JPS63286471A - Luster composition for floor - Google Patents

Abstract

PURPOSE:To obtain the titled composition suitable for homogeneous tiles of vinyl chloride type or for dry care system, having excellent adhesivity, durability, dust resistance and proper gloss, by copolymerizing an amide monomer with an ethylene unsaturated carboxylic acid in a specific ratio. CONSTITUTION:The aimed high-quality composition which is obtained by polymerizing (A) 75-98wt.% monomer [e.g. one consisting of 20-95wt.% acrylic acid ester and/or methacrylic acid ester and 0-8wt.% styrene] with 2-25wt.% sum of (B) ethylenic unsaturated carboxylic acid and (C) acrylamide and/or methacrylamide in the ratio of the component B/C of 0.20/0.80-0.95/0.05 and has 20-80 deg.C glass transition temperature, 0.05-0.25mu average particle diameter range, 80,000-350,000 weight-average molecular weight and balanced resistance, adhesivity, dust resistance and gloss.

Description

Detailed Description of the Invention a [Field of Industrial Application] The present invention relates to a floor gloss composition that can be applied to various flooring materials and is made of a copolymer emulsion in which specific monomer components are copolymerized. It is something.

b [Prior art] Traditionally, vinyl asbestos tiles have been the mainstream flooring material, overwhelmingly more common than other tiles, and therefore most floor gloss compositions have been targeted at vinyl asbestos tiles. . However, the use of PVC homogeneous styles and cushioned floors is gradually increasing due to their soft feel when walking, fashionability, and luxury, and is expected to increase rapidly in the future. On the other hand, the number of labor-saving dry care systems for vinyl asbestos tiles is gradually increasing.

Conventional floor gloss compositions targeted at vinyl asbestos include PVC-based homogeneous styles made of different materials, cushions, N70A, and dry care systems (apply the floor gloss composition and when it gets dirty, puff it with a high-speed puff machine). The problem is that the adhesion, durability, and dust adhesion resistance required for maintenance methods such as cleaning the floor by cleaning the floor and applying a glossy floor composition by spraying at the same time are poor.

C [Problem that the invention seeks to solve] The present invention is the result of intensive research aimed at solving the above-mentioned drawbacks.

In preparing an emulsion copolymer for a floor gloss composition, an amide monomer and an ethylenically unsaturated caldic acid were copolymerized with other monomers in specific proportions. A copolymer emulsion with specific properties is used. A glossy floor composition containing this copolymer emulsion has a balance of adhesion, durability, and dust resistance, and provides a suitable level of gloss for use in PVC floor styles, cushion floors, dry care systems, etc. Find out what you have.

Based on this knowledge, we have completed the present invention.

d [Means for solving the problem] The present invention is based on the following (b) (c) copolymerizable with (a) monomer 75 to 98 wt'Ik% and (b) ethylenically unsaturated power/l. 2 to 25 times the total of /bonic acid and (C) acrylamide and/or methacrylamide! A copolymer containing IkcIb and monopolymerized, and the weight ratio of component (b) and component (e) [(b)/(c)) is 0.2.
070.80~0.9510.05. Glass transition temperature is 20~80℃, average particle size range is 0.05~0.25μ
, M weight average molecular weight is from go, ooo to 350.000.

The present invention will be explained in detail below.

(b) Examples of the ethylenically unsaturated carboxylic acid monomer include monocarboxylic acids such as acrylic acid and methacrylic acid;
Examples include dicarboxylic acids such as 7-maric acid, maleic acid, and itaconic acid, and among these, methacrylic acid and acrylic acid are particularly preferred. These (b) ethylenically unsaturated carboxylic acid monomers can be used alone or in combination of two or more.

Acrylamide and/or methacrylamide is used as component (c) of the present invention.

The copolymerizable monomers which are component (a) of the present invention include aromatic vinyl compounds such as Tetra, styrene, α-methylstyrene, vinyltoluene, and tsutaramethylstyrene; methyl diacrylate, ethyl acrylate, butyl acrylate; 2-ethylhexyl acrylate, methyl methacrylate, 2-
Alkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl acrylate and 2-hydroxyethyl methacrylate,! Tajien, iso! Aliphatic conjugated diene compounds such as lene, 2-chloro-1,3-butadiene, 1-ri-4-1,3-butadiene, acrylonitrile,
Vinyl cyanide compounds such as methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl methyl ethyl ketone,
Vinyl methyl ether, vinyl acetate, vinyl formate, allyl acetate, methalyl acetate, acrylamide, methacryland, N-methylolacrylamide,
Includes glycidyl acrylate, glycidyl methacrylate, etc.

These can be used alone or in combination of two or more.

The preferred monomer composition to achieve component (1) is (a
), (meth)acrylic acid alkyl ester is 60%
~100% by weight of other copolymerizable monomers (excluding component b) and component (c)) from 0 to 40% by weight.

The preferred number of carbon atoms in the alkyl group of the (meth)acrylic acid alkyl ester is 1 to 12.

Preferred other copolymerizable monomers are aromatic vinyl compounds and/or vinyl cyanide compounds. It is preferable to use this copolymer emulsion of component (a), since a more excellent floor gloss composition, which is the object of the present invention, can be obtained.

The amount of the (bl) component used in the present invention is 75 to 98% by weight, preferably 80 to 95% by weight, and the total amount of the (bl) component and (c) component is 2 to 25% by weight, preferably 5 to 20% by weight. t% Dekatsu (b) component/(C) component = 0.2-0.8-0.
9510.05 (weight ratio), preferably 0.4 to 0.6
~0.8510.15 (weight ratio). If the total amount of components (b) and (e) is less than 2% by weight, the desired effect of the present invention cannot be obtained, while if it exceeds 25% by weight, the water resistance of the floor gloss composition will decrease. So I don't like it.

Regarding the weight ratio of component (b)/component (C), if component (b) is less than 0.2, the adhesion of the floor gloss composition will be poor, while if it exceeds 0.95, the adhesion of the floor gloss composition will be poor. Poor water resistance, durability, and coatability.

In addition, in the present invention, (a) l (b) e ((
A preferred combination of components is 80 to 95% by weight of component (a), 3 to 13% by weight of component (b), and 2 to 7% by weight of component (e).

In addition, the composition of component (a) is 20 to 951% by weight of acrylic ester and/or methacrylic ester, 0 to 80% by weight of styrene, and 0 to 30% by weight of other monomers, and the proportion in the copolymer. is preferably 80 to 951i%.

Glass transition temperature of copolymer in copolymer emulsion (
Tg) is 20-80°C, preferably 25-70°C. When Tg is less than 20°C, the durability of the floor gloss composition,
Dust resistance is poor, and if 'rg exceeds 80°C, adhesion is poor. The Tg in the present invention is determined by calculation from the 'rg of the monomers constituting the copolymer and the composition ratio of each monomer.

The average particle diameter of the copolymer in the copolymer emulsion is 0.
．． 05~0.25 a, preferred, <&10.06~
If it is less than 0.05μ, the viscosity of the floor gloss composition will be high and the coating properties will be lowered, so it is preferable h0.If it exceeds 0.25μ, the coating film will be It is not preferred because it does not easily cause clouding and has poor adhesion, durability, water resistance, film-forming properties, and gloss. The average particle size was measured using a NanoCyde model manufactured by Nikkaki. Also, the weight average molecular weight of the copolymer in the copolymer emulsion is s
o, o o o~350.000, preferably 100
If it is less than ,000 to 300,000, the durability will be poor, and if it exceeds 350,000, the adhesion, durability, water resistance, film forming property, and gloss will be poor, which is not preferable. It is not preferred because it has poor durability, water resistance, film-forming properties, and gloss.

The weight average molecular weight (My) was measured using 150 type liquid chromatography manufactured by Waters Co., Ltd., USA, and a column manufactured by Toyo Soda Co., Ltd., H type. The obtained molecular weight is in terms of polystyrene.

The method for polymerizing the copolymer emulsion of the present invention is preferably an emulsion polymerization method, and the emulsion polymerization method is shown below.

Examples of emulsifiers used in emulsion polymerization include anionic emulsifiers such as sodium lauryl sulfate, sodium dodecylbenzenesulfonate, alkylaryl polyether sulfates, polyoxynonylphenyl ether, and oxyethylene-oxyglobylene copolymers. One or more types of ordinary emulsifiers for emulsion polymerization, such as nonionic emulsifiers such as the following, can be appropriately selected and used.

As the polymerization initiator, a water-soluble initiator is preferable, and examples of such a polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, radical generators such as hydrogen peroxide, or There are redox catalysts that combine reducing agents such as ascorbic acid and sulfites.

As a chain transfer agent, octyl mercaptan, n-dodecyl mercaptan, tart-dodecyl mercaptan,
Examples include mercaptans such as n-hexadecylmercaptan, n-tetradecylmercaptan, and tart-tetradecylmercaptan, tetraethylthiuram sulfide, carbon tetrachloride, and ethylene bromide. These chain transfer agents can be used alone or in combination of two or more. Usage methods include bulk addition, divided addition,
Alternatively, either method of continuous addition may be used.

In this way, the copolymer emulsion for floor gloss compositions having the characteristics of combining an ethylenically unsaturated carboxylic acid and an amide monomer as discussed in the present invention is generally used in the production of floor gloss compositions. An excellent floor gloss composition that is well-balanced in adhesion, durability, dust resistance, and gloss when mixed with other ingredients used in PVC homogeneous styles, Kutsushiran floors, and dry care systems (maintenance methods). give,.

Other components that are usually used include waxes such as paraffin, montan, and polyethylene wax (5%), ethylene glycol monoethyl (/?) ether, film-forming aids such as butyl cellosolve, rosin-modified maleic acid resin,
Examples include alkali-soluble resins such as styrene-maleic acid resins, and leveling agents mainly containing fluorine-based surfactants.

In some cases, antistatic agents are used to further improve dust resistance.

In addition, fillers, dispersants (sodium polyacrylate, ammonium polyacrylate, sodium hexametaphosphate, potassium birophosphate), thickeners (e.g., tt
f hydroxyethyl cellulose, high molecular weight sodium polyacrylate), plasticizer (e.g. DOP, DBP, epoxidized fatty acid ester), auxiliary agent (n-7' lobil alcohol, ethyl cellosolve, calpitol, ethylene glycol, diethylene glycol), curing Agents (melamine-formalin resins, glyoxol resins, epoxy compounds, inorganic metal complexes, aziridine compounds), etc. may be combined to form the desired formulation for each application.

Examples of polyvalent metal compounds include zinc, zirconium,
Polyvalent metals such as magnesium, copper, iron, cobalt, nickel, and calcium or their oxide salts are dissolved in acids such as carbonic acid, formic acid, glutacic acid, and Scheler's acid, or these acids and polyvalent metals are dissolved. An aqueous solution of salts such as ammonia, amines, etc. K! ! 1) Those that can be easily obtained by adjusting the pH to 7 to 11, and those in the form of metal ions can also be included.

The preferred amount of the polyvalent metal compound added is 0.3 to 20 parts by weight per part by weight of the copolymer emulsion.

Next, examples of the invention will be shown. In the examples, parts and 忤 are parts by weight, respectively.

e Example 1 [Production of copolymer emulsion for floor gloss composition] 100 parts of water and sodium dodecylbenzenesulfonate were placed in a glass reaction vessel equipped with a thermometer stirrer, 1 dropping funnel, a gas introduction pipe, and a reflux condenser. 0.3 parts of sodium persulfate and 0.5 parts of sodium persulfate were added, and the inside of the container was replaced with nitrogen, and then heated in a hot water bath. After the temperature of the liquid was increased by 60°C, a mixture of emulsified monomers shown in A in Table 1 was continuously added dropwise for 3 hours at a reaction temperature of 80°C to form a copolymer emulsion with a solid content of 40°C. I got an A.

The Tg of this emulsion polymer A was 30°C. The above monomers were varied as shown in Table 1, and polymerization was carried out in the same manner to obtain copolymer emulsions A to F and A shown in Table 1.

[Production method of floor gloss composition]

A floor gloss composition was prepared using the copolymer emulsions A to F obtained above, and the following formulation.

Copolymer emulsion (solid content adjusted to well over 20) 8
0 parts Alkali-soluble resin 00 5 parts Wax emulsion soda 9■ 1
5 parts fluorine surfactant *o (adjusted to 1% solid content)
2 parts Calpitol (adjusted to 30% solids)
4 parts Antistatic agent 0■ 0.5
Part Water Umbrella■ Variability-■ r Ellen 19F88 (manufactured by Resident f Erets Co., Ltd.) l・
■ Hitic E-4B WAX (manufactured by Toho Chemical Co., Ltd.)
I Umbrella■ FC-129 (manufactured by Jujutsu 3M Co., Ltd.) I Umbrella■
Emaldan 404 (manufactured by Kao Atlas Co., Ltd.) Ishin solid content 1
Amount required for adjustment of 8 inches [Method for evaluating floor gloss composition] The properties of the floor gloss composition were measured by the following method. The flooring is PVC homogeneous style.

☆ The gloss composition for glossy floors was applied three times and the specular reflection gloss was measured at 60°C using a gloss meter ☆ Overcoatability Evaluate the surface condition when multiple coats are applied at 30 minute intervals.

◎ Completely coated O Non-coated area is less than 20% x No coating at all ☆ Apply an adhesive floor gloss composition and stick 1-diameter cellophane tape over it. , Peel it off at an angle of 90° to the painted surface to determine the state of adhesion between the tile and the paint film.

◎ Items that are completely adhered O Items with less than 20% peeling area
Determine the state of peeling after soaking for a minute.

◎ Completely peeled off 050% or more peeled off × means that it has not peeled off at all ☆ Water resistance Determined using the method of Japan Floor Polish Industry Standards.

◎ Items that do not whiten at all ○ Items that are whitened overall × Items that are noticeably whitened ☆ After drying the white tiles coated with a durable floor gloss composition at room temperature for one day and testing them with a shoe machine, the heel of the shoe was tested. Judging from the amount of dirt and scratches on the piece.

◎ Hardly any black stains from the heel of the shoes. O Only a few black stains from the heel of the shoes. × Black stains from the heel of the shoes get all over the surface. ☆ Anti-friction 25x35x156n box with about 208 carbon fibers. Add a piece of sponge and a tile, let it sit for about 1 minute, and judge by the degree of carbon adhesion.

◎ Hardly adheres ○ Slightly adheres × Adheres to the entire surface The results of evaluating Examples 1 to 7 and Comparative Examples 1 to 10 are shown in the second table.
Shown in the table.

In Examples 1 to 7, the monomer composition used in the present invention was changed within the scope of the present invention, and the ethylenically unsaturated carboxylic acid and (meth)
The proportion, total amount, Tg, and particle size of acrylamide were all within the range of the present invention, and this copolymer emulsion was used in a floor gloss composition. Examples 1 and 2 are
MAA/MAM, which are different types of ethylenically unsaturated carboxylic acid and (meth)acrylamide,
As can be seen from Table 2, both AA/AAM combinations exhibit well-balanced and excellent physical properties in all physical properties.

Examples 3 and 4 are cases where T is divided into high T and low T, and T 60°C has very good durability and T11
At 0°C, adhesion is very good and other physical properties are also well-balanced. Examples 5 and 6 are examples in which the ratios of ethylenically unsaturated carboxylic acid and (meth)acrylamide are changed.1 In both cases, examples 5 and 6 are examples in which the ratios of ethylenically unsaturated carboxylic acid and (meth)acrylamide are changed. Example 7 is Example 1
The results were evaluated using a vinyl asbestos tile using a copolymer emulsion (T-F), and compared with Example IK, the water resistance and coating suitability were slightly inferior, but other physical properties were almost the same.

On the other hand, Comparative Examples 1 to 10 are cases where copolymer emulsions outside the scope of the present invention were used in floor gloss compositions.

In Comparative Examples 1 and 2, the Tg was outside the range of the present invention, and as can be seen from Table 2, durability, adhesion, and stiffness resistance were poor, and other physical properties were also at a low level. Comparative Examples 3 and 4 are examples using copolymer emulsions in which the total amount and ratio of ethylenically unsaturated carboxylic acid and (meth)acrylamide were outside the range of the present invention, and the durability, adhesion, and removability were , water resistance is poor and other physical properties are also at a low level. Comparative Example 5 is an example in which the (meth)acrylamide of the present invention was not used, and the durability was poor. Comparative Example 6 is an example in which a crosslinking monomer was introduced instead of (meth)acrylamide, and the durability, adhesion, and removability were poor. Comparative Example 7 is an example of a copolymer emulsion using N-methylolacrylamide instead of (meth)acrylamide, and is inferior in durability, adhesion, and removability.

Comparative Examples 8 and 9 are examples in which the weight average molecular weight is outside the range of the present invention), Comparative Example 8 has poor durability, and Comparative Example 9 has
Poor durability, adhesion, and water resistance. Comparative Example 10 is an example in which the average particle diameter was outside the range of the present invention, and durability, adhesion,
Poor water resistance and gloss.

f [Effects of the Invention] The floor gloss composition containing the copolymer emulsion of the present invention has better adhesion than conventional compositions.

It is a well-balanced and high-level gloss composition for floors, which has excellent durability and scuff resistance, and also has a moderate gloss, and is suitable for use in PVC homogeneous styles and dry care systems.

Claims (3)

[Claims] (1) As the total of (a) 75 to 98% by weight of monomer copolymerizable with (b) and (c) below, (b) ethylenically unsaturated carboxylic acid, and (c) acrylamide and/or methacrylamide. A copolymer formed by polymerization containing 2 to 25% by weight, and the weight ratio of component (b) to component (c) [(b)/(c)] is 0.20/0.80. ~0.95/
0.05, glass transition temperature 20~80℃, average particle size range 0.05~0.25μ, weight average molecular weight 80,
A floor gloss composition comprising a copolymer emulsion having a molecular weight of 000 to 350,000. (2) The copolymer contains (a) 80 to 95% by weight of monomer
, (b) 3 to 13% by weight of ethylenically unsaturated carboxylic acid and (c) acrylamide and/or methacrylamide 2
The floor gloss composition according to claim 1, which is copolymerized with ~7% by weight. (3) The monomer (a) is an acrylic ester and/or
or 20 to 95% by weight of methacrylic acid ester, 0 to 80% by weight of styrene, and 0 to 30% by weight of other monomers, and is 80 to 95% by weight of the copolymer according to claim 1. floor gloss composition.