KR101921871B1 - Gel compositions for ultrasound examination and Process for Thereby) - Google Patents

Abstract

The present invention relates to an ultrasonic inspection gel composition. The ultrasonic inspection gel composition includes: 0.5-0.7 wt% of a binder; 0.1-0.4 wt% of a tackifier expressed as the chemical formula 1; 1.0-1.5 wt% of a neutralizing agent; 1.2-2.6 wt% of a moisturizer; 0.1-0.3 wt% of a preservative; and 95.0-97.0 wt% of distilled water. [chemical formula 1] n represents a number in the range of 10,000 and 60,000 while A represents -COOH and -COOR. The molar ratio of -COOH to -COOR is in the range of 7/3 to 8/2. R represents C_18H_35-O-(CH_2-CH_2-O-)_m-CH_2-CH_2- while m represents a number in the range of 4 to 11. The ultrasonic inspection gel composition can improve the gel flow properties, workability in both high and low temperature conditions, and storage stability at a high temperature by being mixed with the tackifier of chemical formula 1.

Description

 Technical Field [0001] The present invention relates to a gel composition for ultrasound examination,

The present invention relates to a gel composition for ultrasonic inspection and a method for producing the gel composition, and more particularly, to a gel composition and a gel composition for use as a sound transmission medium in ultrasonic examination by using a tackifier .

Ultrasonic inspection is performed by using an apparatus that emits an ultrasound into the human body and graphically images and decodes the signal reflected from each organs. It is widely used in obstetrics and gynecology to examine the status and function of various internal organs, and is now being developed and used in physical therapy and cosmetology.

In the ultrasonic inspection, the probe of the ultrasonic generator is contacted with the human body and the ultrasonic wave is generated and projected into the human body. If the contact area is not perfect, the ultrasonic wave is leaked, It does not come out. For this reason, in order to transmit the ultrasonic wave to the human body, a gel having good ultrasonic transmission ability is applied to the contact part,

Gel is usually prepared by dissolving a water-soluble polymer material having a large number of carboxyl groups (-COOH) in water and adding a tackifier, a neutralizer, a humectant, and an antiseptic thereto.

As a conventional technique related thereto, Patent Document 0001 discloses "gel for ultrasonic inspection using natural materials", but discloses a technique of adding aloe vera, cucumber, and gardenia extract to a gel to obtain a therapeutic effect .

Patent Document 0002 discloses a composition of a gel for biosonic ultrasonic examination and a method for producing the same, but it has been disclosed that a mixture of sodium carboxy methyl cellulose, aloe vera, DL-panthenol and the like This is only a technique that has got good results in skin moisturizing and skin care.

Patent Document No. 3 discloses a method for manufacturing an ultrasonic cosmetic gel and its use, which is referred to as " an ultrasonic gel for treating arthritis, and a method for producing the same ", which is made of polyglycerylmethacrylate, polyethylene glycol Discloses a technique in which an ultrasound cosmetic gel is prepared by mixing PEG, carboxylvinylpolymer, ethylenediaminetetraacetate, plant extract (mulberry extract, green tea extract, cucumber extract, barley extract, etc.) There is only.

Patent Document 0004 discloses a gel for ultrasound therapy for treating arthritis and a method for producing the gel. However, the present invention is applicable to a gel for ultrasound examination, such as mints, camphor, methyl salicylic acid, And the like, and discloses a technique of using ultrasonic waves in the treatment of arthritis.

However, the prior art discloses a gel for ultrasonic inspection using various natural materials, and it is difficult to form a gel film having a proper thickness because of low workability due to low temperature at a low temperature, There is a disadvantage that the workability is poor due to the lowering and the storage stability due to phase separation is weak.

Therefore, there is an urgent need to develop a new gel for ultrasonic inspection to solve the above problems.

Korean Patent Publication No. 2000-0002401 (2000. 01. 15.) Korean Patent No. 10-0318049 (December 06, 2001) Korean Patent Publication No. 2001-0000373 (2001. 01. 15.) Korean Patent Registration No. 10-0461049 (December 01, 2004)

Disclosed is a gel composition for ultrasonic inspection having excellent workability and storage stability, and a method for producing the same.

The present invention relates to an adhesive composition comprising 0.5 to 0.7% by weight of a binder, 0.1 to 0.4% by weight of a tackifier represented by the formula (I), 1.0 to 1.5% by weight of a neutralizer, 1.2 to 2.6% by weight of a moisturizer, 0.1 to 0.3% To 97.0% by weight of a gel composition for ultrasonic inspection.

[화학식 1]

[Chemical Formula 1]

Wherein n is from 10,000 to 60,000,

A is -COOH or -COOR, the molar ratio of -COOH / -COOR is 7/3 to 8/2,

R is C ₁₈ H ₃₅ -O- (CH ₂ -CH ₂ -O-) _m -CH ₂ -CH ₂ -

and m is 4 to 11.

Means for solving the other specific problems according to the present invention are described in the detailed description of the invention.

As a result of adding the tackifier of the formula (1) to the ultrasonic gel composition, the gel composition for ultrasonic inspection according to the present invention has improved phase separation characteristics at high temperature and low temperature, changed the tack plasticity index, It got better.

Further, the gel composition for ultrasonic inspection has an advantage of improving the flow-down phenomenon at high temperature, and also improving storage stability and workability.

Hereinafter, the present invention will be described in more detail with reference to examples, production examples and accompanying drawings. The embodiments of the present invention may be modified in various forms, and the scope of the present invention should not be construed as being limited to the following embodiments. This embodiment is provided to more fully illustrate the present invention to those skilled in the art. It is to be understood that the terminology used herein is for the purpose of describing preferred embodiments of the present invention.

The gel composition for ultrasonic examination according to the present invention comprises 0.5 to 0.7% by weight of a binder, 0.1 to 0.4% by weight of a tackifier of Formula 1, 1.0 to 1.5% by weight of a neutralizer, 1.2 to 2.6% by weight of a moisturizer, By weight, and 95.0 to 97.0% by weight of distilled water.

[화학식 1]

[Chemical Formula 1]

Wherein n is from 10,000 to 60,000,

A is -COOH or -COOR, the molar ratio of -COOH / -COOR is 7/3 to 8/2,

R is C ₁₈ H ₃₅ -O- (CH ₂ -CH ₂ -O-) _m -CH ₂ -CH ₂ -

and m is 4 to 11.

As a binder which is one of constituent components of the gel for ultrasonic inspection, carboxymethylcellulose (CMC), sodium carboxymethylcellulose, polyvinylpyrrolidone, polyvinylpyrrolidone, polyvinylpyrrolidone and polyvinylpyrrolidone, which are soluble in water and have a large number of reactive carboxyl groups (-COOH) Acrylic acid or the like can be used. These have a large number of carboxyl groups and have high tackiness when swollen in water. An appropriate amount of the binder to be used is preferably from 0.5 to 0.7% by weight in the gel composition. When the content is less than 0.5% by weight, the viscosity of the mixture is low and the gel coat is too thin when applied. When it exceeds 0.7% by weight, It falls out. Examples of usable binders include HK-940, 941, HV-501, 504, 505, and Carbomer 934, 940, and 941 of RUBRIZOL C0, available from Sumitomo Seika Chemical Co.,

Generally, the tackifier uses a lot of cellulose system which exhibits sticky properties when it is pulverized in water. Examples of the solvent include hydroxypropyl methyl cellulose, ethyl cellulose, hydroxy ethyl cellulose, methyl cellulose hydroxy propyl cellulose, pectin , Starch, carboxyl vinyl polymer, and the like.

However, in the present invention, the tackifier as shown in the formula (1) is directly used for the esterification reaction of polyoxyethylene oleyl ether, which is a higher alcohol such as the formula (3) Modified alcohol-modified polyacrylic acid.

[화학식 2]

(2)

 In the above formula, n is 10,000 to 60,000.

[화학식 3]

(3)

In the above formula, n is 5 to 12.

The compound of Formula 3 may be obtained by reacting polyoxyethylene with oleyl alcohol. Since it contains an oleyl alcohol having an unsaturated double bond in the molecule, it does not crystallize at a relatively low temperature and exhibits a smooth flow characteristic. Examples of usable polyoxyethylene oleyl ether include MONOPOL-OACE5, MONOPOL-OACE8 and MONOPOL-OACE9 from Dongnam Chemical Co., Ltd. and Koremul-OE5, Koremul-OE7 and Koremul-

However, the conventional gel, which is usually a salt made by mixing polyacrylic acid and an alkali, is not smooth at a low temperature of 10 DEG C due to excessive hydrogen bonding, and exhibits a rigid flow state. When an external force is applied, there is a problem that the fluid initially does not move well and suddenly moves after a certain period of time.

Such hydrogen bond-forming salts exhibit a phenomenon in which the hydrogen bonding force between acid and base is deteriorated at a temperature higher than 40 ° C, and this phenomenon actually deteriorates the workability of a gel requiring a constant film thickness. In addition, since the electrostatic hydrogen bonding force is weakened due to the temperature rise during coating at a temperature of 35 ° C or higher or in a case of a patient having a high fever, a relatively thin gel film is formed, and therefore, the non-ideal scattering or leakage And the result of the correct inspection can not be expected.

In order to solve the above-mentioned disadvantages, the tackifier of the formula (1) obtained by reacting the polyacrylic acid of the formula (2) with the polyoxyethylene oleyl ether of the formula (3) is added to the gel composition.

More specifically, the polyacrylic acid of formula (2) has a molecular weight of 1,000,000 to 4,000,000 and a repeating unit (n) of 10,000 to 60,000. 20 to 30% of the carboxyl groups present in the polyacrylic acid are dissolved in a hydroxyl group (-OH) at the end of the polyoxyethylene oleyl ether of formula (3) and N, N-dimethylformamide as a solvent, For 2 to 5 hours under a catalyst such as paratoluene sulfonic acid, sulfuric acid, nitric acid, zinc acetate or the like to obtain a tackifier of the formula (1).

Since the tackifier is partially converted to a higher alcohol chain in polyacrylic acid, it exhibits a decrease in the hydrogen bonding force, the development of the steric hindrance property by the generated side chain, the change of the solubility index to water, and the change of the mixing property. Ultimately, these factors can lead to visible changes in viscosity, flow, water solubility, spreadability at high temperature, and storage stability.

When the tackifier of the above formula (1) is mixed with the gel composition, the mixing characteristics of the gel composition are improved by incorporating polyoxyethylene oleyl ether as a surfactant. Specifically, the phase separation characteristics at high temperature and low temperature are improved, and the thixotropy index is lowered, so that workability is improved when used. Also, the flow-down at high temperature is improved, and storage stability and workability are also improved. For this reason, it is possible to control the abrupt slip phenomenon, which is caused by the breakdown of hydrogen bonds when receiving an external force at a low temperature of 10 ° C., and to improve the film thickness thinning and streaking phenomenon caused by weak hydrogen bonding at a high temperature of 40 ° C. .

Further, in the reaction between the polyacrylic acid of the general formula (2) and the polyoxyethylene oleyl ether of the general formula (3), the molecular weight of the polyacrylic acid, the kind of the polyoxyethylene oleyl ether and the content ratio of -COOH / It is possible to control the thixotropy index which affects the oil ratio (HLB) value, solubility in water, and workability. If the amount of the tackifier is 0.1 to 0.4% by weight, the amount of the polyoxyethylene oleyl ether to be added is small so that the gel flowability, thixotropy index and storage stability are improved. And if the amount exceeds 0.4% by weight, the hydrogen bonding force is excessively reduced, and the workability is likewise deteriorated.

As the neutralizing agent, sodium hydroxide (NaOH), potassium hydroxide (KOH), triethanolamine, diethanolamine and the like which are basic and soluble in water can be used. If the amount is less than 1.0% by weight, hydrogen bonds are less formed between the base and the acid, and the viscosity of the mixture is lowered, resulting in poor workability. The amount of unreacted base is increased, which can lead to toxicity to the human body.

The neutralizing agent forms a water-soluble salt by acid-base neutralization reaction when it is contacted with an acidic binder in water, and the aqueous solution containing the salt has a high viscosity and low flowability. The aqueous solution in which the salt is dissolved exhibits the characteristics of a non-newtonian fluid, among which the characteristic of a pseudoplastic fluid. That is, when the external force continues to be applied to the liquid, the flow velocity increases exponentially. This is because the carboxyl group (-COOH) of the organic acid and the hydroxyl group (-OH) or the amine (= NH) of the base meet with each other in the water to form a hydrogen bond. Hydrogen bonds are electrically hydrogen atom and d represents the charged of d ^{+ -} electrically electrostatic attraction generated when the hayeoteul atoms to each other band voice such as nitrogen (N), halogen, oxygen (O) indicating the charged . This attraction is not a real coupling, so gravity works when hydrogen (H) and oxygen (O), which are opposite to each other, are close to each other.

On the other hand, at the time of ultrasonic examination, the flow characteristics of the gel appearing due to the formation and breaking of hydrogen bonds in the gel are utilized. When the gel is applied to the skin and the probe is moved over it, the hydrogen bond breaks and slides smoothly, making movement smooth. However, when the probe is stopped, the gel recovers hydrogen bonds and stops flowing.

As the moisturizing agent, it is preferable to use ethylene glycol, propylene glycol, glycerin or the like. A proper amount of the surfactant is 1.2 to 2.6% by weight. When the content of the surfactant is less than 1.2% by weight, the moisture contained in the gel composition is evaporated during testing, thereby forming a hard gel film on the surface of the skin. In addition, when the content exceeds 2.6% by weight, there is a large amount of residue in the skin after the test, thereby deteriorating the cleanliness of the skin.

As the preservative, it is preferable to use methylparaben (MP), ethylparaben (EP), butylparaben (BP), sodium benzoate and the like. When the content is less than 0.1% by weight, the preservative effect is not exhibited. When the content is more than 0.3% by weight, the residue remains in the human body, thereby deteriorating the cleanliness of the skin.

As the solvent, it is preferable to use tertiary distilled water (TDW) in which ions are removed by ion exchange or electrical method. The amount of the solvent used is not particularly limited except for the total added amount of binder, tackifier, neutralizing agent, humectant, As the remainder, the appropriate amount used is 95.0-97.0 wt% of the total components. When the amount is less than 95.0% by weight, fluidity is deteriorated. When the amount is more than 97.0% by weight, there is a problem that the gel is caused to flow down.

(1) 0.5 to 0.7% by weight of a binder and 0.1 to 0.4% by weight of a tackifier of formula (1) are added to 95.0 to 97.0% by weight of distilled water, Stirring for 2 hours at ~ 50 rpm; 2) a second step of adding 0.1 to 0.3% by weight of a preservative and 1.2 to 2.6% by weight of a moisturizer to the mixed solution stirred in the first step, and stirring the mixture at room temperature and 10 to 40 rpm for 10 minutes; 3) a third step of adding 1.0 to 1.5% by weight of a neutralizing agent to the mixed solution stirred in the second step, stirring the mixture at room temperature, 10 to 20 rpm for 20 minutes, and removing bubbles in vacuum.

≪ Preparation Example > Preparation of tackifier

50 g of polyacrylic acid HK-940, 86 g of polyoxyethylene oleyl ether, Monopol-OACE 5, 1300 g of N, N-dimethylformamide as a solvent and 1 g of para-toluene sulfonic acid as a catalyst were charged in a reactor, And the mixture was stirred at 100 rpm to cause a condensation reaction. When the acid value of the solution became 20 or less, N, N-dimethyl formamide was removed by vacuuming at a pressure of 10 torr or more,

Hereinafter, the process of preparing a gel for ultrasonic inspection using the tackifier obtained in the above Preparation Example will be described in more detail with reference to Examples and Experimental Examples.

<Examples>

As shown in Table 1, the amounts of the raw materials were set, and then the solvent, the binder and the tackifier were added to the mixer, and the mixture was stirred at room temperature for 2 hours at a rotation speed of 30 rpm. Visually, the binder and the tackifier were completely solved in the solvent. Next, a humectant and preservative were added, and the mixture was stirred at room temperature for 10 minutes at a rotation speed of 20 rpm, and visually confirmed whether the mixture was well mixed. Then, a neutralizing agent was added and mixed at room temperature for 20 minutes at a rotation speed of 15 rpm. When the gel composition was judged to be well mixed, a vacuum was applied at a vacuum of 10-20 torr to remove the bubbles contained in the gel composition as much as possible. The gel composition thus prepared was sealed and stored in a cool dark place.

Percentage of each component Raw material name practice
Example 1 practice
Example 2 practice
Example 3 practice
Example 4 practice
Example 5 practice
Example 6 practice
Example 7 practice
Example 8 compare
Example 1 compare
Example 2 CMC 0.60 0.65 0.75 0.45 0.55 0.60 0.55 0.60 0.60 0.55 Tackifier
(Formula 1) 0.30 0.20 0.09 0.50 0.30 0.08 0.30 0.32 HEC 0.28 HPMC 0.30 NaOH 1.20 1.30 1.30 2.00 0.09 1.60 1.20 0.09 1.30 1.40 EG 1.40 2.00 1.50 2.00 2.00 1.00 2.80 2.70 2.00 1.50 BP 0.15 0.20 0.20 0.20 0.10 0.30 0.15 0.15 0.20 0.20 Distilled water 96.35 95.65 96.16 94.85 96.96 96.42 95.00 96.14 95.62 96.05 system 100 100 100 100 100 100 100 100 100 100

<Experimental Example>

The physical properties of the gel compositions prepared in Examples 1 to 8 and Comparative Examples 1 and 2 were tested as follows. The results are shown in Table 2.

1) Viscosity

   B-type viscometer (manufactured by Brook Field Co.). 6 to 6 rpm.

2) Ticks plasticity index

   Spindle No. 6 was measured at a viscosity ratio of 3 rpm / 12 rpm.

3) Specific gravity

  And were measured with a sickle cell.

4) Spreadability

  A cylindrical hollow having an inner diameter of 20 mm was placed on a glass plate, and 10 g of a sample was placed therein. After removing the cylinder, the cylinder was placed in a 40 캜 drying oven and 10 minutes later, the spread of the droplet was investigated as a ratio to the first diameter.

5) High temperature storage stability

  50 g of a sample was placed in a glass cylinder having a diameter of 20 mm and a length of 100 mm, and the sample was placed vertically and placed in a 40 ° C. drying furnace.

6) Resolution

  The images were analyzed by an ultrasound tester (manufactured by Aquasonic Co., USA).

7) Toxicity

   A 500-won coin size was applied near the cuff or armpit for 60 minutes in the morning and afternoon, followed by itching, red spot, and inflammation.

<Analysis of experimental results>

In the case of Examples 1 and 2 in which the tackifier of Formula 1 according to the present invention was added in the range of 0.1 to 0.4% by weight, the gel compositions prepared in Examples 3 to 8 and Comparative Examples 1 and 2, In particular, no toxicity was observed in human toxicity test results.

While the present invention has been described with reference to exemplary embodiments and examples thereof, it is to be understood that the invention is not limited to those precise embodiments and various changes and modifications may be made without departing from the scope of the present invention. I will understand. Accordingly, it should be apparent that the true scope of the present invention is defined by the following claims.

Claims (12)

0.5 to 0.7% by weight of a binder, 0.1 to 0.4% by weight of a tackifier represented by the formula (I), 1.0 to 1.5% by weight of a neutralizing agent, 1.2 to 2.6% by weight of a moisturizer, 0.1 to 0.3% by weight of a preservative, %, Based on the total weight of the gel composition.

[Chemical Formula 1]
Wherein n is from 10,000 to 60,000,
A is -COOH or -COOR, the molar ratio of -COOH / -COOR is 7/3 to 8/2,
R is C ₁₈ H ₃₅ -O- (CH ₂ -CH ₂ -O-) _m -CH ₂ -CH ₂ -
and m is 4 to 11.
The method according to claim 1,
Wherein the binder is any one selected from the group consisting of polyacrylic acid, carboxymethylcellulose, and sodium carboxymethylcellulose.
The method of claim 2,
Wherein the tackifier is prepared by reacting a polyacrylic acid of formula (2) with a polyoxy-ethylene oleyl ether of formula (3).

(2)
In the above formula, n is 10,000 to 60,000.

(3)
In the above formula, n is 5 to 12.
The method of claim 3,
Wherein the neutralizing agent is any one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), triethanolamine, and diethanolamine.
The method of claim 4,
Wherein the humectant is any one selected from the group consisting of ethylene glycol, propylene glycol, and glycerin.
The method of claim 5,
Wherein the preservative is any one selected from methylparaben, ethylparaben, butylparaben, and sodium benzoate.
1) a step of adding 0.5 to 0.7% by weight of a binder and 0.1 to 0.4% by weight of a tackifier of formula (1) to 95.0 to 97.0% by weight of distilled water and stirring at room temperature and 50 rpm for 2 hours;
2) a second step of adding 0.1 to 0.3% by weight of a preservative and 1.2 to 2.6% by weight of a moisturizer to the mixed solution stirred in the first step, and stirring the mixture at room temperature and 10 to 40 rpm for 10 minutes;
3) a third step of adding 1.0 to 1.5% by weight of a neutralizing agent to the mixed solution stirred in the second step, stirring the mixture at room temperature, 10 to 20 rpm for 20 minutes, and removing bubbles in vacuum. Gt; &lt; / RTI &gt;

[Chemical Formula 1]
Wherein n is from 10,000 to 60,000,
A is -COOH or -COOR, the molar ratio of -COOH / -COOR is 7/3 to 8/2,
R is C ₁₈ H ₃₅ -O- (CH ₂ -CH ₂ -O-) _m -CH ₂ -CH ₂ -
and m is 4 to 11.
In addition, the compounding ratio (% by weight) of the components in the first to third steps is calculated on the basis of the gel composition produced through the third step.
The method of claim 7,
Wherein the binder is any one selected from the group consisting of polyacrylic acid, carboxymethylcellulose, and sodium carboxymethylcellulose.
The method of claim 8,
Wherein the tackifier is produced by reacting a polyacrylic acid of formula (2) with a polyoxyethylene oleyl ether of formula (3).

(2)
In the above formula, n is 10,000 to 60,000.

(3)
In the above formula, n is 5 to 12.
The method of claim 9,
Wherein the neutralizing agent is any one selected from the group consisting of sodium hydroxide (NaOH), potassium hydroxide (KOH), triethanolamine, and diethanolamine.
The method of claim 10,
Wherein the humectant is any one selected from the group consisting of ethylene glycol, propylene glycol, and glycerin.
The method of claim 11,
Wherein the preservative is any one selected from methylparaben, ethylparaben, butylparaben, and sodium benzoate.