JP2001200029A - Rosin-containing, water-based acrylic/urethane copolymer, coating agent and adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rosin-containing, water-based acrylic/urethane copolymer exhibiting excellent adhesion properties to a plastic film having poor adhesion, and a coating agent excellent in adhesion properties and an adhesive. SOLUTION: The rosin-containing, water based acrylic/urethane copolymer comprises a water-based polyurethane-based resin obtained by chain extension, in water using at least one chain extender (e) selected among water-soluble polyamines, hydrazine and derivatives thereof, of a neutralized isocyanate group- terminated prepolymer obtained from (a) an organic polyisocyanate compound, (b) a high molecular-weight polyol, (c) a compound bearing an anionic hydrophilic group and at least two active hydrogens and (d) a chain extender optionally employed, where the high molecular-weight polyol (b) comprises, in addition to 5-60 wt.% of an acrylic polyol having a hydroxyl value of 5-200 mg KOH/g, a rosin-modified polyol or a ring-opening polymer of lactones obtained employing as a reaction-starting point a rosin-modified polyol. There are also provided a coating agent containing the same and a copolymerized product.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a rosin-containing aqueous acrylic-urethane copolymer, a coating agent and an adhesive. More specifically, the present invention relates to a rosin-containing aqueous acrylic-urethane copolymer having excellent adhesion to a poorly-adhesive plastic film such as polypropylene or polyester, and an adhesive containing the copolymer. The present invention relates to coating agents and adhesives having excellent properties.

[0002]

2. Description of the Related Art Organic solvent-based compositions have been mainly used in the field of various coating agents such as paints and printing inks and adhesives. However, in recent years, it has been replaced with an aqueous composition using water as a medium because of problems such as air pollution and improvement of working environment. Various resins having a carboxyl group, mainly acrylic resins, polyester resins, and polyurethane resins have been proposed as binders in aqueous coating agents. In addition, as with other resins, various attempts have been made to solubilize or disperse water with respect to acrylic resins and urethane resins. Various aqueous resins have been developed that combine the advantageous properties of urethane resins such as resistance, blocking resistance and chemical resistance with the advantageous properties of acrylic resins such as low cost, weather resistance, light resistance and high solids concentration. I have. For example, U.S. Pat.
No. 318,833 discloses an aqueous acrylic-urethane coating composition having excellent storage stability, which is useful as an automotive topcoat, comprising an ethylenically unsaturated monomer in the presence of a completely reacted water-soluble polyurethane. An aqueous coating composition obtained by polymerizing the compound has been proposed. However, this composition has a disadvantage that it is difficult to obtain a uniform molecular mixture. Also, US Pat. No. 4,644,030 discloses that
Water-based acrylic that gives coatings with water resistance and solvent resistance
As a urethane resin composition, an isocyanate group-terminated polyurethane prepolymer is prepared in the presence of an ethylenically unsaturated monomer, and the prepolymer is dispersed in water to extend the chain. The resulting composition has been proposed. Further, Japanese Patent No. 2634470 discloses a water-dispersible acryl-urethane resin which forms a hard and abrasion-resistant coating film having excellent toughness, durability and gloss when air-dried. A composition obtained by polymerizing an acrylic monomer in the presence of a polyurethane and an acid-functional acrylic carrier resin has been proposed. However, these compositions have the disadvantage that none of them can obtain the properties of the complete acrylic-urethane copolymer. Therefore, at present, conventional water-based acrylic-urethane copolymers do not exhibit sufficient performance for poorly adherent plastic films.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a rosin-containing aqueous acrylic-urethane copolymer having excellent adhesion to a poorly-adhesive plastic film such as polypropylene or polyester, and a copolymer comprising the same. The object of the present invention is to provide a coating agent and an adhesive having excellent adhesiveness.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the isocyanate group-terminated prepolymer synthesized by using a high molecular weight polyol including an acrylic polyol and a rosin-modified polyol. Aqueous acrylic obtained by chain extension of a neutralized polymer in water
The urethane copolymer was found to have excellent adhesion to a poorly adhesive plastic film, and the present invention was completed based on this finding. That is, the present invention relates to (1) (a) an organic polyisocyanate compound, (b)
High molecular weight polyol, (c) a compound having an anionic hydrophilic group and two or more active hydrogens and optionally used
(d) neutralizing the isocyanate group-terminated prepolymer obtained from the chain extender with (e) one or more chain extenders selected from water-soluble polyamines, hydrazines and derivatives thereof in water to extend the chain in water; (B) the high molecular weight polyol is an acrylic polyol 5 having a hydroxyl value of 5 to 200 mgKOH / g,
A rosin-containing aqueous acrylic-urethane copolymer characterized by containing a rosin-modified polyol or a ring-opened polymer of a lactone obtained using the rosin-modified polyol as a reaction initiation point, b) The content of the rosin-modified polyol or the lactone ring-opening polymer obtained from the rosin-modified polyol in the high molecular weight polyol as a reaction starting point is 3 to 4 of the acryl-urethane copolymer.
The rosin-containing aqueous acrylic resin according to claim 1, which is 0% by weight.
The rosin-containing aqueous acrylic-urethane copolymer according to claim 1, wherein the urethane copolymer, (3) (a) the organic polyisocyanate compound is at least one selected from aliphatic diisocyanate compounds and alicyclic diisocyanate compounds. Product, (4) (b) a high molecular weight polyol, in addition to an acrylic polyol, a rosin-modified polyol or a ring-opened polymer of a lactone obtained by using a rosin-modified polyol as a reaction starting point; 3. The rosin-containing aqueous acrylic-urethane copolymer according to item 1 or 2, which contains at least one selected from ether polyols, (5) (c).
The anionic hydrophilic group of the compound having an anionic hydrophilic group and two or more active hydrogens is a carboxyl group, and the content of the carboxyl group is 0.3 to 2.5% by weight of the acryl-urethane copolymer. A rosin-containing aqueous acryl-urethane copolymer according to Item 1, and (6) a rosin-containing aqueous acryl-urethane copolymer according to any one of Items 1 to 5. Coating agent, and
(7) An adhesive comprising the rosin-containing aqueous acrylic-urethane copolymer according to any one of (1) to (5).

[0005]

DETAILED DESCRIPTION OF THE INVENTION The rosin-containing aqueous acrylic-urethane copolymer of the present invention comprises (a) an organic polyisocyanate compound, (b) a high molecular weight polyol, (c) an anionic hydrophilic group and at least two active hydrogens. And (e) one or more chain extenders selected from water-soluble polyamines, hydrazines and derivatives thereof. In the aqueous polyurethane resin obtained by chain extension in water using (b), a high molecular weight polyol,
Rosin-containing aqueous acrylic-urethane copolymer containing a rosin-modified polyol or a lactone ring-opening polymer obtained using rosin-modified polyol as a reaction starting point in addition to an acrylic polyol having a hydroxyl value of 5 to 200 mgKOH / g in an amount of 5 to 60% by weight. Things. There is no particular limitation on the (a) organic polyisocyanate compound used in the present invention, for example, hexamethylene diisocyanate, aliphatic diisocyanate compounds such as trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, norbornane diisocyanate and the like. Alicyclic diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, tolidine diisocyanate, and xylylene diisocyanate. These organic polyisocyanate compounds,
One kind may be used alone, or two or more kinds may be used in combination. Among these, aliphatic diisocyanate compounds and alicyclic diisocyanate compounds can be suitably used because they give a non-yellowing film, and hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and norbornane diisocyanate are particularly preferred. Can be used.

The high-molecular-weight polyol (b) used in the present invention comprises, in addition to 5 to 60% by weight of an acrylic polyol having a hydroxyl value of 5 to 200 mgKOH / g, a rosin-modified polyol or a lactone obtained by using a rosin-modified polyol as a reaction starting point. Contains a ring-opening polymer. The acrylic polyol is a homopolymer or a copolymer obtained from an acrylic monomer having one ethylenically unsaturated group and a hydroxyl group by a bulk polymerization method, a solution polymerization method, or the like. Examples of the acrylic monomer having one ethylenically unsaturated group and a hydroxyl group include, for example, 2-hydroxyethyl acrylate, 3-chloro-2-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 6-hydroxyhexyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
6-hydroxyhexyl methacrylate, 5,6-dihydroxyhexyl methacrylate and the like can be mentioned. One of these monomers can be used alone, or two or more thereof can be used in combination. Examples of monomers copolymerizable with an acrylic monomer having one ethylenically unsaturated group and a hydroxyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n
-Amyl (meth) acrylate, isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylbutyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclopentyl (meth) acrylate , Cyclohexyl (meth)
Acrylate, phenyl (meth) acrylate, benzyl
(Meth) acrylate, 2-phenylethyl (meth) acrylate, cinnamyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxybutyl (meth)
Acrylate, 3-methoxybutyl (meth) acrylate, 2-n-butoxyethyl (meth) acrylate, 2-
Phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, furfuryl (meth) acrylate, trifluoroethyl (meth) acrylate, 2-
Acrylic monomers such as chloroethyl (meth) acrylate, hexafluoroisopropyl (meth) acrylate, 2-nitro-2-methylpropyl (meth) acrylate, tetrapyranyl (meth) acrylate, (meth) acrylic acid, acrylonitrile, vinyl acetate , Vinyl pyridine,
Examples include ethylenic monomers such as vinylpyrrolidone, methylcrotonate, maleic anhydride, styrene, and α-methylstyrene. Incidentally, (meth) acrylate means acrylate and methacrylate,
(Meth) acrylic acid means acrylic acid and methacrylic acid. One of these copolymerizable monomers can be used alone, or two or more can be used in combination. Acrylic polyols can also be obtained by polymerizing the above monomers in (b) polyester polyols, polycarbonate polyols, polyether polyols and the like which are high molecular weight polyols.

In the present invention, the acrylic polyol contained in the (b) high molecular weight polyol has a hydroxyl value of 5 to 200 mgKOH / g, more preferably 10 to 1 mgKOH / g.
00 mgKOH / g, more preferably 30-70 mgK
OH / g. Further, the glass transition temperature (Tg) of the acrylic polyol is preferably from 0 to 100 ° C.,
More preferably, the temperature is 30 to 80 ° C. When the hydroxyl value of the acrylic polyol is less than 5 mgKOH / g,
The bonding point between the acrylic component and the urethane component may decrease, and the performance as a copolymer may not be sufficiently exhibited. If the hydroxyl value exceeds 200 mgKOH / g, gelation proceeds due to an increase in crosslink density during the synthesis of the isocyanate group-terminated prepolymer, and production may be difficult.
When the glass transition temperature is lower than 0 ° C., the water resistance and alkali resistance of the film may be insufficient. If the glass transition temperature exceeds 100 ° C., the film-forming properties and crack resistance may be insufficient. The acrylic polyol used in the present invention has a weight average molecular weight of 1,000 to 100,000.
It is preferably 0, more preferably 5,000 to 50,000, even more preferably 8,000 to 30,000. In the present invention, the content of the acrylic polyol in the high molecular weight polyol is 5 to 60% by weight, more preferably 7 to 50% by weight, and further preferably 10 to 30% by weight. When the content of the acrylic polyol in the high-molecular-weight polyol is less than 5% by weight, the acrylic component may not sufficiently exhibit advantageous properties such as weather resistance, high solid content, and toughness. When the content of the acrylic polyol in the high-molecular-weight polyol exceeds 60% by weight, the urethane component may not sufficiently exhibit advantageous properties such as chemical resistance, gloss, abrasion resistance, and elasticity.

The rosin-modified polyol used in the present invention is
It is a reaction product composed of one molecule of a diepoxy compound and two molecules of a rosin. There is no particular limitation on the rosins used, for example, natural rosins such as gum rosin, wood rosin, tall oil rosin, purified rosin, disproportionated rosin, purified disproportionated rosin, processed rosin such as hydrogenated rosin, and the like,
These mixtures can be mentioned. The diepoxy compound to be used is not particularly limited, and examples thereof include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, and tripropylene glycol diglycidyl ether. Aliphatic diglycidyl ethers such as propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 2,2-bis (4-hydroxycyclohexyl) Alicyclic diglycidyl ether such as propane diglycidyl ether, 2,2-bis (4-hydroxyphenyl) propane jig Aromatics such as ricidyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyldiglycidyl ether, 2,2-bis (4- (β-hydroxyethyl) phenyl) propane diglycidyl ether Examples thereof include cyclic oxirane compounds such as diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and vinylcyclohexane dioxide. The reaction conditions of the diepoxy compound and the rosins are not particularly limited. For example, by heating 1 mol of the diepoxy compound and 2 mol of the rosins to 120 to 200 ° C. in the presence of a catalyst, two rosin skeletons and two A reaction product having a hydroxyl group can be obtained. There is no particular limitation on the catalyst used, and examples thereof include trimethylamine, triethylamine, tributylamine, benzylmethylamine, pyridine,
Amine catalysts such as -methylimidazole, quaternary ammonium salts such as benzyltrimethylammonium chloride, Lewis acids, borate esters, organometallic compounds,
Organic metal salts and the like can be mentioned. In the present invention, the rosin-modified polyol preferably has an acid value of 5 mgKOH / g or less, more preferably 3 mgKOH / g or less.

The lactone ring-opened polymer obtained by using the rosin-modified polyol used as a reaction starting point in the present invention is obtained by using the above-mentioned rosin-modified polyol as a reaction starting point, ε-caprolactone, γ-caprolactone, γ-valerolactone, It is a polymer obtained by polymerizing lactones such as δ-valerolactone and γ-butyrolactone. One of these lactones can be used alone, or two or more can be used in combination. The conditions for the ring-opening polymerization reaction of the lactones with the rosin-modified polyol as the reaction starting point are not particularly limited.
More preferably, ring-opening polymerization can be performed by heating to 140 to 180 ° C. At this time, as a polymerization catalyst, tetrabutyl titanate, an organic titanium compound such as tetrapropyl titanate, dibutyltin laurate,
Organic tin compounds such as tin octylate and dibutyltin oxide, and stannous halides such as stannous chloride, stannous bromide, and stannous iodide can be used. The amount of the catalyst used is preferably 0.01 to 1,000 ppm based on the total amount of the rosin-modified polyol and lactones. The ring-opened polymer thus obtained is a diol compound having a relatively narrow molecular weight distribution in which lactones are ring-opened and polymerized starting from the hydroxyl group of the rosin-modified polyol. In the present invention, the content of the rosin-modified polyol or the lactone ring-opening polymer obtained from the rosin-modified polyol in the high-molecular-weight polyol as a reaction starting point is 3 to 40% by weight of the acryl-urethane copolymer. And more preferably 5 to 25% by weight.
When the content of the rosin-modified polyol in the high-molecular-weight polyol or the lactone ring-opening polymer obtained using the rosin-modified polyol as a reaction starting point is less than 3% by weight of the acryl-urethane copolymer, the poorly adhesive plastic There is a possibility that the expression of adhesion to the substrate may be insufficient. The content of the rosin-modified polyol or the lactone ring-opening polymer obtained from the rosin-modified polyol in the high molecular weight polyol as a reaction starting point is 40% of the acrylic-urethane copolymer.
If the content is more than 10% by weight, the film may be too hard, and the manifestation of advantageous properties such as elasticity by the urethane resin may be insufficient.

In the present invention, the high molecular weight polyol (b) may further include, if necessary, an acrylic polyol, a rosin-modified polyol or a lactone-opened polymer obtained from a rosin-modified polyol as a reaction starting point. Other polyols can be included. The other polyol to be contained is not particularly limited, but, for example, polyester polyol, polycarbonate polyol, polyether polyol and the like can be suitably used.
As the polyester polyol, for example, polyethylene adipate, polybutylene adipate, polyethylene butylene adipate, polyhexamethylene isophthalate adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, poly-ε-caprolactone diol, Poly (3-methyl-1,5-pentylene adipate), 1,6
-Polycondensates of hexanediol and dimer acid. Examples of the polycarbonate polyol include polytetramethylene carbonate diol and polyhexamethylene carbonate diol. Examples of the polyether polyol include a homopolymer, a block copolymer, and a random copolymer of polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Further, a polyetherester polyol obtained by combining a polyether polyol and a polyester polyol can also be used. These other polyols
One kind may be used alone, or two or more kinds may be used in combination.

[0011] The (c) anionic hydrophilic group and 2
As the compound having two or more active hydrogens, for example,
2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and the like can be mentioned. One of these compounds can be used alone, or two or more of them can be used in combination. In the present invention, the anionic hydrophilic group and the anionic hydrophilic group of the compound having two or more active hydrogens, before or after the preparation of isocyanate group-terminated prepolymer, trimethylamine, triethylamine, tri-n-propylamine, tributylamine, Neutralize with amines such as N-methyl-diethanolamine, N, N-dimethylmonoethanolamine, triethanolamine, potassium hydroxide, sodium hydroxide, ammonia and the like. In the present invention, the neutralized product of the isocyanate group-terminated prepolymer is, before or after the preparation of the isocyanate group-terminated prepolymer, (c) an anionic hydrophilic group and an anionic hydrophilic group of a compound having two or more active hydrogens. Is obtained by neutralizing In the rosin-containing aqueous acrylic-urethane copolymer of the present invention, it is preferred that (c) the anionic hydrophilic group of the compound having an anionic hydrophilic group and two or more active hydrogens is a carboxyl group. The content of the carboxyl group is preferably from 0.3 to 2.5% by weight, more preferably from 0.5 to 1.5% by weight of the acryl-urethane copolymer. If the content of the carboxyl group is less than 0.3% by weight of the acryl-urethane copolymer, it may be difficult to emulsify the acryl-urethane copolymer or the emulsion stability may be insufficient. When the content of the carboxyl group exceeds 2.5% by weight of the acryl-urethane copolymer, the water resistance of the coating film may be reduced.

In the present invention, (d) a chain extender can be used, if necessary, when preparing an isocyanate group-terminated prepolymer. Examples of the chain extender include ethylene glycol, 1,4-butanediol,
6-hexanediol, trimethylolpropane, pentaerythritol, low molecular weight polyhydric alcohols such as sorbitol, ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine, etc. And the like low molecular weight polyamines. One of these chain extenders can be used alone, or two or more can be used in combination. In the present invention, a prepolymer having a terminal isocyanate group is prepared using the component (a), the component (b), the component (c) and, if necessary, the component (d). The prepolymer is prepared, for example, by a one-shot method (single-stage method) or a multi-stage isocyanate polyaddition reaction at a reaction temperature of 4.
It can be performed under the condition of 0 to 150 ° C. At this time, if necessary, a reaction catalyst such as dibutyltin dilaurate, stannas octoate, dibutyltin-2-ethylhexanoate, triethylamine, triethylenediamine, N-methylmorpholine and the like can be added. During or after the reaction, an organic solvent that does not react with the isocyanate group can be added. As organic solvents,
For example, acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, dimethylformamide, N-methylpyrrolidone and the like can be mentioned.

Next, the resulting neutralized isocyanate group-terminated prepolymer is subjected to chain extension in water. When the (c) anionic hydrophilic group in the prepolymer and the anionic hydrophilic group of the compound unit having two or more active hydrogens are not neutralized, the anionic hydrophilic group is neutralized and then emulsified in water. Dispersed and (e) made high molecular weight using one or more chain extenders selected from water-soluble polyamines, hydrazine and derivatives thereof. Examples of the water-soluble polyamine used as a chain extender include ethylenediamine, propylenediamine, hexamethylenediamine, diaminocyclohexylmethane, piperazine, 2-methylpiperazine, isophoronediamine, diethylenetriamine, and triethylenetetramine. Examples of the water-soluble amine derivative used as a chain extender include an amidoamine derived from a diprimary amine and a monocarboxylic acid, and a monoketimine of a diprimary amine. Examples of the hydrazine derivative used as a chain extender include a compound having at least two hydrazino groups in a molecule, and a dicarboxylic acid dihydrazide having 2 to 10 carbon atoms, or an aliphatic water solution having 2 to 4 carbon atoms. Sexual dihydrazine is preferred. Examples of the dihydrazide of a dicarboxylic acid having 2 to 10 carbon atoms include, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic dihydrazide. And the like. Examples of the aliphatic water-soluble dihydrazine having 2 to 4 carbon atoms used as a chain extender include 1,1′-ethylenedihydrazine, 1,1′-trimethylenedihydrazine, 1,1 ′-(1, 4-butylene) dihydrazine and the like. One of these chain extenders can be used alone, or two or more can be used in combination.

In the present invention, when the isocyanate group-terminated prepolymer is synthesized using a solvent, for example,
After completion of the chain elongation reaction, the solvent is preferably removed by distillation under reduced pressure or the like. Surfactants, for example, anionic surfactants such as higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonates, higher alkyl sulfonates, alkyl allyl sulfonates, sulfonated castor oil, sulfosuccinates, etc., ethylene oxide The emulsifiability can also be maintained by using a nonionic surfactant such as a reaction product of a nonionic surfactant with a long-chain aliphatic alcohol or phenol. The rosin-containing aqueous acrylic-urethane copolymer of the present invention thus obtained forms a coating film excellent in durability, weather resistance, light resistance, water resistance, etc., and further, an aqueous oxazoline-based crosslinking agent By using a crosslinking agent having reactivity with a carboxyl group, such as an aqueous (poly) carbodiimide-based crosslinking agent or an aqueous epoxy resin-based crosslinking agent, it is possible to impart more excellent water resistance. The rosin-containing aqueous acrylic-urethane copolymer of the present invention has excellent adhesiveness to an adherend, and particularly exhibits excellent adhesiveness to a plastic film such as polypropylene or polyester having poor adhesion. Also,
The dried coating film has good flexibility, abrasion resistance, washing resistance, glossiness, etc., and can be used for various applications where these performances are required. In particular, paints, printing inks, etc. Can be suitably used as a coating agent or an adhesive. The reason that the rosin-containing aqueous urethane-acrylic copolymer of the present invention exhibits the above-mentioned effects is presumed to be that the acrylic component is a completely uniform copolymer incorporated in the urethane component.

[0015]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. Production Example 1 A round bottom flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube was charged with 200 parts by weight of gum rosin [WG, made in China, acid value 166.1 mgKOH / g], and heated under a stream of nitrogen gas. Melted, 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether [epoxy equivalent 1
83.9] 108.9 parts by weight are added with stirring,
At 140 ° C, 0.058 parts by weight of 2-methylimidazole was added and reacted at 150 ° C for 5 hours. 308.6 parts by weight of a rosin-modified polyol having a hydroxyl value of 113.0 mgKOH / g and an acid value of 1.4 mgKOH / g were added. Obtained. This rosin-modified polyol is referred to as rosin-modified polyol A. Production Example 2 The same reactor as in Production Example 1 was charged with 182.7 parts by weight of the rosin-modified polyol A obtained in Production Example 1, 168.4 parts by weight of ε-caprolactone, and 0.08 parts by weight of dibutyltin laurate. For 11 hours to obtain 351.0 parts by weight of a ring-opened ε-caprolactone polymer using a rosin-modified polyol having a hydroxyl value of 52.1 mgKOH / g and an acid value of 0.8 mgKOH / g as a polymerization initiator. Production Example 3 1,6-hexanediol diglycidyl ether [epoxy equivalent: 15.9] instead of 2,2-bis (4-hydroxyphenyl) propane diglycidyl ether 89.
Except that 4 parts by weight were used, 289.0 parts by weight of a rosin-modified polyol having a hydroxyl value of 120.0 mgKOH / g and an acid value of 2.0 mgKOH / g were obtained in the same manner as in Production Example 1. This rosin-modified polyol is referred to as rosin-modified polyol B.

Example 1 In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, an acrylic polyol [Dainippon Ink Chemical Industry Co., Ltd., Acrydic A-808T, non-volatile content: 50% by weight, hydroxyl value about 20 mgKOH / g, glass transition temperature 97 ° C] 56 parts by weight, polyhexamethylene carbonate diol [number average molecular weight 1,000] 60 parts by weight, rosin-modified polyol A1 obtained in Production Example 1
9.8 parts by weight, 0.9 parts by weight of 1,4-butanediol, 2,
6.7 parts by weight of 2-dimethylolpropionic acid, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone are charged and uniformly mixed, and then 52.4 parts by weight of dicyclohexylmethane diisocyanate is added. The reaction was carried out to obtain a solution of a urethane prepolymer in methyl ethyl ketone having a free isocyanate group content of 1.65% by weight based on the nonvolatile content. This solution is
After cooling to 0 ° C. and neutralizing by adding 5 parts by weight of triethylamine, 350 parts by weight of water was gradually added to emulsify and disperse, 15 parts by weight of a 20% by weight aqueous solution of ethylenediamine was added, and stirring was continued for 2 hours. . Next, the solvent was removed while the temperature was raised to 60 ° C. over 2 hours under reduced pressure to obtain a rosin-containing aqueous acrylic-urethane copolymer having a solid content of about 35% by weight. 2,2 in this acrylic-urethane copolymer
The content of carboxyl groups derived from dimethylolpropionic acid is 1.3% by weight. Example 2 An acrylic polyol [Dainippon Ink & Chemicals, Inc., Acridic A-809,
About 50% by weight of non-volatile content, about 20 mg KOH / hydroxyl number
g, glass transition temperature 61 ° C.] 112 parts by weight, polybutylene adipate diol [number average molecular weight 1,700] 68
Parts by weight, polyethylene glycol [number average molecular weight 1,0
100 parts by weight, 65 parts by weight of a ring-opened polymer of ε-caprolactone obtained using the rosin-modified polyol obtained in Production Example 2 as a polymerization initiator, 7.4 parts by weight of 2,2-dimethylolbutanoic acid, After 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone were mixed and mixed uniformly, 44.6 parts by weight of isophorone diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours. A 9% by weight urethane prepolymer solution in methyl ethyl ketone was obtained. The solution was cooled to 30 ° C., neutralized by adding 5 parts by weight of triethylamine, emulsified and dispersed by gradually adding 480 parts by weight of water, added with 15 parts by weight of a 20% by weight aqueous solution of ethylenediamine, and stirred for 2 hours. Continued. Next, the solvent was removed while the temperature was raised to 60 ° C. over 2 hours under reduced pressure to obtain a rosin-containing aqueous acrylic-urethane copolymer having a solid content of about 35% by weight. The content of carboxyl groups derived from 2,2-dimethylolbutanoic acid in this acryl-urethane copolymer is 0.9% by weight.

Example 3 Acrylic polyol [Dainippon Ink and Chemicals, Acridic A-811;
Non-volatile content about 50% by weight, hydroxyl value about 17 mgKOH /
g, glass transition temperature 59 ° C] 64 parts by weight, poly-ε-caprolactone diol [number average molecular weight 2,000] 80
Parts by weight, rosin-modified polyol B2 obtained in Production Example 3
8 parts by weight, 6.7 parts by weight of 2,2-dimethylolpropionic acid, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone were charged and uniformly mixed, and then 44.6 parts by weight of isophorone diisocyanate was added. The reaction was carried out at 80 ° C. for 2 hours to obtain a urethane prepolymer solution in methyl ethyl ketone having a free isocyanate group content of 2.1% by weight based on the nonvolatile content. Add this solution to 30
After cooling to 5 ° C. and neutralizing by adding 5 parts by weight of triethylamine, 370 parts by weight of water was gradually added to emulsify and disperse, 5.8 parts by weight of a 60% by weight aqueous solution of hydrazine hydrate was added, and the mixture was stirred for 2 hours. Continued. Next, the solvent was removed while heating to 60 ° C. over 2 hours under reduced pressure to obtain a rosin-containing aqueous urethane-acrylic copolymer having a solid content of about 35% by weight. 2,2 in this acrylic-urethane copolymer
The carboxyl group content from dimethylolpropionic acid is 1.16% by weight; Example 4 An acrylic polyol [Dainippon Ink and Chemicals, Inc., Acrydic 44-19] was placed in a reaction vessel similar to that of Example 1.
8. Non-volatile content about 50% by weight, hydroxyl value about 20 mg KO
H / g, glass transition temperature 70 ° C] 56 parts by weight, poly (3-
Methyl-1,5-pentylene adipate) [number-average molecular weight 1,000] 50 parts by weight, polypropylene glycol [number-average molecular weight 1,000] 10 parts by weight, rosin-modified polyol B obtained in Production Example 3 18.7 parts by weight Parts and 2,2
6.7 parts by weight of dimethylolpropionic acid are dissolved in 30 parts by weight of methyl ethyl ketone, neutralized by adding 5 parts by weight of triethylamine, and then dibutyltin dilaurate is added in an amount of 0.5%.
After 001 parts by weight and 30 parts by weight of methyl ethyl ketone were charged and uniformly mixed, 52.4 parts by weight of dicyclohexylmethane diisocyanate was added, and the mixture was reacted at 80 ° C. for 2 hours. A solution of urethane prepolymer in methyl ethyl ketone was obtained. The solution was cooled to 30 ° C.
0 parts by weight was gradually added and emulsified and dispersed, 18 parts by weight of a 20% by weight aqueous solution of ethylenediamine was added, and stirring was continued for 2 hours. Next, the solvent was removed while heating to 60 ° C. over 2 hours under reduced pressure to obtain a rosin-containing aqueous acrylic-urethane copolymer having a solid content of about 35% by weight. The carboxyl group content derived from 2,2-dimethylolpropionic acid in this acrylic-urethane copolymer is 1.3% by weight.
It is.

Comparative Example 1 Acrylic polyol [Dainippon Ink and Chemicals, Acridic A-809;
About 50% by weight of non-volatile content, about 20 mg KOH / hydroxyl number
g, glass transition temperature 61 ° C.] 112 parts by weight, polybutylene adipate diol [number average molecular weight 1,700] 68
Parts by weight, polyethylene glycol [number average molecular weight 1,0
00] 10 parts by weight, 2.4 parts by weight of 1,6-hexanediol, 6.7 parts by weight of 2,2-dimethylolpropionic acid, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone were charged and uniformly mixed. After mixing, 52.4 parts by weight of dicyclohexylmethane diisocyanate was added and reacted at 80 ° C. for 2 hours to obtain a solution of a urethane prepolymer having a free isocyanate group content of 1.7% by weight based on nonvolatile matter in methyl ethyl ketone. The solution was cooled to 30 ° C., neutralized by adding 5 parts by weight of triethylamine, and then gradually added to 350 parts by weight of water to emulsify and disperse. 18 parts by weight of a 20% aqueous solution of ethylenediamine was added, followed by stirring for 2 hours. Continued. Next, the solvent was removed while heating to 60 ° C. over 2 hours under reduced pressure, and the solid content was reduced to about 3%.
5% by weight of an aqueous acrylic-urethane copolymer was obtained. The content of carboxyl groups derived from 2,2-dimethylolpropionic acid in the acrylic-urethane copolymer is 1.1.
% By weight. Comparative Example 2 70 parts by weight of polyhexamethylene carbonate diol [number average molecular weight 1,000], 1.2 parts by weight of ethylene glycol, and 6.7 parts by weight of 2,2-dimethylolpropionic acid were placed in the same reaction vessel as in Example 1. , 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone, and after mixing uniformly, 52.4 parts by weight of dicyclohexylmethane diisocyanate was added.
The reaction was carried out for a period of time to obtain a urethane prepolymer solution in methyl ethyl ketone having a free isocyanate group content of 2.7% by weight based on the nonvolatile content. Cool the solution to 30 ° C.
After neutralization by adding 5 parts by weight of triethylamine, water 3
50 parts by weight were gradually added to emulsify and disperse, 18 parts by weight of a 20% by weight aqueous solution of ethylenediamine was added, and stirring was continued for 2 hours. Next, the solvent was removed while heating to 60 ° C. over 2 hours under reduced pressure to obtain an aqueous urethane resin having a solid content of about 35% by weight. The content of carboxyl groups derived from 2,2-dimethylolpropionic acid in this urethane resin is 1.6% by weight. Comparative Example 3 In a reaction vessel similar to that in Example 1, 100 parts by weight of poly-ε-caprolactone diol [number average molecular weight 2,000] was added.
2.4 parts by weight of 1,6-hexanediol, 6.7 parts by weight of 2,2-dimethylolpropionic acid, 0.001 part by weight of dibutyltin dilaurate and 60 parts by weight of methyl ethyl ketone are charged and uniformly mixed, and then mixed with dicyclohexylmethane. 52.4 parts by weight of diisocyanate was added and reacted at 80 ° C. for 2 hours to obtain a solution of urethane prepolymer in methyl ethyl ketone having a free isocyanate group content of 1.9% by weight based on nonvolatile components. The solution was cooled to 30 ° C. and neutralized by adding 5 parts by weight of triethylamine.
350 parts by weight of water was gradually added to emulsify and disperse, 4 parts by weight of a 60% by weight aqueous solution of hydrazine hydrate was added, and stirring was continued for 2 hours. Next, the solvent was removed while heating to 60 ° C. over 2 hours under reduced pressure to obtain an aqueous urethane resin having a solid content of about 35% by weight. The content of carboxyl groups derived from 2,2-dimethylolpropionic acid in this urethane resin is 1.3% by weight.

The aqueous resins obtained in Examples 1 to 4 and Comparative Examples 1 to 3 were each diluted with pure water so that the resin solid content concentration became 10% by weight, and a bar coater (No. 8) was used. Then, it is applied to a discharge-treated surface of a biaxially stretched polypropylene film (OPP) having been subjected to a corona discharge treatment having a thickness of 20 μm and one surface of a biaxially stretched polyethylene terephthalate film (PET) having a thickness of 11 μm. After drying, a coated film was obtained. The obtained coated film was aged at a temperature of 40 ° C. and a humidity of 10% RH for 24 hours using a thermo-hygrostat, and a cellophane adhesive tape [Nichiban Co., Ltd.] was adhered to the coated surface and the angle was 60 ° C. The appearance of the coating film when rapidly peeled was observed and evaluated according to the following criteria. (1) Transparency ：: Very good ：: Good ：: Normal ×: Poor (2) Gloss 非常: Very good ：: Good ：: Normal ×: Poor (3) Adhesive ◎: 95% or more of coating film Remains on the film side. ：: 80% or more of the coating film remains on the film side. Δ: 50% or more and less than 80% of the coating film remains on the film side. X: Less than 50% of the coating film remains on the film side. Table 1 shows the evaluation results.

[0020]

[Table 1]

As can be seen from Table 1, the rosin-containing aqueous acrylic-urethane copolymers of the present invention of Examples 1 to 4 are excellent in transparency and gloss, and can be used with polyethylene terephthalate films for polypropylene films. A coating film having good adhesiveness is obtained. On the other hand, the coating film obtained from the aqueous acrylic-urethane copolymer of Comparative Example 1 containing no rosin component is excellent in transparency and gloss, but slightly inferior in adhesiveness, and the acrylic component is also rosin component. The coating film obtained from the aqueous urethane resin of Comparative Examples 2 and 3 which does not contain
All of the adhesion is poor.

[0022]

Since the rosin-containing aqueous acrylic-urethane copolymer of the present invention is a homogeneous copolymer, when it is applied to a poorly-adhesive plastic film such as polypropylene, polyethylene terephthalate, etc. Compared with the case of using a single resin, a blended resin thereof, and a resin mixture partially copolymerized, not only adhesiveness, but also excellent performance in appearance such as transparency and gloss is exhibited. A wide range of development is possible as an aqueous adhesive.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI theme coat ゛ (Reference) C09J 175/04 C09J 175/04 (72) Inventor Takahiro Inatsugu 4-23-1, Bunkyo, Fukui-shi, Fukui Sun Within Huaka Chemical Co., Ltd. (72) Inventor Shinichi Umetani 4-23-1, Bunkyo, Fukui City, Fukui Prefecture F-term within Nikka Chemical Co., Ltd. 4J034 BA06 BA07 BA08 BA09 CA03 CA15 DA01 DB05 DB07 DF01 DF02 DF11 DF12 DG01 DQ04 EA14 HA01 HC03 HC12 HC17 HC22 HC46 HC52 HC61 HC71 HC73 JA02 JA13 JA42 RA07 RA08 4J038 DG051 DG101 DG102 DG111 DG112 DG121 DG122 DG131 DG132 DG191 DG262 DG272 GA06 MA08 PC08 4J040 EF052 EF052 EF051 EF051 EF052 EF292 GA07 JA03 JB02 LA06 MA10 MB09

Claims (7)

[Claims] (A) an organic polyisocyanate compound,
(B) a high molecular weight polyol, (c) a compound having an anionic hydrophilic group and two or more active hydrogens, and (d) a neutralized isocyanate group-terminated prepolymer obtained from a chain extender, e) water-soluble polyamine,
In an aqueous polyurethane resin obtained by extending a chain in water using one or more chain extenders selected from hydrazine and derivatives thereof, (b) a high-molecular-weight polyol having a hydroxyl value of 5-200 mgKOH / g acrylic A rosin-containing aqueous acrylic-urethane copolymer characterized by containing a rosin-modified polyol or a ring-opened polymer of a lactone obtained using the rosin-modified polyol as a reaction starting point, in addition to the polyol 5 to 60% by weight. 2. The content of the rosin-modified polyol or the lactone ring-opened polymer obtained from the rosin-modified polyol in the high molecular weight polyol as a reaction starting point is 3 to 40% by weight of the acryl-urethane copolymer. %.
A rosin-containing aqueous acrylic-urethane copolymer as described in the above. 3. The method according to claim 1, wherein (a) the organic polyisocyanate compound is
The rosin-containing aqueous acrylic-urethane copolymer according to claim 1, which is at least one member selected from an aliphatic diisocyanate compound and an alicyclic diisocyanate compound. (B) a rosin-modified polyol or a ring-opened polymer of a lactone obtained by using a rosin-modified polyol as a reaction starting point in addition to an acrylic polyol as a high molecular weight polyol; 3. The method according to claim 1, which comprises at least one selected from ether polyols.
A rosin-containing aqueous acrylic-urethane copolymer as described in the above. 5. The compound having (c) an anionic hydrophilic group and two or more active hydrogens, wherein the anionic hydrophilic group is a carboxyl group, and the content of the carboxyl group is 0.1% in the acryl-urethane copolymer. 2. The rosin-containing aqueous acrylic-urethane copolymer according to claim 1, wherein the amount is 3 to 2.5% by weight. 6. A coating agent comprising the rosin-containing aqueous acrylic-urethane copolymer according to any one of claims 1 to 5. 7. An adhesive comprising the rosin-containing aqueous acrylic-urethane copolymer according to any one of claims 1 to 5.