin, dipentaerythritol, triglycerin, tripentaerythritol, galactose, Sorbitol, sucrose, etc.), their alkylene oxide (co) adducts, and polylactone polyols obtained by ring-opening addition polymerization of lactones starting from 4- to 8-hydric polyhydric alcohols. These can be used in combination of two or more. Preferred among these are PO adducts of one or more polyhydric alcohols selected from pentaerythritol, dipentaerythritol and sorbitol, and E
It is a block or random co-adduct of O and PO. The hydroxyl equivalent of (B1) is usually 30 to 300, preferably 50 to 300, particularly preferably 70 to 250,
The number of functional groups is usually 4 to 8, preferably 5 to 7.
If the hydroxyl group equivalent is less than 50, the flexibility of the cured film of the adhesive will be poor and the adhesiveness will be reduced, and if it exceeds 300, the boiling water resistance will be undesirably reduced. On the other hand, if the number of functional groups is less than 4, the boiling water resistance becomes insufficient, and if it exceeds 8, the adhesiveness decreases, which is not preferable.

The polyurethane polyol (B2) constituting the component (B) comprises a carboxylic acid (salt) group, a sulfamic acid (salt) group, a sulfonic acid (salt) group, and a phosphate ester in the molecular side chain and / or main chain. Polyol having at least one organic acid (salt) group selected from (salt) groups (b
1) and an organic polyisocyanate (b2).

Examples of the polyol (b11) having a carboxylic acid (salt) group among the polyols (b1) include, for example, α, α-dimethylolalkanoic acid (α, α-dimethylolpropionic acid, α, α-dicarboxylic acid). Methylolbutanoic acid,
α, α-dimethylolnonanoic acid), tartaric acid, esterified product of 1 mol of citric acid and 1 mol of ethylene glycol (molecular weight; 240, acid value; 468, hydroxyl value; 46)
8), an esterified product of 1 mol of malic acid and 1 mol of ethylene glycol (molecular weight; 178, acid value; 315, hydroxyl value; 630) and salts thereof (sodium salt, potassium salt, ammonium salt, amine salt, etc.) No.
Of these, α, α-dimethylolalkanoic acid is preferable, and α, α-dimethylolpropionic acid and α, α-dimethylolbutanoic acid are more preferable.

In the polyol (b1), the sulfamic acid (salt) group in the polyol (b12) having a sulfamic acid (salt) group is represented by the following general formula: Wherein X represents hydrogen, an alkali metal, a tertiary amine or a quaternary ammonium group. Examples of the alkali metal include potassium, sodium, and lithium. Examples of the tertiary amine include a trialkylamine having 1 to 8 carbon atoms in an alkyl group (eg, trimethylamine, triethylamine, tributylamine, etc.) and a trialkanolamine having 2 to 4 carbon atoms in a hydroxyalkyl group (eg, triethanolamine, etc.). No.
Examples of the quaternary ammonium group include a methyltriethylammonium group and a methyltributylammonium group. Of these, preferred are alkali metals, and particularly preferred are potassium and sodium.

As the (b12), for example, a sulfamic acid (salt) group-containing diol (EO and / or PO addition mole number 2 to 4) obtained by reacting sulfamic acid (salt) with EO and / or PO ),
A sulfamic acid (salt) group-containing polyether polyol obtained by further reacting EO and / or PO with the sulfamic acid (salt) group-containing diol in a conventional manner, and the above-mentioned sulfamic acid (salt) group-containing diols and known polyether polyols. And a sulfamic acid (salt) group-containing polyester polyol obtained by polycondensation with a polyvalent carboxylic acid and a sulfamic acid (salt) group-containing polyester polyol obtained by polycondensation of a sulfamic acid (salt) group-containing dicarboxylic acid and glycol. . Of these, preferred are sulfamic acid (salt) group-containing polyether polyols and sulfamic acid (salt) group-containing polyester polyols.

The above raw material sulfamic acid (salt)
Examples thereof include sulfamic acid, sodium sulfamate, triethylamine sulfamate, triethanolamine sulfamate, methyltriethylammonium sulfamate and the like. As the synthesis method, for example, sulfamic acid (salt) is mixed in EO and / or PO, and gradually heated at normal pressure or under pressure in the presence of an alkaline catalyst (for example, potassium hydroxide or the like) to form a mixture. The method obtained by making it react at -200 degreeC can be illustrated.

The number average molecular weight of the above-mentioned polyether polyol having a sulfamic acid (salt) group is usually from 300 to 300.
It is 5,000, preferably 400 to 4,000, more preferably 500 to 3,000.

The known polyvalent carboxylic acids constituting the above-mentioned sulfamic acid (salt) group-containing polyester polyol include the dicarboxylic acids exemplified in the above section (a3).
Trivalent carboxylic acids (trimellitic acid, trimesic acid, etc.)
And mixtures of two or more of these. The sulfamic acid (salt) group-containing polyester polyol can be obtained by esterification by a known method. The equivalent ratio (OH / COOH) of the hydroxyl group to the carboxyl group in the esterification is usually (1.1 to 5) /
1, preferably (1.5 to 3) / 1. The number average molecular weight of the polyester polyol is usually 500 to 5,0.
00, preferably 600 to 4,000.

The above raw material, sulfamic acid (salt)
Examples of the group-containing polycarboxylic acid include a reaction product of an amino group-containing polycarboxylic acid (such as 2-aminoterephthalic acid, 3-aminophthalic acid, or 5-aminoisophthalic acid) with a pyridine / sulfur trioxide complex. Can be As a synthesis method, for example, after reacting the amino group-containing polycarboxylic acid with a pyridine-sulfur trioxide complex in an aqueous alkali solution at a temperature of about 0 to 40 ° C., the reaction product is ethanol,
An example is a method of purifying the product by a method such as recrystallization with acetone or the like to obtain the desired product. Examples of known glycols include alkylene glycols having 2 to 10 carbon atoms (ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, etc.), and carbon atoms having 6 to 1 carbon atoms.
Low molecular diols having two cyclic groups (cyclohexanediol, cyclohexanedimethanol, xylylene glycol, etc.), and mixtures of two or more of these. If necessary, a trihydric alcohol such as trimethylolpropane or glycerin may be used in combination. The sulfamic acid (salt) group-containing polyester polyol is obtained by esterifying the above raw material by a known method.
The equivalent ratio (OH / COOH) of the hydroxyl group to the carboxyl group at the time of the esterification is usually (1.1 to 5) / 1, preferably (1.5 to 3) / 1. The number average molecular weight of the polyester polyol is usually 500 to 5,000,
Preferably it is 600-4,000.

The polyol (b13) having a sulfonic acid (salt) group among the polyols (b1) in the present invention
Is obtained by esterifying a dicarboxylic acid containing a sulfonic acid (salt) group with the above-mentioned glycol by a known method.

The dicarboxylic acid containing a sulfonic acid (salt) group includes 5-sulfoisophthalic acid, 2-sulfoterephthalic acid, 5-sulfoisophthalic acid sodium salt,
-Sulfoisophthalic acid potassium salt, 2-sulfoterephthalic acid sodium salt, 2-sulfophthalic acid potassium salt and the like. Of these, preferred are sodium 5-sulfoisophthalate and potassium 5-sulfoisophthalate. The equivalent ratio (OH / COOH) of the hydroxyl group of the glycol component to the carboxyl group of the sulfonic acid (salt) group-containing dicarboxylic acid in (b13) is usually (1.
1-5) / 1, preferably (1.5-3) / 1.
The number average molecular weight of the polyester polyol is usually 50
It is 0 to 5,000, preferably 600 to 4,000.

The polyol (b14) having a phosphate (salt) group among the polyols (b1) in the present invention
Is a phosphate ester (salt) group represented by the following general formula [Wherein, R ′ represents an alkyl group having 1 to 24 carbon atoms;
X is the same as in the general formula (1). ] It is a group represented by these. Preferred as R 'is an alkyl group having 3 to 18 carbon atoms. Particularly preferred as X are potassium and sodium. Examples of (b14) include polycondensates of trihydric alcohols (eg, glycerin, trimethylolpropane, etc.) and / or their alkylene oxide (co) adducts and phosphoric acid monoesters, and alkali metal salts or organic amines thereof. Salt. Of these, a polycondensate of a PO adduct of glycerin (molecular weight of 250 to 1,000 or more) and a phosphoric acid monoester, and a sodium salt thereof are preferable. Examples of the phosphoric acid monoesters include monoalkyl phosphates having 1 to 18 carbon atoms such as monomethyl phosphate, monobutyl phosphate, and the like.
Monohexyl phosphate, monooctyl phosphate, monolauryl phosphate, monostearyl phosphate, etc.).

As a method for synthesizing (b14), for example, 1 to 5 mol of PO adduct of glycerin (preferably 1.2 mol)
To 4 mol) and 1 mol of monobutyl phosphate in a solvent inert to both (for example, methyl ethyl ketone or the like) or under a solvent-free condition. The reaction temperature is usually from 40 to 160 ° C. The number average molecular weight of (b14) is usually from 500 to 5,000,
Preferably it is 600-4,000.

(B1) [(b11) to (b1)]
(B14)] may be used in combination of two or more. (B1)
(B11) and (b12) are preferred. In addition, (b1) may be used in combination with a polyol having no organic acid (salt) group [for example, those exemplified as the aforementioned (a3)], if necessary.

Examples of the organic polyisocyanate (b2) constituting the polyurethane polyol (B2) include the organic polyisocyanates exemplified as (a2) in the component (A). Preferred among these are IPDI, HMDI and HDI.

The equivalent ratio (OH / NCO) of the hydroxyl group of (b1) and the isocyanate group of (b2) in (B2)
Is usually (1.1-4) / 1, preferably (1.2-4)
3) / 1. When the equivalent ratio of (b1) and (b2) is in this range, the performance is excellent. In (2), an organic acid (salt) group may be introduced after the reaction of (b1) with the precursor of (b1). Further, the urethane group (-NHCOO) in the (B2)
-) The content is usually 5 to 17% by weight, preferably 7 to 15% by weight.
% By weight.

The reaction temperature for obtaining (B2) is usually 5
The temperature is 0 to 100 ° C, and an organic solvent (for example, cyclohexane, toluene, xylene, methyl ethyl ketone, methyl acetate, ethyl acetate, N, N-dimethylformamide, etc.) can be used if necessary. Further, the catalyst exemplified in the section of the component (A) can be used to promote the reaction. 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 (b1) and (b2).

The organic acid (salt) group equivalent of (B2) is usually from 1,000 to 30,000, preferably from 1,200 to 2,000.
5,000, more preferably 1,500 to 20,000
0. When the organic acid (salt) group equivalent is less than 1,000, boiling water resistance becomes insufficient, and when it exceeds 30,000, image clarity and pigment dispersion stability become insufficient, which is not preferable.

In the present invention, the weight ratio of the polyfunctional polyol (B1) and the polyurethane polyol (B2) constituting the polyol component (B) is usually (1-70) :( 99-
30), preferably (4-50): (96-50), particularly preferably (10-40): (90-60).
When the ratio of (B1) is less than 1, the boiling water resistance becomes insufficient, and when it exceeds 70, the sharpness and the pigment dispersibility become insufficient, which is not preferable.

The polyol component (B) in the present invention, together with the polyols (B1) and (B2), which are essential components, has an organic acid (salt) group if necessary and has a hydroxyl equivalent of 1,000 to 30,000. Polyurethane polyol (B3) may be used in combination. As (B3), one or more of the polyols exemplified as (a3) in the above-mentioned component (A) and the organic polyisocyanate exemplified as (b2) in the same equivalent ratio as in (B2). Examples include polyurethane polyols obtained by the reaction. When the (B3) is used in combination, the content of the component (B)
Less than 50% by weight, preferably 30% by weight, based on the total weight of
% By weight or less. When the content of (B3) is 50% by weight or more, the pigment dispersion stability and the sharpness tend to be insufficient.

The equivalent ratio (NCO / OH) of the isocyanate group of the isocyanate component (A) to the hydroxyl group of the polyol component (B) in the adhesive of the present invention is usually (1.0 to 1.0).
8) / 1, preferably (1.5 to 6) / 1. If the component (A) is less than 1.0, the boiling water resistance becomes insufficient, and 8
If it exceeds, the adhesiveness to the plastic film becomes insufficient, which is not preferable.

The adhesive of the present invention may contain a curing acceleration catalyst as needed for the purpose of accelerating the curing reaction between the components (A) and (B). Examples of the curing accelerating catalyst include metal salts of alkyl (C2 to C20) phosphonic acids (salts such as potassium and sodium);
20 metal salts of fatty acids (sodium, potassium, nickel, cobalt, cadmium, barium, calcium, zinc, etc.); organic tin compounds [dibutyltin dilaurate, dioctyltin maleate, dibutyldibutoxytin,
Bis (2-ethylhexyl) tin oxide, 1,1,
3,3-tetrabutyl-1,3-diacetoxydistannoxane, etc.); amine compounds (triethylamine, triethylenediamine, N-pentamethyldiethylenetriamine, etc.); organic titanium compounds (tetrabutoxytitanium,
Tetrapropoxy titanium, isopropoxy trisdioctylphosphonyl titanium, isopropoxy triisostearate titanium, etc.); and mixtures of two or more of these. Preferred among these are organotin compounds, amine compounds, and organotitanium compounds,
Even more preferred are dibutyltin dilaurate, dioctyltin maleate and isopropoxy triisostearate titanium. The amount of the curing accelerating catalyst to be added is usually 0.01 to the total weight of the components (A) and (B).
-4% by weight, preferably 0.1-3% 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 based on the total weight of the components (A) and (B).
%, Preferably 0.5 to 3% by weight. There is no particular limitation on the method of adding these curing promoting catalysts and additives, but it is desirable that they are previously contained in the component (B).

The adhesive of the present invention may contain coloring pigments, extender pigments, etc. to impart a design property to the inorganic plate or to fill and smooth the unevenness of the inorganic plate. Examples of the coloring pigment include inorganic pigments (carbon black, titanium oxide, etc.) and organic pigments (azo pigments, phthalocyanine pigments, anthraquinone pigments, etc.). Examples of extenders include carbonates (calcium carbonate, magnesium carbonate, etc.), clays (kaolin clay, montmorillonite clay, etc.), barium sulfates (barite powder, precipitated barium sulfate, etc.), silicas (silica Alga earth, colloidal silica, etc.), and silicates (finely divided magnesium silicate, talc, etc.). Among these, carbon black and titanium oxide are preferred as color pigments. Preferred as extenders are carbonates and clays. The amount of these pigments used is a total of 10 for the components (A) and (B).
The amount is usually 0.1 to 300 parts by weight, preferably 1 to 200 parts by weight, particularly preferably 3 to 150 parts by weight, per 0 parts by weight.

The adhesive for two-component dry lamination of the present invention is a dry laminate adhesive between various plastic films or sheets; a dry laminate adhesive between the plastic film or sheet and an inorganic plate, a plastic molded plate, a metal plate, etc .; It is useful for dry lamination bonding between a laminated film and an inorganic plate, a plastic molded plate, a metal plate, and the like, and is suitably used for applications such as packaging, building material decoration, unit bath interior, kitchen interior, and marking film. Among them, it is particularly suitably used for dry lamination bonding between a plastic film and / or a paint laminated film and an inorganic plate or a plastic molded plate.

Examples of the plastic film (sheet) include a polypropylene film, a polyethylene film, a polyester film, a polyacryl film, a polyvinyl chloride film, a polystyrene film,
Examples include a nylon film, an ethylene vinyl alcohol copolymer film, a polyvinyl alcohol film, and a plastic film whose surface is subjected to a vapor deposition treatment with aluminum or silica or a coating treatment with polyvinylidene chloride. Examples of the paint laminated film include those obtained by applying various paints such as an acrylic UV paint, a urethane clear paint, a polyester clear paint, and an acrylic silicone clear paint to form a film.
Examples of the inorganic plate include a slate plate, a calcium silicate plate, a gypsum board, a wool cement plate, a foamed concrete plate, and the like. Examples of the plastic molded plate include an ABS resin molded plate, a polystyrene resin molded plate, a polyester resin molded plate, an acrylic resin molded plate, and a polycarbonate resin molded plate. Examples of the metal plate include a stainless steel plate, a zinc steel plate, a chemical conversion treated steel plate, and an aluminum plate.

A gravure coater, a reverse roll coater, a comma coater, or the like is used for coating the adhesive in laminating the plastic films or sheets. The coating amount (solid content) of the adhesive is usually 1 to 5
0 g / m ² . In addition, for bonding plastic film and inorganic plate, plastic molded plate or metal plate,
A comma coater, a die coater, a knife coater and the like are used. The coating amount of the adhesive (solids) is usually 5 to 500 g / m ² in the case of inorganic board, when a plastic molded plate and a metal plate is usually 2~300g / 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 150 hours.

[0043]

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.

[Isocyanate Component] Production Example 1 2 L equipped with a stirrer, thermometer, cooling tube and nitrogen inlet tube
In a four-neck flask having a capacity, 526.6 parts of polybutadiene polyol (“poly bdR-15HT”, manufactured by Idemitsu Petrochemical Co., number average molecular weight 1,278, hydroxyl equivalent 556) and 200 parts of toluene were charged, and a liquid temperature of 30 ° C. was added. Mix uniformly for minutes. Subsequently, 273.4 parts of isophorone diisocyanate and 0.06 part of dibutyltin dilaurate were added with stirring, and the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream.
Aged at 0 ° C for 2 hours, free isocyanate group (NCO)
Content 6.3%, viscosity 1,000 mPa · s (25
C), and a solution (A-1) of an isocyanate-terminated urethane prepolymer having a solid content of 80% was obtained.

Comparative Production Example 1 In a reaction vessel similar to that of Production Example 1, 483.9 parts of polyoxypropylene diol (number average molecular weight 1,200) and polyoxypropylene triol (PO adduct of glycerin, number average molecular weight 250) 25.2 parts and toluene 2
00 parts were uniformly mixed at a liquid temperature of 50 ° C. for 30 minutes.
Subsequently, 290.9 of isophorone diisocyanate was stirred.
And 0.06 part of dibutyltin dilaurate were added, reacted at 80 ° C. for 5 hours under a nitrogen stream, aged at 80 ° C. for 2 hours, and had a free isocyanate group (NCO) content of 6.3.
%, A viscosity of 850 mPa · s (25 ° C.) and a solution of an isocyanate-terminated urethane prepolymer having a solid content of 80% (A ′
-1) was obtained.

Production Example 2 [Production of carboxyl group-containing polyurethane polyol] In a reaction vessel similar to that of Production Example 1, 108.4 parts of polyoxypropylene diol (number average molecular weight 951) and polyoxypropylene diol (number average molecular weight 403) were placed. 268.
1 part, 114.0 parts of polyoxypropylene triol (PO adduct of glycerin, number average molecular weight 1,000)
Charge 15.3 parts of dipropylene glycol, 12.7 parts of dimethylolpropionic acid, 181.4 parts of IPDI, and 300 parts of ethyl acetate, and put in a nitrogen stream at 80 to 100 ° C.
For 5 hours, 0.1 part of dibutyltin dilaurate was added, and the mixture was further reacted for 10 hours. The infrared absorption spectrum confirmed that the isocyanate group had disappeared, and the carboxyl group equivalent was 6,400. Hydroxyl value (solid content conversion) 47, solid content 70%, viscosity 800 mPa · s
A solution (B-2) of a carboxyl group-containing polyurethane polyol at / 25 ° C was obtained.

Production Example 3 [Production of polyether polyol containing sulfamic acid (salt) group] In a pressurized reaction vessel equipped with a stirrer and a thermometer, 6 parts of potassium hydroxide, 135 parts (1 mol) of potassium sulfamate and xylene were added. 600 parts were charged and mixed and dispersed in a slurry. The dispersion was gradually heated, and 176 parts (4 mol) of EO was injected at 130 ° C. over about 10 hours to carry out a reaction. Further, at this temperature, 464 parts (8 mol) of PO were injected over about 20 hours to carry out a reaction. 30 parts of synthetic aluminum silicate was added to the reaction mixture, and potassium hydroxide as a catalyst was adsorbed at about 80 ° C. for about 1 hour, followed by filtration. The filtrate was desolvated under reduced pressure at about 100 ° C. to give the product (b-
1) 744 parts were obtained. The (b-1) structure of, by NMR analysis _{[H- [OCH (CH 3)} CH 2] 4 (OCH 2 CH 2) 2]
It was confirmed to be ₂ NSO ₃ K. The hydroxyl value of (b-1) is 14
5 (molecular weight: 774), and the yield was 96%.

Production Example 4 [Production of Sulfamate Group-Containing Polyurethane Polyol] In a reaction vessel similar to that of Production Example 1, 100.8 parts of polyoxypropylene diol (number average molecular weight 951) and polyoxypropylene diol (number average molecular weight 403) were placed. ) 242.
0 parts, polyoxypropylene triol (propylene oxide adduct of glycerin, number average molecular weight of 1,000
0) 106.0 parts, dipropylene glycol 14.2
Part, 68.4 parts of (b-1) obtained in Production Example 3, IPDI1
68.6 parts and 300 parts of ethyl acetate were charged and reacted at 80 to 100 ° C. for 5 hours under a nitrogen stream, and then 0.1 part of dibutyltin dilaurate was added and reacted for another 10 hours to obtain an infrared absorption spectrum. To confirm that the isocyanate group has disappeared, the sulfamate equivalent 6,300, the hydroxyl value (in terms of solid content) 48, and the solid content 70.
%, And a solution (B-3) of a sulfamate group-containing polyurethane polyol having a viscosity of 950 mPa · s / 25 ° C. was obtained.

[Polyol Component] Production Example 5 In a reaction vessel similar to that of Production Example 1, a sorbitol PO adduct [“Sanix Hexaol SP-750”, manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight 700, hydroxyl equivalent 116,
(Hydroxyl value 484) 185 parts of (B-1) and 815 parts of (B-2) prepared in Production Example 1 were charged and mixed at 50 ° C. for 1 hour to obtain a polyol component (C-1) having a solid content of 78%. Was.

Production Example 6 188 parts of (B-1) used in Production Example 5 and 812 parts of (B-3) produced in Production Example 4 were charged and mixed at 50 ° C. for 1 hour to obtain a polyol having a solid content of 76%. The component (C-2) was obtained.

Comparative Production Example 2 According to the method described in Example 1 of JP-A-7-11225, 194.2 parts of dimethyl terephthalate, 248.3 parts of ethylene glycol,
Charge 0.2 parts of zinc acetate, and in a nitrogen stream, 160 to 220
A transesterification reaction was performed at ℃. After predetermined methanol distillation, 83.1 parts of isophthalic acid was added,
After distilling out a predetermined amount of water, 282.3 parts of azelaic acid was added, and the esterification reaction was performed at 220 to 230 ° C, and the pressure was gradually reduced to 220 to 230 ° C.
After condensation for 0 minutes, condensation was performed at 220 to 230 ° C. for 4 hours at 1-2 mmHg. A polyester polyol having a hydroxyl value of 139 was obtained. 50 parts of the polyol was dissolved in 67 parts of ethyl acetate, and 2 parts of phthalic anhydride, 0.1 part of phosphoric acid, 0.1 part of morpholine, and 15 parts of Epicoat 1002 [epoxy resin manufactured by Shell Chemical Co., Ltd.] were added. A comparative polyol solution (C'-1) having a solid content of 50% was obtained.

Example 1 100 parts of (A-1) prepared in Production Example 1 and 16.5 parts of (C-1) prepared in Production Example 5 (NCO / OH equivalent ratio = 4)
/ 1), 5 parts of titanium oxide, 74.2 parts of ethyl acetate, and 0.1 part of dibutyltin dilaurate were uniformly mixed with a sand mill to obtain an adhesive of the present invention (solid content: 50%).
This adhesive is applied to the surface of a 38 μm-thick corona discharge treated polyester film (hereinafter abbreviated as surface-treated PET) using a 7-mil applicator, and heated with hot air at 50 to 70 ° C. for 5 minutes.
Dried for minutes. Adhesive application amount after drying is 85 g / m ²
Met. The adhesive coated film was attached to a slate plate having a thickness of about 3 mm, left for 2 days at room temperature, and then cured at 40 ° C. for 48 hours. Table 1 shows the performance evaluation results.

Example 2 100 parts of (A-1) prepared in Production Example 1 and 16.2 parts of (C-2) prepared in Production Example 6 (NCO / OH equivalent ratio = 4)
/ 1), titanium oxide 5 parts, calcium carbonate 50 parts, ethyl acetate 123 parts, and dibutyltin dilaurate 0.1 part.
One part was uniformly mixed with a sand mill to obtain the adhesive of the present invention (solid content: 50%). Using this adhesive, a laminated adhesive was prepared in the same manner as in Example 1, and the performance was evaluated. Table 1 shows the performance evaluation results.

Comparative Example 1 Example 1 was repeated except that the same amount of (A′-1) prepared in Comparative Production Example 1 was used instead of (A-1).
A comparative adhesive (solid content: 50%) was prepared in the same manner as described above. Using this adhesive, a laminated adhesive was prepared in the same manner as in Example 1, and the performance was evaluated. Table 1 shows the results.
Shown in

Comparative Example 2 In Example 1, 4.1 parts of the sorbitol PO adduct (B-1) was used instead of 16.5 parts of (C-1), and ethyl acetate 69 was used instead of 74.2 parts of ethyl acetate. A comparative adhesive (solid content: 50%) was prepared in the same manner as in Example 1 except that 0.0 part of each was used. Using this adhesive, a laminated adhesive was prepared in the same manner as in Example 1, and the performance was evaluated. Table 1 shows the results.

Comparative Example 3 A solution of a reaction product of 1 mol of trimethylolpropane and 3 mol of tolylene diisocyanate prepared in accordance with the method described in Example 8 of JP-A-7-11225 in ethyl acetate (A'-2) ) [NCO group content 14.0%, solid content 7
5%, viscosity at 25 ° C. 1,000 mPa · s] 7.5 parts,
100 parts of (C'-1) prepared in Comparative Production Example 2, 5 parts of titanium oxide and 8.7 parts of ethyl acetate were uniformly mixed by a sand mill to prepare a comparative adhesive (solid content: 50%).
Using this adhesive, a laminated adhesive was prepared in the same manner as in Example 1, and the performance was evaluated. Table 1 shows the results.

The performance evaluation items and evaluation methods in Table 1 are as follows. Sharpness: The appearance of the adhesive test piece on the film side was evaluated using a sharpness evaluation device (PGD meter). A measuring instrument that reads projected characters of different sizes and digitizes them. The larger the numerical value, the better the sharpness. Pigment dispersibility: The cured surface of the adhesive was evaluated using a gloss meter (Gloss meter, manufactured by Nippon Denshoku). Value at an incident angle of 60 degrees. The larger the value, the better the pigment dispersibility. Adhesion: Adhesion test pieces were cross-cut so as to form 16 grids in a 4 mm square from the film side, crimped with cellophane tape, and then pulled in the direction of 90 ° to determine the number of bonded squares remaining. It was measured. The higher the value, the better the adhesion. Boiling water resistance: Adhesion test piece was immersed in “boiling water for 4 hours + 60 ° C x 2
The "time drying" was defined as one cycle, and a 10 cycle test was performed. The following judgment was made on the appearance of the adhesive film after the test, and the adhesiveness after the test was measured by the cross-cut peeling test described above, and the number of remaining squares was measured and evaluated. During the test (1
If an abnormality was found in the film appearance such as cracks, blisters and blisters (less than 0 cycles), the test was terminated at that point, and the number of cycles in which no abnormality was observed was indicated. <Appearance criteria> ○: No abnormality in film appearance such as cracks, blisters and blisters ×: Abnormality in film appearance such as cracks, blisters and blisters

[0058]

[Table 1]

[0059]

The adhesive for two-component dry lamination of the present invention is different from the conventional adhesive for the same application in the adhesiveness between various plastic films and the inorganic plate, the sharpness, the dispersibility of the pigment and the resistance to pigment. Particularly excellent in boiling water. Because of the above effects, the two-component dry laminate adhesive of the present invention is
In particular, it is extremely useful for the production of a laminated adhesive used for applications such as packaging films, decorative building materials, unit bath interior building materials, and marking films.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J034 BA05 CA03 CA04 CA22 CB04 CB05 CB07 CB08 CC02 CC03 CC08 CD01 CD04 CD09 CD18 DA01 DB03 DB07 DD02 DD05 DF02 DF11 DF12 DF16 DF20 DF21 DF22 DF32 DF33 DG04 DG36 DG02 DG10 DG12 DG14 DG22 DG27 DG28 DG33 DH02 DH06 GA05 GA06 GA33 HA01 HA02 HA07 HB06 HB08 HB11 HB12 HC03 HC09 HC12 HC17 HC22 HC26 HC35 HC46 HC52 HC53 HC61 HC64 HC67 HC71 JA01 JA02 JA14 JA42 KA01 KB02 KD04 MA02 MA14 QA02 RA08 4J040 EF081 EF091 EF251 EF321 GA05 JA13 LA01 LA07 MA01 MA10 NA08

Claims (3)

[Claims] 1. An isocyanate component containing at least 50% by weight of an isocyanate-terminated urethane prepolymer (A1) derived from a polydiene polyol (a1) having a hydroxyl equivalent of 300 to 2,000 and an excess of an organic polyisocyanate (a2). (A) and a polyfunctional polyol having 4 to 8 functional groups and a hydroxyl equivalent of 30 to 300 (B1)
And a carboxylic acid (salt) group, a sulfamic acid (salt) group,
It has at least one organic acid (salt) group selected from the group consisting of a sulfonic acid (salt) group and a phosphate ester (salt) group, and has an organic acid (salt) group equivalent of 1,000 to 30,000.
And a polyol component (B) containing at least 50% by weight of a polyol mixture consisting of a polyurethane polyol (B2). 2. The weight ratio of (B1) to (B2) constituting (B) is (1 to 70) :( 99 to 30).
The adhesive as described. 3. The adhesive according to claim 1, wherein 0.1 to 300 parts by weight of a pigment is contained per 100 parts by weight of the total of (A) and (B).