JPS62213758A - Emulsion type adhesive polymer - 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] (Used bones on the teiwan) The present invention relates to emulsion-polymer binders.

This invention relates to a polyacrylate emulsion adhesive suitable for application to special leather armor and a method for producing the same.

(Prior Art) A technique for producing a polymer by emulsion polymerization is known. This method is preferable because it does not use grinding or grinding, which is undesirable from a pollution standpoint. Emulsion polymerization methods use surfactants to create stable emulsions of monomers and other components and to prevent agglomeration of first gold polymer emulsions. Usually non-polymerizable surfactants are used.

However, the surfactant remaining in the polymer is extracted with water,
This makes the polymer sensitive to water. To avoid this problem, the use of polymerizable surfactants is proposed. For example, British Patent No. 1,480,186 discloses emulsion polymerized polymers as industrial adhesives suitable for masking tapes and lists copolymerizable surfactants suitable for this purpose. British Patent No. 1,220,476 discloses copolymerizable surfactants having the following general formula, among others.

OF[2=C-C-0-(OH2)mY(CH2')n
0-0-R (in the formula, m is an integer of 2 to 4, n is an integer of 1 or 2, 几 is C
The alkyl group of l-022, Y is -8(02)OM and M is hydrogen, ammonia or an alkali metal. ) Such surfactants are used in emulsion polymerization reactions.
This emulsion polymer is used with a vinyl compound of 100 to make an emulsion polymer that can be used to coat substrates such as textiles and plastics to provide banding prevention properties or as a dyeing aid.

(Means for Solving the Problems) The present inventor selected from the above compounds the following general formula % formula %) (In the formula, ru is an alkyl group of cto-at4, ■ is hydrogen,
Ammonia or an alkali metal. ) to conduct an emulsion polymerization reaction with one or more copolymerizable acrylic monomers using a copolymerizable surfactant. It was found that the emulsion-like polymer was transferred by 1.

According to the present invention, an emulsion-like adhesive polymer comprising residues of one or more acrylic monomers and residues of a compound of general formula (I) is provided.

(In the formula, 11 is an alkyl group of 010"""014, and N is hydrogen, ammonia, or an alkali metal.) General formula f
The compounds of l) form stable emulsions with the acrylic monomers and prevent such emulsions from aggregating during the emulsion polymerization process.

The residue of the compound of general formula (I1 forms a part of the produced polymer.1rt made by emulsion polymerization reaction)
, the combination is one adhesive combination, that is, one acrylic adhesive combination.

The adhesive polymer of the plate is a pressure sensitive adhesive that can be used on the skin, for example, as a surgical or medical dressing.

In order to maintain good adhesion to the skin, it is particularly desirable that these adhesion agents be water-sensitive (not 3 (water does not have a significant effect on their adhesive performance)). None of the above-mentioned British patents disclose pressure sensitive adhesives for use on skin, W, as for example in surgical or medical dressings.

Suitable compounds of general formula (I) are in the form of ammonia or alkali metal salts, but also in the form of sodium or potassium salts. A preferred form of the compound of general formula ([) is the sodium salt.

The alkyl group is suitably one having 10 to 14 carbon atoms, more suitably one having 11 to 18 carbon atoms, and preferably an alkyl group having 12 carbon atoms.

Therefore, in the production of a preferred adhesive polymer, a compound in which tl in the general formula (I) is an alkyl group having 12 carbon atoms and M is sodium is used, that is, sodium monolauryl itaconoxypropanesulfonate. It is preferable that the emulsion-like osteosynthetic sparrow aggregate of the present invention contains 0.1 to 5% by weight, preferably 0.1 to 1% by weight, of a residue of the compound of general formula (I) or a salt thereof. In a suitable polymer of the present invention, the acrylic polymer component mainly consists of residues in which the single d-isomer is an alkyl ester of acrylic acid or methacrylic acid and has 2 to 111 carbon atoms. Alkyl acrylate monomers which make advantageous pressure-sensitive stimulants have 3 to 12 carbon atoms, preferably 4 to 9 carbon atoms.
2 is an alkylnoacrylate ester. This type of alkyl acrylate is n-butyl acrylate, 2
- Contains ethylhexyl acrylate and other octyl acrylates. Preferred monomers are n-butyl acrylate and 2-ethylhexyl acrylate.

These acrylic residues are suitably derived from a compound of two types of monomers, 1! However, it is advantageous for the adhesive polymers of the present invention to contain other acrylic mono-11 residues as described below. In such instances, the acrylic residues are 80-98.5% direct placement,
Preferably it forms 88-9411%.

The pressure-sensitive d-containing polymer of the present invention preferably contains an acrylic μmer residue. A-A suitable F-4 is an acrylic monoester such as an alkyl acrylic acid or methacrylic acid ester which may be hydroxylated or alkoxylated.

Other preferred overall acrylic groups include lower alkyl, hydroxylated or alkoxylated alkyl monoesters of methacrylic acid, such as methyl methacrylate, n-butyl methacrylate, hydroxyethyl methacrylate and methoxyethyl methacrylate. Preferred single! The substances are hydroxyethyl methacrylate, methyl methacrylate and n-butyl methacrylate. Also suitable, but not preferred, are polyhydric esters such as glycidyl methacrylate.
(pogyesters).

Such FJI groups constitute up to 20% of the polymer, suitably up to 12%, but between 5 and 12% of the polymer.
is preferred. Of such residue! The role is also appropriate; 1 case depends to some extent on the plate tilt of each single unit, the main body of the 4-piece type 41, the emulsion polymerization process and the cold (W) properties of the pressure-sensitive adhesive. Therefore, hydroxyethyl methacrylate residues are present at 8 to 5 q% of the polymer, and lower alkyl methacrylate residues are present at 1 to 5 q% of the polymer.
It can be present in an amount of 15% by weight.

Suitable pressure-sensitive adhesive polymers contain 36-50% by weight of n-butyl acrylate residues, 39-59% by weight of 2-ethylhexyl acrylate residues, and 1-15i! of lower alkyl methacrylate residues! ff1%, hydroxyethyl methacrylate residues 0.8 to 5% by weight, and hydroxyethyl methacrylate residues from 0.1 to 5% by weight. The term lower alkyl used in and \ means an alkyl group having 1 to 6 carbon atoms.

Desirable pressure-sensitive adhesive polymers include 39 to 45% by weight of 11-butyl acrylate residues, 47 to 49.5 q% by weight of 2-ethylhexyl acrylate residues, and lower alkyl methacrylates! 15-10%, hydroxyethyl methacrylate residue 0.8-8iQ%, compound residue in one-stage formula 0.
It is composed of 1 to 1% by weight.

Preferred pressure-sensitive adhesive polymers include n-butyl acrylate residues at 44.5%, 2-ethylhexyl acrylate residues at 49.5%, n-butyl methacrylate residues at 5Tftffi%, hydroxyethyl methacrylate residues at type 1%, It consists of the sodium salt of monolauryl itaconoxypropane sulfonic acid.

The pressure sensitive adhesives of the present invention can be used as surgical and medical adhesive dressings, and thus surgical and medical adhesive dressings using the adhesives of the present invention are an important aspect of the invention.

Accordingly, the adhesive of the present invention can be coated over known backing materials found used in surgical and medical bone fractures. The backing material is, for example, a customary non-woven, woven, knitted fabric, paper or synthetic film. Preferred backing materials include porous polyvinyl chloride film, polyurethane film, and integral net.
ralnets) etc. A preferred backing material for moisture permeable adhesive dressings is described in British Patent No. 1280631.
and European Patent Application No. 50985@, backing materials that allow the passage of tissue or wound exudates include nonwovens, textiles, knits, nets, and perforated films.

The backing material can be in any form suitable for making adhesive-coated sheets, such as adhesive tapes, strings, wound dressings, surgical cloths, and the like.

The emulsion-like pressure-sensitive adhesive polymer is applied to the backing material by any suitable method. For example, the coating can be carried out by coating the aqueous portion of the emulsion 1 &[ which has been thickened to 1/2] onto a silicone-coated release paper, and then transferring this onto a suitable backing material.

The compound of general formula (I) is the English! 5
? ? It can be produced by the method described in Japanese Patent No. 11220478. The preferred copolymerizable surfactant beaten monolauryl itaconoxypropane sulfonic acid sodium salt can be prepared in a manner similar to that described in Example 1 of GB 1220476. in the form of an emulsion in the presence of one or more acrylic compounds, the compound of general formula (I) and a total free radical catalyst.
Emulsions that may be made by this method are usually prepared by first preparing an aqueous solution containing a surfactant and a heavy metal chelating agent.

If available, you can add a single low heat ingredient to these four liquids. For example, add hydroxyethyl methacrylate to this solution. The remaining monomers can be premixed and added gradually to the aqueous mixture over a period of 15 minutes to 1 hour while stirring at high speed. The resulting emulsion is left to degas. ? The solids content of the revealed monomer emulsion is typically from 15 to 70% by weight, preferably from 50 to 60% by weight.

? The lfi emulsion thus obtained is added to a water ffJ solution of a free radical catalyst such as animon persulfate, heated typically to 80-95°C, and heated to a temperature of 80°C to 95°C, followed by an inert gas such as carbon dioxide or carbon dioxide. Polymerization takes place in the presence of

It is advantageous to add the monolambda emulsion to the catalyst solution throughout the polymerization reaction. The resulting polymer emulsion is cooled and stored until needed.

The polyacrylate adhesive emulsion of the present invention is neutralized with, for example, ammonium hydroxide prior to use.
It can be thickened using conventional polyacrylate thickeners such as Primae A8 E 60 J™. The adhesive can be applied directly onto a suitable substrate by coating means using conventional coating techniques or by transfer.

Example 4 Example 1 (Production of emulsion polyacrylate adhesive) Water 651 was placed in an open-topped beaker. A "Silverson" stirrer head with a high shear head was placed in the above water and 0.02 f of sodium tripolyphosphate, sodium monolauryl itaconoxypropanesulfonate o, Iry and 0.85 f of hydroxyethyl methacrylate were added. Stir throughout. 2-
Ethylhexyl acrylate 421% n-butyl acrylate a8y and n-butyl methacrylate 4.25
Another mixture of f was made. This second mixture was added to the stirring contents of the beaker over 20 minutes. When the addition was complete, the mixture was continued to stir for an additional 15 minutes, after which the stirrer was turned off. The mixture was degassed for 80 minutes.

60 f of water was placed in a reaction flask equipped with a heating device and a stirrer. 11 water! Heat to 82°C without stirring, then i
0.000442f of M,4Q ammonium was added. The above monomer mixture was added to the flask over a period of 8 hours, during which time stirring was continued and the temperature was maintained at 85-90°C.

The resulting polymer emulsion was heated for 40 min before being transferred to a storage container.
'C.

Actually, Convention 2 (Production of emulsion-like polyacrylate adhesive) An emulsion-like lk combination was obtained in the same manner as in Example 1 except that methyl methacrylate 4.251 was used instead of n-butyl methacrylate.

Example 3 (Production of emulsion-like polyacrylate adhesive) An emulsion-like adhesive was prepared in the same manner as in Example J except that 8.5 da of n-butyl methacrylate and 38.75 y of n-butyl acrylate were added. Obtained union.

Example 4 (Manufacture of surgical adhesive tape) The polyacrylate adhesive emulsion prepared in Example 1 was added with a thickener [Puri? Primad A8E60 (Takagen, manufactured by Rohm and Haas)" was added for aging, and an antioxidant "
0.6 wt. 1% of Nonox WS L (Shang Shun) was added based on the weight of the emulsion. This mixture was coated with silicone 2II! 11 papers (“Stellarly-x (9
teral! ese) (Plateau, Steering Coated Paper (3terlingCoated Pa
Plate coater (manufactured by Per Limted)
oater) and heated to 1100±5°C
A dry pressure sensitive adhesive with a weight of 40 y/neu was obtained by drying in a Type 44 oven.
νKag Example 2 of British Patent No. 1,531,715, as described in either of the following examples:
), 1'J1;'H on the outside → tape of 2.5 tM width
did. The obtained surgical tape was dried on human skin...
It adhered well to skin (g), wet skin, and sweaty skin (a). .

Ding, g+,';(-2

Claims (1)

[Claims] One, one or more acrylic monomer residues and the following general formula (I); ▲ Numerical formulas, chemical formulas, tables, etc. an alkyl group, M is hydrogen, ammonia, or an alkali metal. 2. The emulsion-like adhesive polymer according to claim 1, which contains 0.1 to 5% of the compound residue of general formula (I). 3. The emulsion-like adhesive polymer according to claim 1 or 2, wherein the compound of general formula (I) is sodium monolaurylitaconooxypropane sulfonate. 4. Acrylic monomer residue accounts for 95-99.9% of the polymer
An emulsion-like adhesive polymer according to any one of claims 1 to 3. 5. The emulsion-like adhesive polymer according to any one of claims 1 to 4, wherein the acrylic monomer is an acrylic acid or methacrylic acid alkyl ester of an alkyl group having 3 to 12 carbon atoms. 6. Acrylic 6. The emulsion-like adhesive polymer according to claim 5, wherein the monomer comprises a mixture of n-butyl acrylate and 2-ethylhexyl acrylate. 7. Acrylic monomers include methacrylic acid esters of groups selected from the group consisting of lower alkyl, hydroxyalkyl, and alkoxyalkyl in an amount of 0.1 to 20% by weight (based on the weight of the polymer) and alkyl having 8 to 12 carbon atoms. The emulsion-like adhesive polymer according to claim 1, which contains 80 to 98.5% by weight (based on the weight of the polymer) of acrylic acid or methacrylic acid ester. 8. The emulsion adhesive polymer according to claim 7, wherein the acrylic monomer contains 0.3 to 5% by weight of hydroxyethyl methacrylate. 9. The emulsion-like adhesive polymer according to claim 7, wherein the acrylic monomer is a lower alkyl methacrylate ester in an amount of 1 to 15% by weight. 10, n-butyl acrylate residue 36-50% by weight,
2-ethylhexyl acrylate residues 39-59% by weight
, lower alkyl methacrylate residues 1-15% by weight, hydroxyethyl methacrylate residues 0.3-5
8. The emulsion-like adhesive polymer according to claim 7, which is a pressure-sensitive adhesive comprising 0.1 to 5% by weight of monolauryl itaconoxypropane sulfonate residues. 11, n-butyl acrylate residue 39-45% by weight,
47-49.5% by weight of 2-ethylhexyl acrylate residues, 5-1% of lower alkyl methacrylate residues
0% by weight, hydroxyethyl methacrylate residue 0.8
11. The emulsion-like adhesive polymer according to claim 10, which is a polymer consisting of ~3% by weight and 0.1-1.0% by weight of monolauryl itaconoxypropane sulfonic acid sodium salt. 12. One or more acrylic monomers and the general formula (
I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 is an alkyl group of C_1_0 to C_1_4, and M is hydrogen, ammonia, or an alkali metal.) A method for producing an emulsion-like adhesive polymer, which comprises polymerizing in the presence of a metal ion chelating agent. 13. The manufacturing method according to claim 12, wherein the metal ion chelating agent is sodium polyphosphate. 14. One or more acrylic monomer residues and the following general formula (I); ▲Mathematical formulas, chemical formulas, tables, etc. are available▼(I) (In the formula, R_1 is an alkyl group of C_1_0 to C_1_4 , M is hydrogen, ammonia, or an alkali metal.