JPS58183746A - Aqueous emulsion resin composition - Google Patents

Abstract

PURPOSE:To prepare the titled composition useful as a coating agent having excellent dispersion stability, abrasion resistance, slipperiness, etc., by mixing a specific neutralized urethane polymer as an emulsifier with a vinyl chloride/ vinyl acetate copolymer or vinyl chloride/vinyl acetate/vinyl alcohol terpolymer. CONSTITUTION:The objective composition is prepared by mixing (A) a dispersing agent comprising a neutralized urethane polymer having a group selected from carboxyl group, sulfone group and amino group with (B) a vinyl chloride/vinyl acetate copolymer or a vinyl chloride/vinyl acetate/vinyl alcohol copolymer at a weight ratio (A:B) of preferably 1:(0.2-3). For example, the urethane polymer is synthesized in the presence of a solvent which dissolves both components (A) and (B), and the component (B) is added and dissolved in the solution. An aqueous solution of a base or an acid is added to the solution in an amount to neutralize the carboxyl group, etc., and the solvent is evaporated under reduced pressure to obtain a solid content of e.g. about 25%. The composition is preferably introduced with unsaturated double bond, and crosslinked and cured by irradiation with ionizing radiation after coating.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an aqueous emulsion type resin composition with excellent dispersion stability, which is formed by mixing different types of resins.

For more details on the history, when dispersing vinyl chloride/vinyl acetate copolymer or vinyl chloride/vinyl acetate/vinyl alcohol copolymer in water, a water-soluble or water-dispersible urethane polymer is used as a dispersant, and various physical properties are used. Concerning an excellent aqueous emulsion type resin composition. Conventionally, polyurethane emulsion, acrylic emulsion, etc. have been known as aqueous resins, and have been used in paints, printing inks, adhesives, etc. On the other hand, emulsion: +7 of vinyl chloride/vinyl acetate copolymer or vinyl chloride/vinyl acetate/vinyl alcohol copolymer is also known, but it is known that it can be produced by emulsion polymerization from monomers in water. It is being

Polyurethane emulsion has good wear resistance, but
Pigment dispersibility and slipperiness are problematic; acrylic emulsions have good pigment dispersibility and slipperiness, but
On the other hand, vinyl chloride/vinyl acetate copolymer or vinyl chloride/vinyl acetate/vinyl alcohol copolymer has good emulsion lubricating properties and pigment dispersibility, but the strength of the coating film is poor. Moreover, although a single resin emulsion has excellent dispersion stability, it is difficult to necessarily satisfy the required physical properties. Attempts have been made to create more than 61 types of emulsions. However, such mixing is difficult due to differences in the stabilizing pH depending on whether the anionic or cationic type is used.
It was easy.

In addition, as an attempt to improve the drawbacks of polyurethane emulsions, methods to extend C'+7rtk, such as amine extension in water and crosslinking with shrimp chlorhydride, are being considered; It is difficult to apply these methods when there are resins.

The purpose of the present invention is to have excellent dispersion stability, corrosion resistance 1≠corrosion resistance,
Provides an aqueous emulsion-type resin composition with excellent physical properties such as pigment dispersibility and slipperiness, and furthermore, provides coating films and films obtained from the aqueous emulsion-type resin composition.
The present invention also provides a composition that can be cured by radiation irradiation and can bond resins together more firmly.

That is, a neutralized urethane polymer having one or more of one selected from carboxyl groups, sulfone groups, and amine groups, and vinyl chloride/vinyl acetate copolymer or vinyl chloride/vinyl acetate/vinyl alcohol copolymer. It is an aqueous emulsion type resin composition containing ichigoitai tok.

A neutralized urethane polymer having one or more of one selected from carboxyl groups, sulfone groups, and amino groups is used as a dispersant, and vinyl chloride/vinyl acetate copolymer or vinyl chloride/vinyl acetate copolymer is used as a dispersant. /An aqueous emulsion type resin composition in which a vinyl alcohol copolymer is dispersed. In order to form an even stronger coating film, it is preferable that all unsaturated double bonds be introduced into the aqueous emulsion type resin composition of the present invention, and after the coating film is formed, it is crosslinked and cured by irradiation with radiation. The urethane polymer used in the present invention and either vinyl chloride/vinyl acetate copolymer, vinyl chloride/vinyl acetate, vinyl alcohol copolymer, or both are unsaturated and polymerizable by radiation irradiation. If a double bond is introduced,
An even stronger coating or film is formed.

The urethane polymer has a carboxyl group, sulfone group, or amine group introduced into the side chain or both ends, and the dispersion stability of the emulsion can be improved by introducing these functional groups. Carboxyl groups, sulfo/amine groups, and amine groups can be introduced into the urethane polymer by conventionally known methods. One example is a method in which a glycol in which one hydroxyl group of a trifunctional alcohol is esterified with a carboxylic acid such as maleic anhydride is used as an extender; 2.2
'-dimethylolpropionic acid as an extender, amine extension and reaction with sultones such as 1,3-propane sultone, terminal amine group, hydroxyl group such as lactic acid and carboxyl group. A method is available in which a compound having both groups is reacted with a trifunctional ino/anate and a compound having two isombu-F groups is used.

These functional groups should usually be designed to have an acid value or alkali value of about 10 to 150.

In the case of the aqueous emulsion type resin composition of the present invention, the polyvinyl chloride/vinyl acetate copolymer or the vinyl chloride/vinyl alcohol copolymer is used. When dispersing, it is in a neutralized state with a neutralizing agent. As a neutralizing agent, anomonia, (seven-no, g, tri) methylamine,
(7) -, di, tri)ethylamine, (mono, di, tri) ethanolamine, morpholine, sodium hydroxide, potassium hydroxide, etc., and acetic acid, propic acid, etc. are used for amine groups. be done.

1. The resin composition of the present invention can be cured by radiation such as ultraviolet rays or electron beams by bonding unsaturated double bonds to the main chain, side chains, or both ends of the skeleton as the urethane polymer according to the present invention. 1. The resulting coating film or film can have better rt.

The unsaturated double bond in the present invention refers to a double bond having radical polymerizability, and includes an acrylic double bond such as acrylic acid, meccrylic acid or an ester compound thereof,
Allyl type double bonds such as diallyl phthalate, vinyl ether, vinyl ester type double bonds, unsaturated double bonds such as maleic acid, maleic acid derivatives, unsaturated double bonds such as cinnamic acid, cinnamate esters, etc. Examples include bonds.

Further, as an example of a method for introducing an unsaturated double bond into the urethane polymer, a part of cyinone anate or triinocyanate is mixed with a compound having both a hydroxyl group and a t-saturated double bond, such as 2-hydroquine ethyl methacrylate. An isocyanate compound reacted with a part of a trifunctional triol is used in the structure of the urethane polymer, or an isocyanate compound blocked with a compound having an unsaturated double bond and a hydroxyl group, and a terminal Examples include a method of reacting with a prepolymer of hydroxyl groups.

Various commercially available resins can be used as the vinyl chloride/vinyl acetate copolymer or the vinyl salt/if vinyl/vinyl alcohol copolymer. A method for introducing unsaturated double bonds into vinyl chloride/vinyl acetate copolymer or ld kW, vinyl chloride/vinyl acetate/vinyl alcohol copolymer is esterification with cinnamic acid using the hydroxyl group of vinyl alcohol. or bonding with diyne/anate blocked with 2-hydroquine ethyl methacrylate or the like.

The blending ratio of the urethane polymer and the vinyl chloride/vinyl acetate copolymer or the vinyl chloride/vinyl acetate/vinyl alcohol copolymer is preferably 02 to 3, more preferably 0.2 to 1 (solid content) of the urethane polymer. is 0
．． The weight ratio is between 5 and 2.

Although the method for producing the aqueous emulsion according to the present invention is not particularly limited, for example, using a raw material for a urethane polymer, a urethane polymer and a vinyl chloride/vinyl acetate copolymer or a vinyl chloride/vinyl acetate/vinyl After synthesis, vinyl chloride/vinyl acetate copolymer or vinyl chloride/vinyl acetate/vinyl alcohol copolymer is mixed and dissolved. Thereafter, a base or acid sufficient to neutralize the carboxyl groups and sulfon groups of the urethane polymer as well as the amino groups is removed under reduced pressure to obtain an aqueous emulsion.

This aqueous emulsion is extremely stable.

The details of the reason are unknown, but it is assumed that vinyl chloride/vinyl acetate copolymer or vinyl chloride/vinyl acetate/vinyl alcohol copolymer has poor hydrophilicity.
It is thought that it becomes entangled with the molecules of the highly hydrophilic urethane polymer, and some of the grooves bond with the urethane polymer through hydrogen bonds, allowing the urethane to act as a dispersant and stabilize it in water.

Points to note are that if the urethane polymer and the vinyl chloride/vinyl acetate copolymer or the vinyl chloride/vinyl acetate/vinyl alcohol copolymer are not compatible with each other in a solvent within 1 minute, the properties obtained will be: The problem is that the dispersion stability of L-Flu 75 type resin is not necessarily good. This move seems to support the above 41+ measurement.

If necessary, fillers such as organic pigments and inorganic pigments may be added to the aqueous emulsion type resin composition of the present invention. Further, other resins can be added as long as they do not impede the effects of the present invention. For example, if it is a pigment, it is blended in a weight ratio of -CO,001 to 10, preferably 0.05 to 6, per liter of resin solid content.

The aqueous emulsion type resin composition of the present invention is effective as a coating material for paints and the like. When used as a coating material, in order to obtain an even stronger coating film, it is applied to the substrate, then irradiated with radiation such as ultraviolet rays or electron beams to cause crosslinking, and the water is evaporated, or the coating is applied to the substrate. After drying the water from the holes, UV rays,
Crosslinking is achieved by irradiating radiation such as electron beams. Therefore, a sensitizer may be appropriately added to the aqueous emulsion type resin composition according to the present invention in order to increase the sensitivity to ultraviolet rays. Furthermore, although the aqueous emulsion type resin composition 3) according to the present invention is mainly used as a paint, the pigment may be dispersed during the preparation of the aqueous emulsion type resin composition or after the preparation. Also good.

The present invention will be explained below with reference to Examples and Comparative Examples. In the example “
"Parts" and "1%" refer to parts by weight and weight %.

Example 1 Add tolylene diinocyanate (hereinafter referred to as TDI) to a flask.
: Abbreviated as 1r 174 parts, heated to 70'b, 2
-Hydroxyethyl methacrylate-1- (hereinafter referred to as 2HEMA)
130 parts of the flask was added dropwise over a period of 30 minutes while stirring with a stir bar in the flask. After this, 70°C
This product was referred to as f(A).

In another flask, put a trifunctional polyol polypropylene polyol with a molecular weight of 100 (O-4 manufactured by Asahi Denka Co., Ltd.
77 parts of 001 and 584:16 of (A) were mixed, heated while stirring, and reacted at 7o0c for 2 hours. After that, it was cooled at 300C-i and Ti' l 51f) 0.6
One part of the white was also prepared from a bouquet of 700 (', 71') and reacted for 1 hour. 1,638 parts of PCL-208) were added dropwise over 1 hour with stirring.After reacting at 70°C for 2 hours, 388 parts of 2,2'-bis(hydroquinemethyl)-propionic acid was added, and 70 Ro1 reaction was carried out for 2 hours at °C. Then, 4388 parts of C1 methyl ethyl ketone (hereinafter abbreviated as MIK) was added to obtain a product (BI).

This (B) is a urethane polymer having both an unsaturated double bond and a carfoquinol group in its molecule.

Solid content is 50%.

Furthermore, in another flask, 210 parts of MEK, 74.6 parts of Vinylite VAGH (vinyl chloride/vinyl acetate/vinyl alcohol copolymer) manufactured by Unimets Carbide Co., Ltd.
A)′! ! -155 parts were charged and reacted at 700C for 3 hours to obtain a resin solution (this) with a solid content of 30%.

Add 100 parts of (13) and 1667 parts of (c) to another flask, mix thoroughly at room temperature, and add 3 parts of water.
An aqueous sodium hydroxide solution prepared by dissolving 13 parts of sodium hydroxide in 0.00 parts of sodium hydroxide was added dropwise over 1 hour while stirring vigorously. After that, reduce the pressure with Asubireta to remove MKKi,
A water-dispersed emulsion with a solid content of about 2590 was obtained.

Example 2 116.7 parts of MKK in a flask, vinylite ■A (]
After adding 50 parts of H and stirring thoroughly at room temperature to dissolve, add 100 parts of fzr (B) of Example 1 and stirring thoroughly at room temperature.
00 parts and 13 parts of sodium hydroxide) (L) was added dropwise over 1 hour while stirring vigorously.

After that, MEK was removed by reducing the pressure with an aspirator to obtain a water-dispersed emulsion with a solid content of about 25%.

Example 3 In Example 2, Vinylite V+' II It manufactured by Union Carbide was used instead of Vinylite VAGH.
(vinyl chloride/vinyl acetate copolymer), and in the same manner as in Example 2 except that a water-dispersed emulsion was obtained.

Example 4 A flask was charged with 174 parts of TDI, and 130 parts of IPA (referred to as IPA) was added dropwise to the flask over 30 minutes while stirring. Thereafter, the mixture was reacted at 70°C for 2 hours to obtain (D).

In another flask, add 77 parts of yVca-400'r and 584 parts of (D), raise the temperature while stirring, and heat to 700C for 2 hours.
Allowed time to react. After that, it was cooled to 30°C, and TnI (
5100.6 m was added, the temperature was raised to 70°C while stirring thoroughly, and the reaction was allowed to proceed for 1 hour.

Polyether polyol (PTG100 manufactured by Nippon Polyurethane Co., Ltd.) with a molecular weight of 830 while maintaining the temperature at 700C 1
59.9 parts were added dropwise over 1 hour while stirring.

After reacting at 70°C for 2 hours, 324 parts of 22'-bis(hydroquinomethyl)-furopiA/acid was added and the mixture was heated at 70°C.
React for 2 hours, add 395.9 g of LI EK,
Solid content: 5090 In another flask, add 210 parts of MEK,
Union Carbide Co., Ltd. VYEG (vinyl chloride/vinyl acetate/vinyl alcohol copolymer) (il-84,
2 parts and 58 parts of (D) were charged and reacted at 70°C for 3 hours to obtain a resin solution (F) with a solid content of 30%.

Add 100 parts of (E) and 1667 parts of (F) to another flask and stir well at room temperature to mix. 1 woman, 3 parts water.
00 parts of sodium hydroxide dissolved in 11 parts of sodium hydroxide) was stirred vigorously.

The mixture was added dropwise over an hour while stirring. Thereafter, MEK'i was removed by reducing the pressure with an aspirator to obtain a water-dispersed emulsion with a solid content of about 25%.

Example 5 A flask was charged with 1-400 parts of G-40 and 98 parts of maleic anhydride, and the reaction was allowed to proceed at 70°C for 3 hours. This release product was designated as (G).

In another flask, add 571 parts of G-400 and 134 parts of (A).
After reacting at 70°C for 2 hours while stirring, the mixture was cooled to 40°C, 745 parts of TDN was added, the temperature was raised to 70°C again, and the reaction was carried out at 70°C for 1 hour. While the temperature was maintained at 70°C, PCL-208 was added dropwise over 1 hour and reacted at 70°C for 2 hours.The temperature of the flask was cooled to 40°C, and 1066 parts of G'l In addition, the temperature was raised to 70°C, and the mixture was reacted at 70°C for 3 hours.

After the reaction, 100 parts of MBKi was added and thoroughly stirred to dissolve and mix, to obtain (H) with a solid content of 50%.

100 parts of ()() and 1667 parts of (C) were placed in another flask, stirred at room temperature, and then a sodium hydroxide aqueous solution prepared by dissolving 4 parts of sodium hydroxide in 300 parts of water was stirred vigorously for 1 hour. It dripped. Thereafter, M BKi was removed by reducing the pressure with an aspirator to obtain a water-dispersed emulsion with a solid content of about 25 g.

Example 116 A flask was charged with 60 parts of ethylenediamine and 122 parts of 1,3-propane sultone and reacted at 68°C for 2 hours to obtain (■).

In another flask, add 699 parts of G-400 and 531 parts of (A).
After reacting at 70°C for 2 hours, the mixture was cooled, 912 parts of TDI was added, the temperature was raised, and the reaction was carried out at 70°C for 1 hour. 148.5 parts of 11PCL-208 kept at 70°C was added dropwise over 1 hour, and after kernels were reacted at 70°C for 1 hour, 400 parts of MEKk was added, stirred, and cooled. While stirring further, 31.8 parts of (I) was added, and (J
) was obtained.

This (J) is a urethane polymer having a sulfone group and an unsaturated double bond. Solid content is 50%.

100 parts of (J) and 1667 parts of (C) were placed in separate flasks, and after stirring and mixing thoroughly at room temperature ((, 3 parts of water
A potassium hydroxide aqueous solution prepared by dissolving 122 parts of potassium hydroxide in 0.00 parts of the solution was added dropwise over 1 hour while stirring vigorously. Thereafter, MEK was removed by reducing the pressure with an aspirator to obtain a water-dispersed emulsion with a solid content of about 2,590.

Comparative Example 1 In the same manner as in Example 1, (B) of Example 1 was dispersed in water while being neutralized.

Comparative Example 2 745 parts of G-400 (566 parts of A) were charged in a flask, and after reacting at 70°C for 2 hours, it was cooled and TDI i 97
．． Two parts were added, the temperature was raised again, and the reaction was carried out at 70°C for 2 hours. Next, PToo was heated to 1545°C while keeping the temperature at 70°C.
After 1 hour of reaction, 17.3 parts of ethylene glycol was added dropwise, and 7 parts were reacted at 0°C for 2 hours. After the reaction was completed, 400 parts of MEK was added and dissolved.

This resin solution is a urethane polymer having a solids content of 50% and having unsaturated double bonds. Let this be (K).

In another flask, 100 parts of (K) and 166.7 parts of (C) were charged, and after thoroughly stirring and mixing, 300 parts of water was added dropwise over 1 hour while stirring vigorously.

In this product, water and resin separated immediately, and a stable emulsion could not be obtained.

Example 1.2.3.4.5 and Comparative Example 1 were coated on a tin plate using a 2 mil coater, and the water was evaporated by vacuum drying. It was irradiated with an electron beam of 5M rad using a beam irradiation device. Regarding the resulting coating film, the results listed in F were obtained.

In the table above, the gel fraction means that the coating film is immersed in MEK, +, +
Heating for 1 hour at the boiling point of E K, the extraction residue is o. In other words, it can be calculated as

Evaluation of r-stickiness was carried out by placing a 150g black veneer plate on top of the paint film.
16 When it is pulled at a speed of 10 an/s
).

Abrasion properties were measured by the weight loss per gh when rotated 500 times using a taper abrasion tester and expressed in mg.

Stability evaluation was expressed by the number of days after the resulting aqueous dispersion was left at room temperature and separated. * in the table indicates stability for 30 days or more. Example 2 was separated at 2F-1 and redispersed when stirred.

Claims (1)

[Claims] 1. A neutralized urethane polymer having one or more of one selected from carboxyl groups, sulfone groups, and amine groups, and a vinyl chloride/vinyl acetate copolymer or vinyl chloride/vinyl acetate copolymer. /vinyl alcohol copolymer. 2. Claim 1 in which the urethane polymer further has one or more unsaturated double bonds that polymerize upon radiation irradiation.
The aqueous emulsion type resin composition described in 2. 3 The vinyl chloride/vinyl acetate copolymer or the vinyl chloride/vinyl acetate/vinyl alcohol copolymer has one or more unsaturated double bonds that polymerize upon radiation irradiation, according to claim 1 or 2. Aqueous emulsion type resin composition. 4 Claims consisting of 1 part urethane polymer mixed with vinyl chloride/vinyl acetate copolymer or vinyl chloride/vinyl acetate/vinyl alcohol copolymer CI in a weight ratio of 0.2 to 3, preferably 05 to 2. The aqueous emulsion type resin composition according to any one of Items 1 to 3.