JPH039997A - Detergent - Google Patents

Abstract

PURPOSE:To obtain a detergent which can effectively remove stains without damaging the surface of a medical appliance such as a contact lens by compounding water, a surfactant, and a specified substance together. CONSTITUTION:A detergent comprising water, a surfactant such as sodium lauryl sulfate or polyoxyethylene nonylphenyl ether, and at least one gel which can adsorb proteins, e.g. polyvinyl alcohol copolymer gel, and/or carragheenan supported on cellulose.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is directed to the prevention of damage caused by external factors such as dust firmly attached to the surface of medical devices such as contact lenses.
6. Related to a cleaning agent that can easily and effectively clean and remove dirt substances secreted from a living body and adhered thereto. [Prior Art and its Problems] The prior art will be explained using a contact lens as an example.

A variety of contact lenses have been used in the past, but they are broadly divided into water-containing soft contact lenses that contain polyhydroxyethyl methacrylate as the main component, and other non-water-containing types. They are divided into hard contact lenses whose main ingredients are hard contact lenses, water-free soft contact lenses typified by silicone rubber, and gas permeable hard contact lenses whose main ingredients are polymethyl methacrylate/siloxanyl methacrylate.

When these contact lenses are worn on the eyes, proteins and lipids in the tear fluid adhere in the form of a film or dots, causing unpleasant symptoms such as decreased vision, pain, and redness. In some cases, lens wear may have to be discontinued.

In particular, gas-permeable hard contact lenses have the property of easily forming stubborn stains on their surfaces, but there are restrictions on the types of cleaning agents that can be used due to the chemical safety of the lens material. Therefore, it is desired to develop a cleaning agent suitable for this type of lens, and several types of cleaning agents have already been proposed.

These cleaning agents are divided into the following four types depending on the components that contribute to cleaning.
Divided into types.

Namely, 1) surfactant alone, 2) surfactant in combination with a thickener, 3) surfactant in combination with an inorganic abrasive such as silicon dioxide, and 4) surfactant in combination with a polymer. There are four types: one that combines organic abrasives such as beads.

1) is the most basic method for removing dirt from the lens surface, but since it relies only on the surfactant for cleaning power, the concentration of the surfactant must be relatively high. Since rinsing takes a long time, there is a high risk of losing the lens.Furthermore, when rubbing the lens with one's fingers, the lens becomes slippery and slippery, so the cleaning effect cannot be expected to be very effective.

2) In order to improve the shortcomings of 1), a thickener is added to increase the friction between the finger and the lens, increasing the cleaning power somewhat, but the thickener itself is washed away. Therefore, the lens must be rinsed for a long time, and as in the case of 1), the lens is easily lost, which is not satisfactory for the user.

3) is effective against film-like dirt firmly attached to the lens surface, but it essentially polishes the lens surface with a hard abrasive, which removes not only dirt but also the lens itself. There is a risk that the user will gradually wear it down and eventually change the curvature of the contact lens to such an extent that it no longer serves its original purpose of correcting refractive errors in the cornea of the eye.

Although the method 4) has improved the drawback of scraping off the lens itself compared to the method 3), the polishing ability has significantly decreased, and the primary contribution to the cleaning effect is increased friction. In the end, it was only a slight improvement over 2).

Furthermore, what is common to all four types is that proteins and lipids that have once left the lens surface are retained in the cleaning solution around the contact lens by surfactants, so if the amount of surfactant is If the amount is insufficient, it will easily adhere to the lens surface again.

As described above, although several cleaning agents have been proposed, there is still no one that satisfies users.

[Problem to be solved by the invention]

The above explanation has been given using contact lenses as an example, but the present invention provides an effective cleaning method that does not have a negative effect on objects to be cleaned, such as medical instruments, especially contact lenses, which could not be solved with the conventional techniques. The purpose of the present invention is to provide a cleaning agent that can remove dirt.

[Means to solve the problem]

The present inventors have achieved the present invention as a result of extensive research to solve the problems of the prior art.

The present invention is a cleaning agent containing (1) water, (2) a surfactant, and (3) at least one type of gel and/or carrageenan supported on cellulose having protein adsorption ability.

The present invention will be explained in detail below.

Typical examples of gels having protein adsorption ability that can be used in the present invention include polymerizable carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl caproate, and vinyl adipate; Polyfunctional monomers such as lucyanurate, ethylene glycol dimethacrylate, butanediol divinyl ether, etc. can be mixed with organic solvents such as toluene and xylene that dissolve the monomers but are difficult to dissolve in water, or with the organic solvents and the monomers. Examples include particulate coelectric materials obtained by suspension polymerization in the coexistence of dissolved linear polymers such as polyvinyl acetate and polystyrene, and chemically modified copolymers.

Examples of preferable gels that can be used in the present invention include A) a gel made of a vinyl acetate copolymer, B) a gel made of a polyvinyl alcohol copolymer, and C) a gel made of the polyvinyl alcohol copolymer with a hydroxyl group of 1.5 to 2.
D) Gel esterified with an alkyl group having 3 to 30 carbon atoms with a density in the range of 0 meq/H, D) 0.1 to 1.0 in the hydroxyl group of the gel made of the polyvinyl alcohol copolymer.
There are gels in which carboxyl groups have been introduced at a density in the range of meq/g, and each can be used alone or in combination of two or more. Examples of methods for producing these gels are as follows.

That is, A) the gel made of vinyl acetate copolymer is
Vinyl acetate and triallyl isocyanurate are mixed in the coexistence of an organic solvent that dissolves the monomer but is difficult to dissolve in water.
．． 55 using 2'-azobisisobutyronitrile as a catalyst
Suspension polymerization is carried out at ~80°C for ~25 hours, and the resulting granular copolymer is filtered, washed with water, extracted with acetone, and dried.

B) A gel made of polyvinyl alcohol copolymer is
It can also be obtained by hydrolyzing a gel made of the above-mentioned vinyl acetate copolymer in a solution of sodium hydroxide and methanol, but vinyl propionate,
A granular copolymer obtained by suspension copolymerization of other carboxylic acid vinyl esters such as vinyl adipate alone or in combination with a crosslinking agent such as triallylisocyanurate is prepared from sodium hydroxide and methanol. It can also be obtained by carrying out a hydrolysis reaction in a solution at 40 to 50°C for 15 to 20 hours. Details are disclosed in, for example, Japanese Patent Laid-Open No. 57-30945 filed by the present applicant.

C) A gel in which the hydroxyl groups of the gel made of the polyvinyl alcohol copolymer are esterified with an alkyl group having 3 to 30 carbon atoms at a density in the range of 1.5 to 2.0 meq/g is obtained by esterifying the hydroxyl groups of the gel made of the polyvinyl alcohol copolymer with alkyl groups having 3 to 30 carbon atoms. It is obtained by hydrolyzing a particulate copolymer obtained by suspension polymerizing monomers, and then heating and refluxing the hydrolyzate together with a carboxylic acid chloride having 3 to 30 carbon atoms in a basic organic solvent such as pyridine under a nitrogen stream. It is obtained by filtering the reaction product and washing with chloroform and acetone, but in order to achieve the purpose of the present invention, stearic acid chloride is most preferably used as the carboxylic acid chloride. Details are disclosed in, for example, Japanese Patent Laid-Open No. 63-225606 filed by the present applicant.

D) A gel in which carboxyl groups are introduced into the hydroxyl groups of a polyvinyl alcohol polymer at a density in the range of 0.1 to 1.0 meq/g is a granular copolymer obtained by suspension polymerizing the vinyl carboxylate and a polyfunctional monomer. The combined product is hydrolyzed, and the hydrolyzate is further treated in an acid anhydride of a dibasic acid such as succinic anhydride or glutaric anhydride, or a halogenated acetic acid such as monochloroacetic acid or motupromacetic acid, and a basic organic solvent such as pyridine. Although it can be obtained by introducing a carboxyl group by reaction, it is preferable to use monochloroacetic acid in order to achieve the object of the present invention. Details are disclosed in Japanese Patent Laid-Open No. 59-232102 filed by the present applicant.

The gel described above traps and supports proteins within its fine pores.

Taking the case of a gel made of a polyvinyl alcohol copolymer as an example, to explain further, this gel is obtained by copolymerizing vinyl acetate hetamine with the above-mentioned crosslinking agent and then saponifying it. A portion of the hydroxyl groups in the chain are blocked by reacting with a hydrophobic group, and the balance between hydrophilicity and hydrophobicity is controlled by the degree of blocking or the structure of the hydrophobic group.

The hydrophilicity/hydrophobicity balance controlled in this manner determines the affinity with various proteins, and the proteins are captured and supported within the fine pores of the gel.

- Once the supported proteins are not easily eluted from the gel, extremely large amounts of solvent are required if they are to be eluted.

When contact lenses are washed with a gel that has the ability to adsorb proteins as described above, water, and a surfactant, if necessary, an isotonic agent and a buffering agent, when rubbed with a finger, due to the action of the surfactant. , the proteins leave the lens surface, are captured and carried by the gel, and are easily washed away by rinsing.

Therefore, if the gel used in the present invention is simply bead-shaped, no matter how much the affinity with proteins is increased, no effect beyond physical wiping, that is, extremely gentle polishing, can be expected. The effect is similar to that obtained by combining organic abrasives such as polymer beads described in .

As mentioned above, by incorporating a gel having protein adsorption ability, the cleaning effect is significantly enhanced.

The gel may have a particle size in the range of 1 to 500 μm to achieve the object of the present invention. Preferably 5 to 200 μm, more preferably 10 to 100 μm
It is. It is preferable to use particles with a specific particle size depending on the type of contact lens to be cleaned and the type or degree of dirt. In order to adjust the size of the gel, it may be used after being classified. Furthermore, two or more classified materials may be mixed and used. The particle size of the gel is measured by an electrical resistance method using a Coulter Counter manufactured by Aji Nikikaki.゛In addition, in order to achieve the purpose of the present invention, the gel should be present in a cleaning agent containing 0.05 to 15% by weight in order to obtain a sufficient cleaning effect and to facilitate dispersion of the gel in the liquid. It can be used in a range of 0.05 to 5% by weight, for example. Desirably 0.2 to 4, more preferably 1 to
It is more desirable to use it in a range of 3% by weight. 5% by weight
The effect is almost the same even if the amount is used in excess of this range, and the above range is desirable for economical reasons as well.

The carrageenan used in the present invention is a sulfate ester metal salt of a polysaccharide containing galactose and acihydrogalactose extracted from red algae with water, and its unique
It is widely used in food applications due to its reactivity with proteins.

Carrageenan is classified into three types, K (kappa), ■ (iota), and L (lambda), depending on the position and amount of the sulfate ester bonded, and each type has different characteristics such as water solubility and gel-forming ability. Since they are different, an appropriate type is selected depending on the purpose and a mixture is used.

In the present invention, the amount of carrageenan used in the cleaning solution is 0.3 to 5% by weight, preferably 0.3 to 5% by weight, in order to obtain a sufficient cleaning effect and maintain fluidity of the cleaning solution. It ranges from 5 to 2.5% by weight, more preferably from 1 to 2% by weight.

By being supported on cellulose particles, carrageenan, which exhibits this unique reactivity with proteins, can come into contact with proteins at a high concentration that cannot be reached by simply dissolving it in a solution. Become.

In other words, when carrageenan is supported on cellulose particles and proteins are captured by carrageenan,
A strong gel supported by cellulose particles can be formed. Gels formed in this way do not transfer to the lens surface and are easily washed away by rinsing.

Conversely, when carrageenan is dissolved in a solution, even if the protein forms a gel with the carrageenan, the gel is retained in the cleaning solution around the contact lens, so when you rub the contact lens with your fingertips, , which results in rubbing against the lens surface, significantly defeating the purpose of cleaning.

As mentioned above, carrageenan's properties are utilized by supporting it on cellulose. The weight ratio of carrageenan to cellulose is 5 to 15% by weight, preferably 8 to 12% by weight, and 95 to 85% by weight, preferably 92 to 88% by weight of cellulose.

Further, the total weight of carrageenan and cellulose in the detergent is preferably 5 to 50% by weight, more preferably 10 to 25% by weight.

An example of a method for supporting carrageenan on cellulose is to grind and knead a mixture of carrageenan, cellulose, and a disintegrant in the presence of water, then dry and grind.

Cellulose here refers to those obtained by subjecting cellulose raw materials such as linters, pulp, and regenerated fibers to chemical decomposition treatments such as acid hydrolysis and alkali oxidative decomposition, and/or mechanical crushing treatments.For example, cellulose of various types Available in powder and crystalline cellulose.

In order to make the effects of the present invention more noticeable,
It is most suitable to use crystalline cellulose.

Disintegrants are added to facilitate the dispersion of cellulose particles in water, and include monomers such as sucrose, glucose, fructose, and lactose. Starch decomposition products such as dextrin, cyclodextrin, and low-viscosity modified starch can be used alone or in combination, and usually cellulose particles 95
-75% by weight, disintegrant 5-25% by weight.

The carrageenan supported on gel or cellulose having protein adsorption ability may be used alone, or the effect will be even more remarkable when used in combination.

In addition, the surfactants used in the cleaning solution of the present invention include anionic surfactants such as sodium lauryl sulfate and sodium polyoxyethylene alkyl sulfate, polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ether, and polyoxyethylene glycol. One or more types can be selected from the group of nonionic surfactants such as stearate, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene/propylene.

It is desirable to use these surfactants in a concentration higher than CMC (1>-interface micelle formation concentration), but since they are not the main components for removing dirt, they are not needed in large quantities, so they should be used in cleaning agents with zero concentration. It can be used in a range of .1 to 5% by weight, preferably 0.2 to 2.5% by weight, and more preferably 0.5 to 1.5% by weight.

Additionally, other useful additives can be used in the cleaning agent of the present invention, if desired.

For example, the prefecture uses sodium chloride and potassium chloride to adjust the ion concentration of water, buffers such as boric acid and sodium borate to adjust the pH of water, and chemicals to prevent the growth of harmful microorganisms. Preservatives such as roseoxyalkylbenzoic acid and sorbic acid, chelating agents such as ethylenediaminetetraacetic acid disodium salt, which supplements metal ions in water and has a bactericidal effect, and carboxymethylcellulose and polyacrylic to stabilize particle dispersion. Thickeners such as acids, coloring agents such as Food Blue No. 1 to increase commercial value, and fragrances such as Hikari can also be used.

The method for producing the cleaning agent of the present invention containing the above-mentioned useful additives is, for example, as follows.

That is, purified water, buffering agent, etc. in the homomixer,
A gel consisting of a preservative, a hydrolyzed starch-added cellulose particle carrying carrageenan, a surfactant, and a polyvinyl alcohol copolymer was poured in this order, and the total amount was 7,500 to 8.0.
It is obtained by mixing and stirring at 0 rpm for 5 minutes.

This cleaning agent usually accomplishes its cleaning purpose by applying a few drops to the surface of the lens and rubbing it with your fingers, for example in the case of contact lenses, but it can also be applied to a cloth, sponge, pad, etc. May be used.

This cleaning agent can also be used for all other types of contact lenses except hydrous soft contact lenses.

Furthermore, the cleaning agent according to the present invention can be widely used not only for medical instruments and the like, but also for cleaning the skin of hands, fingers, face, etc. Even though the surfactant is added in a range of only 0.1 to 5% by weight, dirt such as dust and secretions can be easily removed and washed off with just a few seconds of rinsing, making it a special skin care product. When this washing was repeated without using a protective agent, it caused extremely little irritation to the skin compared to regular cosmetic soaps. In this case, as described above, the effect can be further enhanced by using a combination of carrageenan supported on cellulose and a gel having protein adsorption ability.

[Example] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples.

Note that parts in the examples represent parts by weight.

Example 1 In a homomixer, 100 parts of purified water, 0 parts of sodium chloride
．． 6 parts, potassium chloride 0.15 part, boric acid 0.43 part,
Sodium borate 0.04 part, ethylenediaminetetraacetic acid disodium salt 0.1 part, butyl oxybenzoate 0
．． 0045 parts, isobutyl paraoxybenzoate 0.00
45 parts, isopropyl paraoxybenzoate 0.006 parts, 10 parts of crystalline cellulose containing 10% hydrolyzed starch and carrying 10% carrageenan, 0.25 parts of polyoxyethylene alkyl sulfate sodium salt, polyoxyethylene, nonylphenol ether Pour 0.25 parts of sodium lauryl sulfate, 0.5 parts of sodium lauryl sulfate, and 2 parts of polyvinyl alcohol copolymer color gel in the order listed, and add 7.500 parts.
A cleaning solution was prepared by mixing and stirring at ~8.00 rpm for 5 minutes.

The prepared cleaning solution was published in Japanese Contact Lens Society Journal No. 24.
vol. 277-283, (1982), the cleaning effect was evaluated by cleaning various resin pieces for contact lenses that had been stained and dyed, and scratches on the surfaces of the resin pieces were observed. The cleaning method is as follows. That is, apply a few drops of cleaning liquid to approximately half of the part of the resin piece to be dyed,
After rubbing with your fingers 10 times, rinse under running water for a few seconds and repeat this process.

The cleaning effect was evaluated by the number of times the method was repeated until stains were completely removed from the area to be cleaned on the surface of the resin piece.

Note that three types of dirt substances were used: mucin (pre-mortem mucous membrane), lysozyme (egg white), and lecithin (egg yolk).

The results are summarized in Table 1.

Example 2 A cleaning solution was obtained and evaluated in the same manner as in Example 1, except that the gel made of polyvinyl alcohol copolymer was removed.

The results are summarized in Table 1.

Example 3 A cleaning solution was obtained and evaluated in the same manner as in Example 1, except that the carrageenan supported on cellulose was removed.

The results are summarized in Table 2.

Comparative Example A cleaning solution was obtained and evaluated in the same manner as in Example 1, except that the gel made of polyvinyl alcohol copolymer and the carrageenan supported on cellulose were removed.

The results are summarized in Table 1.

Table 1 Examples 4 to 6 Cleaning solutions were prepared and evaluated in the same manner as in Example 1, except that the amount of gel made of polyvinyl alcohol copolymer was changed to the parts by weight shown in Table 2. .

The results are summarized in Table 3.

Table 2 Amount of gel added in Examples 4 to 6 (2) Resin pieces A, B, and C are A:P, respectively.
MMA B Nidris(trimethylsiloxy)-T-methacryloxypropylsilane methyl methacrylate methacrylic acid ethylene glycol dimethacrylate copolymer C: Silicone rubber.

55 parts 30 parts 10 parts 5 parts (hereinafter referred to as margins) Table 3 Number of cleaning times required to completely remove dirt substances [Effects of the invention] According to the present invention, dirt firmly attached to the surface of the object to be cleaned However, it can be quickly removed without damaging the surface, and it is possible to prevent dirt that has been removed and is present in the cleaning solution from re-adhering to the same surface.

Claims (1)

[Claims] 1. A cleaning agent containing (1) water, (2) a surfactant, and (3) at least one type of gel having protein adsorption capacity and/or carrageenan supported on cellulose.