JPS59215338A - Aqueous anchor coating agent - Google Patents

Abstract

PURPOSE:To provide an aq. anchor coating agent having excellent bonding properties and dilution and dispersion stabilities in use and excellent storage stability, consisting mainly of a mixture of a conjugated diene polymer and a low-molecular aliph. polyamine. CONSTITUTION:An aq. anchor coating agent consists mainly of a mixture of a conjugated diene polymer and an aliph. polyamine having an MW of 10,000 or below or a reaction product therebetween. Examples of the conjugated diene polymers are homopolymers composed of aliph. conjugated diene polymer chains and rondom, block and graft copolymers of two or more conjugated dienes, and those which have an MW of 1,000-10,000 and are liquid at room temp. are preferred. Examples of pref. aliph. polyamines are alkylene polyamines, polyalkylenepolyamines and polyalkylene mimines having a MW of 200-2,000.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous anchor coating agent. More specifically, the present invention relates to a water-based anchor coating agent suitable for melt-extrusion laminates containing a conjugated diene polymer and an aliphatic polyamine as main components.

Cellophane, paper, metal foil, glass film, etc. are used as base materials, and after coating these with an appropriate melt-extrusion laminating adhesive (hereinafter simply referred to as anchor coating agent), plastics such as polyethylene and polypropylene are melt-extruded. Composite films obtained by lamination are widely used as packaging materials.

Conventionally, anchor coating agents that can be diluted and dissolved in organic solvents such as polyisocyanate compounds and organic titanium compounds have been mainly used, but since they contain solvents, they are flammable, toxic, and air polluting. Water-based anchor coating agents have been studied from the viewpoint of safety and pollution, as well as from economic viewpoints. These water-based anchor coating agents include polyethyleneimine or its fatty conductor, methoxymethylolated melamine, acrylic emulsions, vinyl acetate emulsions, etc., but these have poor physical properties such as moisture resistance and water resistance. It could not always be said that it had satisfactory performance, such as having defects and being limited in the types of substrates to which it could be applied.

In addition, as a method to overcome these drawbacks,
No. 39471 has been disclosed, and this anchor coating agent is composed of a conjugated diene polymer and polyethyleneimine, and one of the components, polyethyleneimine, has a molecular weight of about 70,000 and a viscosity of about 400 to 1. 0
000PS (30% by weight aqueous solution, B-temperature viscometer, 5°C) is only disclosed. Also, the dilution and dispersion stability during use was not fully satisfactory, leaving room for improvement.

In view of the above-mentioned current situation, the present inventors have developed a material that has good storage stability and dilution and dispersion stability during use, and has good adhesive properties.
As a result of intensive research aimed at developing an anchor coating agent with excellent adhesive properties such as moisture resistance and water resistance, it was discovered that the desired purpose could be achieved by using a low molecular weight aliphatic polyamine. , we have completed the present invention.

That is, the present invention has a conjugated tzene-based polymer and a molecular weight of i.
It is an aqueous anchor coating agent mainly composed of a mixture with an aliphatic polyamine of o, ooo or less, or a mixed reaction product thereof.

The characteristics of the present invention are that the conjugated diene polymer has a molecular weight of 10,
We aim to provide an anchor coating agent that has good storage stability, dilution and dispersion stability during use, and has excellent adhesive properties, especially by using a low molecular weight aliphatic polyamine. The object of the present invention is to provide an anchor coating agent which exhibits extremely excellent storage stability and dilution and dispersion stability during use without deteriorating adhesive properties.

The conjugated diene-based polymers used in the present invention include homopolymers of aliphatic conjugated dienes, random, block, and graft copolymers of two or more types of aliphatic conjugated dienes, and polymer chains of monomers constituting the polymer chains. (Capital) Random, block and graft copolymers in which at least % by weight consists of one or more aliphatic conjugated die/diyl compounds and the other comonomer is an aromatic or aliphatic vinyl compound, and mixtures thereof. used.

The aliphatic conjugated dienes include 1,3-butadiene, isogrene 1,3-pentadiene, chlorogrene, cyclopentadiene, etc., and the vinyl monomers include styrene, α-methylstyrene, P-methyl Aromatic vinyl compounds such as styrene, P-nitylstyrene, P-methoxystyrene, chlorostyrene, acrylonitrile, methachlorylonitrile, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, Included are aliphatic vinyl compounds such as butyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, allyl chloride, allyl glycidyl ether, diallyl phthalate, and the like.

The molecular weight of the conjugated diene polymer is number average molecular i200 to i00,000, preferably 1,00
0 to 10,000 and is liquid at room temperature.

The conjugated diene polymer having a functional group used in the present invention is prepared by living polymerization of the above aliphatic conjugated diene or a mixture of this and the above vinyl monomer,
Those with a terminal carboxyl group or hydroxyl group obtained by treating the living terminal with CO2, ethylene oxide, etc., those with a terminal incyanate group obtained by further adding a polyisocyanate compound to these, and conjugated diene polymers. Those to which maleic anhydride is added and those to which double bonds derived from conjugated diene units are epoxidized are used.

Among conjugated diene polymers, those having polybutadiene as a backbone and 60% or more of 1,2-bonds are particularly preferred, such as 1,2-polybutadiene, 1゜2-polybutadiene glycol, 1,2-polybutadiene, Gencarboxylic acid, 1,2-polyptasoene maleate/compound, 1,2-polyptazoe/epoxide are used.

When a conjugated diene polymer having a functional group that reacts with a primary or secondary amine group is used as the conjugated diene polymer, it reacts with the aliphatic polyamine used to obtain a completely water-soluble anchor coating agent. , more preferred.

The aliphatic polyamine used in the present invention has a molecular weight of io, ooo or less, preferably a molecular weight of 200 to 2.0.
00 alkylene polyamines, polyalkylene/polyamines and polyalkylene imines.

If the molecular weight is more than io or ooo, it will not be possible to achieve the objective of the present invention of improving storage stability and dilution dispersion stability during use. Examples of the alkylene polyamines and polyalkylene polyamines include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamino, pentaethylene hexamino, and similar propylene polyamines and butylene holamines. These include polyethyleneimine obtained by polymerizing ethyleneimine and similar polyethyleneimine, polybutyleneimine, etc., and polyethyleneimine is preferred.

The blending ratio of the conjugated diene polymer and the aliphatic polyamine in the present invention is 5 to 200 parts by weight (solid content) of the aliphatic polyamine per 100 parts by weight of the conjugated diene polymer;
Preferably it is 10 to 100 parts by weight. When the amount of aliphatic polyamine used is small, phenomena such as insufficient water dispersion stability and adhesive properties are observed, and water resistance is also decreased.

In the present invention, the mixing of the conjugated diene polymer and the aliphatic polyamine or the IIi mixing reaction is carried out, for example, as follows. In a container equipped with a stirrer and a thermometer, a fixed amount of conjugated diene thread polymer or its water-soluble solvent (tθr
(t-butanol, dioxane, ethylene glycol monobutyl ether, etc.) solution (9), then add a predetermined amount of aliphatic polyamine, an aqueous solution thereof, or a water-soluble solvent solution thereof, and heat to room temperature or 50 to 130 °C. ,0
．． Stir for 5-10 hours. The reason why the conjugated diene polymer is made into an entirely water-soluble solvent solution is to lower the viscosity when the conjugated diene polymer is highly viscous even if it is solid or liquid at room temperature.

If necessary, the following diluent, curing accelerator, and other water-soluble or water-dispersible resins are added to the thus obtained mixture or mixed reaction product solution to prepare an anchor coating agent.

In the present invention, the diluent added at an appropriate time from the time of mixing or mixing reaction to immediately before use as an anchor coating agent may be water alone or a combination of water and a lower alcohol such as methanol or ethanol, and/or other water-soluble solvent. A mixture of is used.

The above-mentioned lower alcohol and water-soluble solvent have the effect of improving the wettability of the surface of the material to be coated and accelerating the rate of diluent evaporation after coating.

Examples of curing accelerators used in the present invention include metal dryer systems represented by heptatenates or octenoates of cobalt, manganese, lead, iron, etc., ammonium persulfate, potassium persulfate, hydrogen peroxide, etc. A water-soluble radical initiator and a redox catalyst comprising a combination of the former two are suitable.

The water-based anchor coating agent according to the present invention has sufficient performance by itself, but in order to further expand its applicability, other water-soluble or water-dispersible resins such as polyvinyl acetate, water-soluble phenol resin, hexamethoxymethylol can be used. It is also possible to add a water-soluble melamine resin such as melamine, but in reality, the water-based anchor coating agent according to the present invention and other water-soluble or water-dispersible resins are simply mixed at room temperature, Alternatively, it is also possible to use a thermal treatment method to generate a slight chemical bond between the two.

The aqueous anchor coating agent of the present invention can be optionally diluted with water or an inexpensive solvent such as methanol or isozorobyl alcohol.Actually, the resin content is 5 to 0.2%, preferably 2 to 0. 2-4f/rr at .5%? c Resin coating amount: 0.01 to 0.089/n? ) Excellent adhesive properties can be obtained with a small amount of coating, and furthermore, because the dilution and dispersion stability is good, the residual liquid can be used even after 3 days, making it extremely economical. Furthermore, the adhesive strength is extremely excellent, with good moisture resistance and water resistance even after wetting.

Next, the present invention will be specifically explained with reference to Examples, Comparative Examples, and 2, but the present BA is not limited by these. and weight %.

Example 1 Molecular weight 140 produced by anionic living polymerization method
0.1,2-vinyl bond 90.0ti, 1.4-tra/
Microstructure with 10.0% of gas bonds, acid value 61. α,ω-Butadiene homopolymer dicarboxylic acid (Nl5SO-P manufactured by Nippon Soda) with a characteristic value of viscosity 150 poise (45°C)
BXe-1ooo) ioo parts, tart-butanol 150 parts, and Evomino 5P-003 (polyethyleneimine manufactured by Nippon Shokubai Chemical Co., Ltd., molecular weight 300) 50 parts were charged into a reaction vessel, and the temperature was raised to 70°C with stirring.
Stirring was continued for an hour. Next, 5 parts of 5% water-soluble cobalt naphthenate, 10 parts of 10% potassium persulfate aqueous solution, 80 parts of ethanol, and 355 parts of water were added and thoroughly stirred to obtain a uniform dispersion (1) with a resin content of 20%. This dispersion has a storage capacity of 6
It was more stable than Chizuki.

Example 2 Molecular weight 196 produced by anionic living polymerization method
α,ω-butadiene homopolymer with a microstructure of 90.0% of 0.1,2-vinyl bonds, 10.0% of t,l,4-trans bonds, an acid value of 37, and a viscosity of 393 poise (at 45°C). Polymer dicarboxylic acid (Nippon Soda N-5SO-PB)
XO-2000) 100 parts, tert-butanol 1
80 parts of Epomino 5p-003 (described above) were charged into a reaction vessel, and the temperature was raised while stirring, and the stirring was continued at 70°C for 3 hours. then 5 parts of 5% water-soluble cobalt naphthenate;
10 parts of 10% potassium persulfate aqueous solution, 100 parts of ethanol
1 part, add 425 parts of water and stir well to obtain a uniform resin content of 2 parts.
A 0% dispersion (It) was obtained. This dispersion was stable on storage for more than 6 months.

Example 3 N-880-FB, 100 parts of 0-1000 (mentioned above), 150 parts of tert-butanol, Epomino 5p-o
50 parts of i8 (polyethyleneimide/manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., molecular weight: xsoo) was charged into a reaction vessel, and the temperature was raised while stirring, and the stirring was continued at 70° C. for 3 hours. Next, 5 parts of 5-fiber water-bathable cobalt nanthenate, 10 parts of 10% potassium persulfate aqueous solution, 80 parts of ethanol, and 355 parts of water were added and thoroughly stirred to obtain a uniform dispersion (lit) with a resin content of 20 parts.

This dispersion was stable on storage for more than 6 months.

Example 4 Molecular weight 123 produced by anionic living polymerization method
0.1.2-vinyl bond 88.0, 1.4- ) years old/
A living polygetadiene homopolymer having a microstructure of 12.0% gas bonding and having an epoxy group added to the terminal with chevichlorohydrin by a known method (epoxy oxygen i 1.5%) 100 parts, ethylene 150 parts of glycol motuptyl ether, EpomiysP-00
6 (polyethyleneimine manufactured by Nippon Shokubai Chemical Co., Ltd., molecule i
600) was charged into a reaction vessel, the temperature was raised while stirring, and the stirring was continued for 1 hour at blade temperature.

Next, 5 parts of 5% water-soluble cobalt naphthenate, 10 parts of 10% potassium persulfate aqueous solution, 80 parts of ethanol, and 355 parts of water.
of the resin and stir well to make a uniform dispersion with a resin content of 20% (
IV) was obtained. This dispersion was stable on storage for more than 6 months.

Example 5 Molecular weight 980 produced by anionic living polymerization method
．． Epoxidizing a part of the branched vinyl groups of a living polygetadiene homopolymer with a microstructure of 91.0% of 1,2-vinyl bonds and 9.0% of 1.4-) u/su bonds with an organic peroxide. 140 parts of tert-butanol and 40 parts of Ebomino 5p-oo6 (described above) were added to 100 parts of the epoxidized polybutadiene (N-880-FB, BF-1000, oxirane oxygen 8.0 g) obtained by this process. The mixture was charged into a reaction vessel, and the temperature was raised while stirring, and stirring was continued for 1 hour at 10°C. Next, 5 parts of 5% water-soluble cobalt naphthenate, 10 parts of 10% hydrium persulfate aqueous solution, and 80 parts of ethanol.
Add 325 parts of water and stir well to obtain a uniform resin content of 20 parts.
% dispersion (V) was obtained. This dispersion was stable on storage for more than 6 months.

Comparative Example 1 As a comparative example, the following dispersion was obtained according to Example 1 of Japanese Patent Publication No. 53-39471.

mxsso -FB, c -10oo (mentioned above)
To 100 parts, tert-butanol (3) parts was added and heated to 50° C. with stirring to obtain a homogeneous solution. Next, the obtained homogeneous solution was subjected to step 1? 76 parts of Miy P-1000 (30% aqueous solution of polyethyleneimine manufactured by Nippon Shokubai Chemical Co., Ltd., molecular weight 70,000) was added dropwise over about 30 minutes, further heated and stirred in i'OU for 3 hours until a yellowish brown color was obtained. A clear and viscous reaction mixture was obtained.

The resulting reaction mixture was then cooled to room temperature and added 5%
Aqueous ratio: 7 parts of cobalt naphthenate, 10 parts of a 10% potassium persulfate aqueous solution, and 382 parts of a mixed solution of water and methanol (8υ: weight ratio) were gradually added dropwise with stirring to form a uniform dispersion with a resin content of 20%. (■) was obtained.

This dispersion formed a precipitate after one month and was unstable.

Comparative Example 2 As a comparative example of a normal water-based anchor coating agent (polyethyleneimine), Epomino p-1ooo (mentioned above) was diluted with a mixture of water and methanol (50:50 heavy needle ratio) to give a resin content of 1 tsp. diluted anchor coating solution (applied to A-P')
I got it.

Examples 1 to 5 and Comparative Example 1 obtained as above
Dispersions (1) to (vl) of water and methanol (50:
Anchor coating solutions (A-1) to (A-VW) were prepared by diluting and dispersing the mixture to a resin content of 1%.

Next, the diluted dispersion stability of these anchor coating solutions was visually observed over time, and the results are shown in Table 1.

Table 1 Also, the anchor coating solution prepared above (A-1
) to (A-W) and the anchor coat solution (A-PE process) obtained in Comparative Example 2, lamination speed was 80 m/min, melt extrusion resin temperature was 310° C.1 using an in-line melt extrusion laminating machine. Anchor coat liquid application amount 0.05~
0.06 f/n? A composite film was prepared by melt-extrusion laminating polyester film with polyethylene in a bath under the conditions of (resin content), and each composite film was
The normal adhesive strength and water-resistant adhesive strength of the lum were measured using an Instron type tester, and the results are shown in Table 2.

Anchor coat 1 (A-1), (AV), (A-
Vl) and the anchor coating liquid obtained in Comparative Example 2 (A
- PE process) using an in-line melt extrusion laminating machine at a lamination speed of 80 m/min, melt extrusion resin temperature of 300°C, and anchor coating liquid coating amount of 0.04 to 0.0.
Composite films were produced by melt-extrusion laminating polyethylene on the various base materials shown in Table 3 under the conditions of 5 t/door (resin content), and the normal adhesive strength and moisture-resistant adhesive strength of each of the obtained composite films were determined. It was measured using an Instron type tester, and the results are shown in Table 3.

Claims (1)

[Claims] 1. An aqueous anchor coating agent containing a mixture of a conjugated diene polymer and an aliphatic polyamine having a molecular weight of io, ooo or less, or a mixed reaction product thereof as a main component.