JPS62112673A - Aqueous lustrous composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention provides black heel mark resistance, scuff resistance,
This invention relates to an aqueous glossy composition with excellent abrasion resistance and adhesion. More specifically, the present invention relates to an aqueous glossy composition comprising a specific copolymer emulsion and a terpolymer having a specific structure and having an ethylene-(meth)acrylic acid-(meth)acrylic acid alkyl ester as a constituent unit.

[Conventional technology]

Conventional aqueous gloss compositions are mainly composed of (a) copolymer emulsions such as water-insoluble polymer emulsions such as rubber emulsions, (b) waxes, and (c) alkali-soluble resins. In addition, it contains (d) a wetting, emulsifying and dispersing agent, (e) a polyvalent metal compound, and (f) water.

Among these, natural or synthetic waxes are used as (b) wax, such as beeswax, carnauba wax,
Candelilla wax, polyethylene wax, polypropylene wax, paraffin wax, etc. are emulsified and dispersed with an ionic or nonionic emulsifier.

The role of such wax is to alleviate the impact given to the paint film and provide self-repair properties for scratches.
Aqueous gloss compositions using these waxes have insufficient black heel mark resistance, scuff resistance, and abrasion resistance (
, it is no longer possible to meet recent required characteristics.

(Problems to be Solved by the Invention) As a result of intensive studies in view of the problems of the prior art, the present inventors have discovered that ethylene-(meth) having a specific copolymer emulsion and a specific copolymer composition It has been discovered that an aqueous glossy composition containing acrylic acid and a terpolymer having a (meth)acrylic acid alkyl ester as a constituent unit has excellent black heel mark resistance, scuff resistance, and abrasion resistance. , the present invention has been achieved.

[Means for solving problems]

That is, in the present invention, (a) the glass transition temperature of the copolymer is 11
A copolymer emulsion having a temperature of 0 to +80°C, and (
(b) (a) ethylene obtained by thermally degrading a relatively high molecular weight ethylene-alkyl (meth)acrylate copolymer;
(b) (meth)acrylic acid and (c) (meth)acrylic acid alkyl ester as constituent units, and (a) component is 8
0 to 98 mol%, component (b) 0.2 to 5 mol%, (c
) component is 1.8 to 15 mol%, viscosity average molecular weight is 3.0
The present invention provides an aqueous gloss composition characterized by containing a low molecular weight terpolymer having a molecular weight of 00 to 20,000.

First, to explain the copolymer emulsion (a) used in the present invention, the glass transition temperature of the copolymer constituting the emulsion must be -10 to +80°C, preferably +15 to +65°C. It is. Such a copolymer emulsion forms a continuous film that protects the floor surface and maintains its aesthetic appearance, and also functions as a binder for other ingredients.

(a) If the glass transition temperature of the copolymer constituting the copolymer emulsion is less than 110°C, the coating film of the resulting composition will be soft and have good black heel mark resistance, scuff resistance, abrasion resistance, Stain resistance worsens, while +80
If the temperature exceeds ℃, the coating film becomes brittle and powdering is likely to occur.

The copolymer emulsion (a) used in the present invention has a glass transition temperature in the range of -110 to +80°C, such as acrylic emulsion, urethane emulsion, styrene-butadiene emulsion, acrylonitrile-butadiene emulsion, etc. emulsion, chloroprene emulsion, vinyl chloride emulsion, vinylidene chloride emulsion, vinyl acetate emulsion,
Examples include ethylene-vinyl acetate emulsion,
Preferred are acrylic emulsions and urethane emulsions.

Specifically, examples of acrylic emulsions include (
Methyl acrylate, ethyl (meth)acrylate,
Butyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)
Monomers that can be copolymerized alone or with (meth)acrylic esters such as lauryl acrylate and stearyl (meth)acrylate; for example, ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, and itaconic acid. Carboxylic acids, such as styrene, aromatic vinyl compounds such as α-methylstyrene, (meth)acrylonitrile, (meth)
Acrylamide, 2-hydroxyethyl acrylate, N
- emulsions of copolymers with monomers such as methylolacrylamide and divinylbenzene. Preferred are emulsions of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, etc. alone or copolymers with acrylic acid, methacrylic acid, itaconic acid, styrene, acrylonitrile, etc.

These (a) copolymer emulsions are appropriately selected from copolymers constituting the emulsion whose glass transition temperature is within the above range.

Further, these (a) copolymer emulsions usually have a solid content concentration of 25 to 70% by weight, preferably 30 to 55% by weight.

Next, the low molecular weight terpolymer used in the present invention corresponds to the wax component conventionally used, and when the resulting composition is applied to a floor surface, it The flow of particles has the effect of softening the transmission of mechanical shock and friction to the floor surface, and at the same time, the particles have the effect of filling in scratches and damaged areas on the film surface by puffing, making the surface smooth. It has the effect of imparting gloss and durability.

In the low molecular weight terpolymer used in the present invention, the (meth)acrylic acid serving as a constituent unit of the terpolymer is acrylic acid and/or methacrylic acid,
In addition, (meth)acrylic acid alkyl esters include methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, 1-propyl acrylate, 1-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 1-butyl acrylate, 1-butyl methacrylate, acrylic acid - has at least one alkyl group having 1 to 4 carbon atoms selected from -butyl, t-butyl methacrylate, etc. (meth)
It is an alkyl ester of acrylic acid.

In such a low molecular weight terpolymer, the above f
The ratio of the three components a), (b), and (c) is important.

(a) Component ethylene unit is 80 to 98 mol%,
Preferably it is 85 to 96 mol%, and component (b) (meth)acrylic acid is 0.2 to 5 mol%, preferably 0.
．． (meth)acrylic acid alkyl ester, which is the c1 component, is 1.8 to 15 mol%, preferably 3.7 to 11 mol%.

The low molecular weight terpolymer used in the present invention has the characteristic of producing a high-quality emulsion without using an emulsifier, but the ethylene content of component (a) is 80 mol%.
If it is less than 98 mol %, the physical properties of the coating film of an aqueous glossy composition using the emulsion will be poor, while if it exceeds 98 mol %, it will be difficult to form an emulsion.

If the amount of the component is less than the above range, the resulting copolymer will have too few carboxyl groups, making it difficult to form an emulsion, while if it is too much than the above range, the water solubility will be too strong and a good quality emulsion will not be obtained. , both are unfavorable.

In addition, due to the presence of component (c), especially (component c1 is 3.
A low molecular weight terpolymer in the range of 7 to 11 mol% is preferable because it can provide an emulsion with a lower viscosity and a higher concentration than an ethylene-acrylic acid copolymer. Moreover, the film obtained from the emulsion is less likely to crack, and as a result provides good black heel mark resistance, scuff resistance, and abrasion resistance, which is preferable.

Furthermore, the viscosity average molecular weight of the low molecular weight terpolymer used in the present invention is 3.000 to 20,000, preferably 6.
．． The range is from 000 to 15,000. If the viscosity average molecular weight is less than 3,000, the resulting aqueous gloss composition will have poor coating film performance such as scuff resistance and abrasion resistance;
,000, it is difficult to obtain a stable and uniform emulsion, and, for example, the particle size of the emulsion becomes non-uniform, which deteriorates the physical properties of the resulting composition.

In particular, a low molecular weight terpolymer having a viscosity average molecular weight of 6,000 or more is preferred because it significantly improves the black heel mark resistance of the coating film.

In addition, the viscosity average molecular weight of the low molecular weight terpolymer is:
This is a value determined from the intrinsic viscosity [η] in a decalin solvent at 135°C using the following formula.

(77) =KM"(K=14.3xlO-' (
d! /g), α=0.82) Such a low molecular weight terpolymer is produced by thermal degradation from a copolymer of a touge component and a component (c).

That is, the desired low molecular weight terpolymer can be obtained by heating a relatively high molecular weight ethylene-(meth)acrylic acid alkyl ester copolymer in the presence of water in an inert atmosphere. can. The relatively high molecular weight ethylene-(meth)acrylic acid alkyl ester copolymer used as the raw material here is obtained by known high-pressure radical copolymerization.

The melt flow index (M, 1.
) is approximately 300 g/10 minutes or less, and the content of (meth)acrylic acid alkyl ester is the content of components (b) and (c) that should be contained in the target low molecular weight terpolymer. It is determined in accordance with the above, but it is 2 to 25 mol%, preferably 4 to 20 mol%. A preferred copolymer as a raw material is an ethylene-ethyl acrylate copolymer.

By performing the thermal degradation reaction in an inert atmosphere, the oxidation reaction can be suppressed and coloration of the product can be prevented. There are no particular restrictions on the method for achieving an inert atmosphere, but a method using an inert gas atmosphere such as nitrogen, carbon dioxide, argon, or helium, a method using a water vapor atmosphere derived from water present in the reaction system, or a combination thereof. is preferred.

At this time, if necessary, the copolymer, which is a relatively high molecular weight raw material to be supplied to the reaction system, may be degassed in a reduced pressure region, or the oxygen dissolved in the water may be removed in advance.

The presence of water during heat degradation is necessary to generate (meth)acrylic acid units by hydrolysis of (meth)acrylic acid alkyl ester during heat degradation. The water present in the reaction system is preferably in a liquid phase, a gas phase (steam), or a mixture thereof.

The reaction temperature, pressure, and time during thermal degradation depend on the molecular weight and copolymer composition of the raw material copolymer, the amount of water, the molecular weight of the desired low molecular weight terpolymer, and the (bl, (c) components). The reaction temperature is determined as appropriate depending on the content ratio of
0 to 500°C, preferably 250 to 400°C, reaction pressure 5 to 500 kg/a+f, preferably 10 to 470
kg/cj, reaction time is 1 to 10 hours, preferably 2 to
5 hours, and the oxygen concentration in the reaction system is preferably 5 hours.
It is preferable to keep the amount at most ppm, more preferably at most 3 ppm.

Such a thermal degradation method is industrially extremely simple compared to methods using oxidation reactions or graft reactions, or methods for producing low molecular weight ternary copolymers by direct polymerization from seven polymers. It is superior in terms of manufacturing cost, molecular weight and composition control of the target product.

Note that when the low molecular weight terpolymer used in the present invention is used together with a copolymer emulsion described below to form an aqueous gloss composition, the terpolymer is usually emulsified in advance and used. .

Here, emulsification of the low molecular weight terpolymer is carried out by mixing the copolymer, a dispersant such as an alkali metal compound, an alkaline earth metal compound, an inorganic basic compound or an organic basic compound, and water in an autoclave. 100~200℃
, preferably by stirring at a temperature in the range of 120 to 170°C.

Specific examples of the dispersant include lithium hydroxide, potassium hydroxide, sodium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, strontium hydroxide, lithium oxide, potassium oxide, sodium oxide, calcium oxide, and Magnesium, strontium oxide, barium oxide, potassium carbonate, sodium carbonate, calcium carbonate, magnesium carbonate, potassium bicarbonate, sodium bicarbonate, calcium bicarbonate, magnesium bicarbonate, sodium formate, potassium formate, sodium acetate, sodium propionate, acetic acid. zinc, magnesium acetate,
Inorganic basic compounds such as ammonium hydroxide and ammonia; monoalkylamines such as methylamine, ethylamine and propylamine; secondary and tertiary amines such as dimethylamine, diethylamine, trimethylamine and triethylamine; ethanolamine; 1-
monoalkanolamines, such as propatoolamines,
Included are polyalkanolamines such as dimethylethanolamine, monocycloalkylamines such as cyclohexylamine, and monocycloalkanolamines such as cyclohexanolamine. Furthermore, morpholine, pyridine, etc. are also suitably used as dispersants.

With the dispersant, the low molecular weight terpolymer used in the present invention can be easily emulsified, but
Emulsification can be made more easily by adding an organic acid such as oleic acid.

The solid content concentration of the low molecular weight terpolymer emulsion can be adjusted in the range of 5 to 50% by weight, preferably 20 to 40% by weight, and the emulsion obtained thereby is stable, but even more stable. In addition to surfactants such as nonionic surfactants and anionic surfactants, we use additives such as antifungal agents, ultraviolet absorbers, heat stabilizers, antifreeze agents, antifoaming agents, and crosslinking agents. may be included within a range that does not impair the purpose of the present invention.

Furthermore, in the low molecular weight terpolymer component of the present invention, the conventionally used waxes may be used in combination in an amount of 70% by weight or less, preferably 30 parts by weight or less, of the terpolymer component. You can also.

The ratio of the above (a) copolymer emulsion and (b) low molecular weight terpolymer is (a) copolymer emulsion 1
Preferably (b) 5 to 40 parts by weight of the low molecular weight terpolymer, more preferably 8 parts by weight per 00 parts by weight (in terms of solid content).
(b) If the low molecular weight copolymer is less than 5 parts by weight, it will not be possible to alleviate external impact and frictional force when the resulting composition is applied to a floor surface, resulting in poor black heel mark resistance, Scatter resistance is poor, while <<.

If the amount exceeds 1 part by weight, the abrasion resistance and gloss of the coating film will be poor, and the appearance will be impaired.

Further, when the (copolymer emulsion and (b) low molecular weight terpolymer of the present invention are used in an aqueous gloss composition, the total solid content concentration of both is usually 10 to 6 oM. %, preferably 20 to 50% by weight.

The aqueous gloss composition of the present invention contains (a copolymer emulsion) and (b) a low molecular weight terpolymer as described above, and further contains (c) an alkali-soluble resin and (d) a moisturizing agent. , an emulsifying and dispersing agent, (e) a polyvalent metal compound, etc. The specific composition in this case is, for example, as follows.

(a) Copolymer emulsion; 100 parts by weight (in terms of solid content) (b) Low molecular weight terpolymer; 5 to 40 parts by weight, preferably 8 to 30 parts by weight (c) Alkali-soluble resin; 0 to 30 parts by weight 50 parts by weight, preferably 5 to 15 parts by weight (d) Wetting, emulsifying and dispersing agent; (a) + (b) + (
c) 0.05 to 20% by weight, preferably 0.05% to 20% by weight of c). 1-I
(e) Polyvalent metal compound; 0.01 to 10 parts by weight, preferably 0.05 to 8 parts by weight; (f) Water; total solids content of 8 to 50 parts by weight; or 10
Amount of ~35% by weight Here, (c) the alkali-soluble resin has the effect of improving the leveling of the polish and improving the releasability, and such resins include, for example, styrene-maleic acid copolymer resin, Examples include shellac and rosin-modified maleic acid resin.

In addition, (d) wetting, emulsifying and dispersing agents are used to improve the dispersion stability of the aqueous gloss composition obtained and the adhesion of the composition to the floor surface. Mention may be made of alkali metal and amine salts of fatty acids, such as sodium, potassium, ammonium or morpholine oleates or polysylates, as well as the customary nonionic surfactants.

Furthermore, (e) polyvalent metal compounds include oxides and salts of zinc, zirconium, magnesium, copper, iron, cobalt, nickel, aluminum, cadmium, etc., such as carbonic acid, acetic acid, formic acid, glutaric acid, benzoic acid, and oxalic acid. or dissolve an aqueous solution of these acids and a polyvalent metal salt to a pH of 7 to 11 with ammonia, amine, etc.
It can be easily obtained by adjusting the metal ions, and metal ion forms can also be included. Preferred polyvalent metal compounds are oxides or salts of zinc and zirconium.

The amines capable of forming a complex include morpholine, monoethanolamine, ethylenediamine, and diethylaminoethanol.

When such a polyvalent metal compound is added to the composition of the present invention, a tough coating film can be obtained due to the crosslinking effect, and good black heel mark resistance, scuff resistance, and abrasion resistance can be obtained, so it is preferable.

In addition, the aqueous gloss composition of the present invention contains leveling agents such as tributoxyphosphate, polyalnyls, and fluorosurfactants; diethylene glycol, isophorone, benzyl alcohol, and monoethyl or monomethyl 3-methoxybutanol-1. Temporary plasticizers such as ether and permanent plasticizers such as benzyl butyl phthalate, dibutyl phthalate, dimethyl phthalate, triphenyl phosphate; antifoaming agents; film forming aids such as calpitol; used in ordinary paints such as pigments. Additives can be added.

The amount of these additives used is 100 parts by weight or less, preferably 50 parts by weight or less, based on 100 parts by weight (in terms of solid content) of the copolymer emulsion (a).

When preparing the aqueous gloss composition of the present invention, (a)
The copolymer emulsion and (b) low molecular weight ternary copolymer can be mixed in any order, but for example, the copolymer emulsion is first placed in a mixing container, and then water, polyvalent metal compounds, and alkali-soluble compounds are mixed while stirring. resin, wetting agent,
It can be easily prepared by a method such as slowly adding a leveling agent and a plasticizer in sequence, and finally adding a low molecular weight terpolymer.

The aqueous gloss composition thus obtained has good dispersibility and good storage stability at room temperature, and such a composition can be quickly applied to a floor surface by wiping, brushing, or raging in a conventional manner. When dried, it is possible to form a transparent film, and if it contains a pigment, it can form a strong, colored film.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, the evaluation of the physical properties of the coating film in the examples is as follows.

(1) Black heel mark resistance After applying the aqueous gloss composition twice with a brush onto the vinyl chloride tile, it was dried for 24 hours, and then subjected to a black heel mark tester (60 rpm for 10 minutes) to evaluate the appearance of black heel marks.

■Those with no black heel at all ○Those with almost no black heel △Those with a slight black heel remaining on the tile ×Those with a noticeable black heel remaining on the tile (2) Water-based gloss composition on scatting-resistant PVC tile After applying the product twice with a brush, it was dried for 24 hours, applied to a black heel marl tester (60 rpm x lO minutes), and evaluated for scuffing.

◎No scuff at all ○Almost no scuff △Some scuff remains on the tile × Significant scuff remains on the tile (3) Brush aqueous gloss composition onto wear-resistant vinyl chloride tiles After applying it twice, it was dried for 24 hours and rubbed with a nylon band to determine the state of surface wear.

◎Almost no scratches and no loss of gloss.

OAlmost no scratches, but the gloss is slightly reduced.

6. Scratches on the surface are noticeable and the gloss is reduced.

×Significant scratches on the surface are noticeable, and the gloss is significantly reduced.

(4) Glass transition temperature After producing an emulsion film by the casting method, it was measured using a differential thermal analyzer manufactured by DuPont.

Reference example (preparation of low molecular weight terpolymer emulsion) Ethylene-ethyl acrylate copolymer (hereinafter simply referred to as E-EA) [ethyl acrylate (EA) content: 7.5 mol%,
Viscosity average molecular weight; 36.000) 1.5 kg was added to 1.5 kg of water.
Placed together with OOOmA in an autoclave with an internal volume of 3゜81, under nitrogen atmosphere, temperature 360℃, pressure 200k.
Heat degraded at g/- for 4 hours, viscosity average molecular weight 5,300,
A low molecular weight ethylene (ET)-acrylic acid (AA)-ethyl acrylate (EA) terpolymer with an acrylic acid (AA) content of 3.2 mol% and an ethyl acrylate content of 3.0 mol% was obtained. .

400 g of this copolymer was taken out and placed in an autoclave with an internal volume of 51 cm, containing 600 g of water and sodium hydroxide (NaOH).
) and stirred at 150° C. for 5 hours to form an emulsion. This sample is designated as 8-1.

For the low molecular weight terpolymer emulsions A-2 to A-11, the raw material ethylene-ethyl acrylate copolymer shown in Table 1 was used, and thermal degradation conditions such as pressure and temperature were changed. Certain low molecular weight terpolymers as shown in Table 1 were prepared.

A predetermined amount of each of the above low molecular weight ternary copolymers was taken out, and predetermined amounts of sodium hydroxide (N a OH), 25% by weight ammonia water (25% NH3 water), and dimethylethanolamine were used as dispersion media. These low molecular weight terpolymers were emulsified in the same manner as in Example 1, and the results are also shown in Table 1.

A-12 was thermally degraded and emulsified in the same manner as A-5 using an ethylene-ethyl methacrylate copolymer (hereinafter referred to as E-EMA) as a raw material, and the results were
Shown in the table.

A-13 uses the autoclave of A-1 to charge 1,760 g of ethylene and 160 g of acrylic acid at a pressure of 1
, 660 kg/cal, temperature 170 ° C., polymerization time 2 hours, radical polymerization was carried out to prepare the low molecular weight ethylene-acrylic acid binary copolymer shown in Table 1, and it was emulsified in the same manner as A-1. , shown in Table 1.

A-14 uses the autoclave of A-1 to charge 1,710 g of ethylene and 120 g of ethyl acrylate at a pressure of 1,600 kg/cd, a temperature of 170°C, and a polymerization time of 1.
A low molecular weight ethylene-ethyl acrylate copolymer shown in Table 1 was prepared by radical polymerization for a period of time, and emulsified in the same manner as A-1.

*1) Dimethylethanolamine *2) AC-392, manufactured by Allied Chemical Co., USA *3)
Manufactured by Allied Chemical Co., USA, AC-540 Examples - 11
and Comparative Examples 1 to 10 Put the (a) copolymer emulsion shown in Table 2 in a glass container, and further add 500 parts by weight of water and components other than the (a) copolymer emulsion shown in the formulation in Table 2. That is, add the low molecular weight terpolymer emulsion shown in the above reference example and other additives, and stir with a stirrer for 3 minutes.
The mixture was stirred for 0 minutes to obtain an aqueous gloss composition.

Next, using the obtained aqueous gloss composition, the physical properties of the coating film,
That is, blank heel mark resistance, scuff resistance, and abrasion resistance were evaluated. The results are shown in Table 2.
(The following is a blank space) As is clear from Table 2, Examples 1 to 11 are aqueous gloss compositions within the scope of the present invention, and are found to have the physical properties of the coating film targeted by the present invention.

On the other hand, in Comparative Example 1, the viscosity average molecular weight of the low molecular weight terpolymer was less than 3,000, so the coating film was soft and poor in black heel mark resistance, scuff resistance, and abrasion resistance. The terpolymer has a viscosity average molecular weight of 20
In Comparative Example 2 in which the number exceeds .000, the coating film becomes brittle and has poor abrasion resistance.

In Comparative Example 3, the ethylene content of the low molecular weight terpolymer was 8
This is a case where the amount is less than 0 mol%, and the physical properties of the coating film such as blank heel mark resistance are poor. Furthermore, in Comparative Example 4 in which the ethylene content of the low molecular weight terpolymer exceeds 98 mol%, it is difficult to form an emulsion and the physical properties of the coating film are poor.

Comparative Examples 5 and 6 each contain a binary copolymer of ethylene-acrylic acid or ethylene-ethyl acrylate as the (b) component, and the resulting compositions have high emulsion viscosity and are difficult to coat. The suitability is poor, and the coating film cracks, resulting in poor scuff resistance and blank heel mark resistance. In Comparative Examples 7 and 8, a commercially available polyethylene wax was used as the component (b), and it can be seen that the coating film strength was low and the scuff resistance and abrasion resistance were poor. In Comparative Examples 9 and 10, the glass transition temperature of the copolymer emulsion (acrylic copolymer) was 120
℃, +95℃, and it can be seen that the physical properties of the resulting coating film are not good.

〔Effect of the invention〕

The aqueous gloss composition of the present invention has a much better balance of physical properties such as black heel mark resistance, scuff resistance, and abrasion resistance than conventional ones, and can meet the strict quality demands of recent years. can provide things.

Claims (4)

[Claims] (1) (a) The glass transition temperature of the copolymer is -10 to +8
(a) ethylene, (b) (b) obtained by thermally degrading a copolymer emulsion at 0°C and (b) a relatively high molecular weight ethylene-alkyl (meth)acrylate copolymer.
The structural units are meth)acrylic acid and (c)(meth)acrylic acid alkyl ester, and the component (a) is 80 to 98%.
mol%, component (b) is 0.2 to 5 mol% and component (c) is 1.8 to 15 mol%, viscosity average molecular weight is 3,000
1. An aqueous gloss composition comprising a low molecular weight terpolymer having a molecular weight of 20,000 to 20,000. (2) Component (b) of the low molecular weight terpolymer is 0.3 to 4
The aqueous gloss composition according to claim 1, wherein the component (c) is 3.7 to 11 mol %. (3) The viscosity average molecular weight of the low molecular weight terpolymer is 6.0
00 to 15,000, the aqueous gloss composition according to claim 1 or 2. (4) The low molecular weight terpolymer is ethylene-acrylic acid-
The aqueous gloss composition according to claim 1, 2 or 3, which is an ethyl acrylate copolymer.