JPH10204234A - Polyisobutylene emulsion with improved stability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion that has increased stability without deterioration in emulsifiability for a long period of time, even under acidic or elevated- temperature conditions and is useful as a base for pressure-sensitive adhesive, binder, agrochemical or waterproof agent for fiber or woven fabric. SOLUTION: This polyisobutylene emulsion comprises (A) 100 pts.wt. of polyisobutylene with a viscosity-average molecular weight of 10,000-70,000, (B) 1-30 pts.wt. of polyoxyethylene-oxypropylene block copolymer wit a number - average molecular weight of 1,500-80,000, (C) 0.1-5 pts.wt. of polyoxyethylene alkyl ether sulfate ester salt or, in addition, (D) 0-2 pts.wt. of stabilizers where the solid content is 1-75wt.% and the rest is water in the emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyisobutylene emulsion having improved stability, and more particularly to an aqueous emulsion containing a polyisobutylene having a viscosity average molecular weight of 10,000 to 70,000, comprising an adhesive, a binder and a binder. And polyisobutylene emulsions with improved stability, useful as bases for agricultural chemicals, textile or textile waterproofing agents and the like.

[0002]

2. Description of the Related Art Polyisobutylene is a hygiene-safe compound, and is used as a base material for cosmetics, for example, hair styling agents, lotion creams, and medical supplies, for example,
It is used as an adhesive base polymer for haptics. When used in such applications, for example, when applying polyisobutylene to a substrate, the emulsion type is easier to operate. The higher the molecular weight of polyisobutylene, the easier it is to use the emulsion type, which is desirable.

[0003] Here, various kinds of compounding agents are further compounded into the emulsion as a base material to produce cosmetics and medical supplies as described above. Alternatively, the emulsifying performance of the emulsifier tends to change, and in some cases, phase separation may occur.

For example, depending on the use of the emulsion,
Preservatives, antibacterial agents, antifungal agents, and the like may be added as a compounding agent, and some of them may reduce their efficacy unless they are acidic. In such a case, an acid such as hydrochloric acid, citric acid, or acetic acid is blended as a pH adjuster. In addition, since the chemicals to be blended have acidity, the emulsion may be acidic as a result.
In addition, in the case of use of cosmetics, there are some in which weak acidity is preferred. In order to eliminate the effects of various compounding agents including such acidic substances, it is naturally important to form a stable emulsion. However, as described above, there are various compounding agents in the compounding agent. It is not easy to test the stability by actually blending.

On the other hand, the present inventors have found that when the particle size of the polyisobutylene emulsion is small, particularly when it is as small as about 1 μm, it is effective to eliminate the influence of the various additives added thereafter on the emulsion particles. In addition, it has been found that, when a product is obtained by adding various compounding agents, the effect of the compounding agent can be expected to be more preferably exerted.

In view of the prior art from this viewpoint, an emulsion using a sucrose fatty acid ester and a polyalkylene glycol monoalkyl ether as an emulsifier (JP-A-58-208341), a sucrose fatty acid ester and a polyoxyethylene sorbitan monoester Emulsions using fatty acid esters or branched dodecylbenzenesulfonates (Japanese Unexamined Patent Publication (Kokai) No. 59-122534) are not preferred because their emulsion particle size is relatively large.

[0007]

As a method of reducing the particle size of the emulsion, there is a method of increasing the shearing force by using a machine. However, even if the particle size is reduced by such a method, the emulsifier on the surface of the emulsion particles may be used. , The emulsifier does not have a sufficient effect, and consequently agglomeration occurs, resulting in a large particle size.

[0008] Even if a large amount of emulsifier having a low emulsifying power is used, self-aggregation and self-emulsification of the emulsifier cause
The concentration of the emulsifier on the surface of the emulsion particles does not increase,
Eventually, the particle size of the emulsion cannot be reduced. Therefore,
The emulsifier must be used in an appropriate amount. Also,
When reducing the particle size, the choice of emulsifier is extremely important.

[0009] An object of the present invention is to reduce the particle size of an emulsion, and to provide a viscous solution that does not lose its emulsifying performance over a long period of time even under acidic conditions or high temperature conditions. It is an object of the present invention to provide an emulsion with improved stability, useful as a base for adhesives, binders, pesticides, textile or textile waterproofing agents and the like.

[0010]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that polyisobutylene having a specific viscosity average molecular weight, polyoxyethylene oxypropylene block having a specific number average molecular weight, A polyisobutylene emulsion containing a polymer and polyoxyethylene alkyl ether sulfate at a specific ratio, or a polyisobutylene emulsion further containing an emulsion stabilizer at a specific ratio has a small emulsion particle size, and is found to have good stability. The present invention has been completed.

That is, the invention of claim 1 of the present invention comprises: (A) 100 parts by weight of polyisobutylene having a viscosity average molecular weight of 10,000 to 70,000; and (B) polyoxybutylene having a number average molecular weight of 1,500 to 80,000. Ethylene oxypropylene block polymer 1 to 30 parts by weight (C) 0.1 to 5 parts by weight of polyoxyethylene alkyl ether sulfate salt Solid content of 1 to 75% by weight and stability of water remaining as water An improved polyisobutylene emulsion.

The invention of claim 2 of the present invention comprises: (A) 100 parts by weight of polyisobutylene having a viscosity average molecular weight of 10,000 to 70,000; and (B) polyoxyethylene oxide having a number average molecular weight of 1,500 to 80,000. 1 to 30 parts by weight of a xypropylene block polymer; (C) 0.1 to 5 parts by weight of a polyoxyethylene alkyl ether sulfate; (D) 0 to 2 parts by weight of a stabilizer; The balance is a polyisobutylene emulsion with improved stability consisting of water.

Further, the invention of claim 3 of the present invention is characterized in that (A) 100 parts by weight of polyisobutylene having a viscosity average molecular weight of 10,000 to 70,000, and (B) polyoxybutylene having a number average molecular weight of 1,500 to 80,000. Ethylene oxypropylene block polymer 1 to 30 parts by weight (C) 0.1 to 5 parts by weight of polyoxyethylene alkyl ether sulfate ester salt (D) 0.1 to 2 parts by weight of solid component consisting of 1 to 75 parts by weight % Polyisobutylene emulsion with the balance being water and the balance being water. Hereinafter, the present invention will be further described.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The polyisobutylene of the component (A) used in the present invention is a product obtained by mainly polymerizing isobutylene, and may be obtained by copolymerizing butene-1 or the like. It is a viscous semi-solid polymer. Such polyisobutylene may be obtained by polymerizing isobutylene in a solvent such as hexane, or by using a C4 fraction from FCC (fluid catalytic cracking) in petroleum refining containing isobutylene or a C4 fraction from naphtha crackers in petrochemicals. Those obtained by polymerization with a Friedel-Crafts catalyst such as aluminum chloride and boron fluoride can be used.

The polyisobutylene (A) used in the present invention has a viscosity average molecular weight of 10,000 to 70,
000 range. When the viscosity average molecular weight exceeds 70,000, it is difficult to form an emulsion, and when the viscosity average molecular weight is less than 10,000, the emulsion becomes unstable depending on acidic conditions or chemicals used, which is not preferable.

As the polyisobutylene of the component (A) used in the present invention, as long as it is a liquid or viscous semi-solid and has a viscosity-average molecular weight within the above range, it is comparatively low with rubber-like polyisobutylene which is a solid at room temperature. It is also possible to use a mixture of polyisobutylene having a high molecular weight or polybutene, which is a relatively low molecular weight polymer mainly composed of isobutylene.

The polyoxyethylene polyoxypropylene block polymer of the component (B) used in the present invention is:
It is a block polymer having at least an ethylene oxide polymer block portion and a propylene oxide polymer block portion in one molecule, and examples thereof include a polymer represented by the following general formula (1).

[0018]

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However, the number average molecular weight of the above block polymer is 1,500 to 80,000, preferably 10,000.
00 to 30,000. Outside this range, that is, the number average molecular weight is less than 1,500, or 80,000.
If it exceeds 30, it is not preferable because sufficient emulsion stability cannot be obtained.

The polyoxyethylene polyoxypropylene block polymer (B) used in the present invention comprises:
1 to 100 parts by weight of the polyisobutylene of the component (A)
Used in the range of ３０30 parts by weight. If the amount of the polyoxyethylene polyoxypropylene block polymer (B) is out of this range, that is, less than 1 part by weight, or more than 30 parts by weight, sufficient emulsion stability cannot be obtained, which is preferable. Absent.

The polyoxyethylene alkyl ether sulfate salt of the component (C) used in the present invention is obtained by sulfating an ethylene oxide adduct such as an alkylphenol such as nonylphenol or a higher alcohol such as lauryl alcohol, and then adding the sulfate ester salt. It is manufactured by doing. Examples of the sulfate ester salt include an alkali metal salt such as sodium, an ammonium salt, and the like. Although the number of moles of ethylene oxide added is not particularly limited, it is usually in the range of 1 to 20 in many cases.

Examples of the component (C) polyoxyethylene alkyl ether sulfate used in the present invention include:
A polyoxyethylene alkyl ether sulfate ammonium salt represented by the following general formula (2) can be exemplified as a more preferable one.

[0023]

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In the above formula (2), those in which R contains an aromatic group are particularly preferred, and specific examples thereof include ammonium polyoxyethylene alkylphenyl ether sulfate.

As described above, the polyoxyethylene alkyl ether sulfate salt of the component (C) is obtained by sulfating an alkyl oxide such as nonylphenol or an ethylene oxide adduct such as a higher alcohol such as lauryl alcohol by a conventional method. It can be produced by forming an ester salt. For sulfation, sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfuric anhydride and the like are used. The obtained sulfate can be neutralized with a metal hydroxide such as sodium hydroxide, aqueous ammonia or the like to form a salt by a conventional method. By reacting with sulfamic acid or the like, an ammonium salt can be directly produced.

The polyoxyethylene alkyl ether sulfate salt of the component (C) used in the present invention is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polyisobutylene of the component (A).
Used in parts by weight. Outside this range, that is, less than 0.1 parts by weight or more than 5 parts by weight is not preferable because sufficient emulsion stability cannot be obtained.

The polyisobutylene emulsion of the present invention can be used with only the above-mentioned components (A) to (C) because the emulsion particle size becomes sufficiently small. However, when an emulsion stabilizer is used in combination as the component (D), an emulsion whose emulsifying performance does not deteriorate over a long period of time can be obtained even under acidic conditions or high temperature conditions.

The stabilizer of the component (D) used in the present invention includes:
The emulsion itself does not usually exhibit emulsifying performance, but the addition thereof increases the stability of the emulsion, and specific examples include polysaccharides such as xanthan gum. This xanthan gum is Xanthomonas Compe separated from cabbage.
This is the name of polysaccharides produced by Strist and used in food additives, medicines, thickeners, dispersants, suspending agents, emulsion stabilizers and the like.

The stabilizer of component (D) used in the present invention, for example, xanthan gum, is used in an amount of 0 to 2 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of polyisobutylene of component (A).
Used in the range of 1 to 2 parts by weight. Outside this range, that is, more than 2 parts by weight is not preferable because sufficient emulsion stability cannot be obtained.

In the emulsion of the present invention, water is blended so that the emulsified solid content is 1 to 75% by weight based on the total of the components (A) to (D) and water, and the remainder is water. .

The emulsion of the present invention can be produced by a conventionally known production method. For example, if an example is given, heating to an appropriate temperature of about 25 to 60 ° C.
The component polyisobutylene and the two emulsifiers of the components (B) and (C) are mixed. At this time, the emulsifiers of the component (B) and the component (C) may be separately mixed one by one or simultaneously. Thereafter, the emulsion of the present invention can be obtained by gradually adding water while stirring. Further, after mixing the emulsifier of the component (B) or the component (C) alone with the polyisobutylene of the component (A), water may be added for emulsification, and after emulsification, the remaining other emulsifier may be mixed.

In the present invention, the component (D) such as a stabilizer or an additive may be blended before or after emulsification. Also,
It may be previously mixed with water or added during emulsification. Furthermore, in the emulsion production of the present invention,
The polyisobutylene of the component (A) may be mixed with one emulsifier of the component (B) or the component (C), and the other emulsifier may be mixed with water. In this case, it is preferable that the lower HLB is on the polyisobutylene side of the component (A), and the higher HLB is on the water side.

In the production of the emulsion of the present invention,
If necessary, not only a simple stirrer but also a planet stirrer, a universal turbine mixer, a colloid mill, a homogenizer and the like can be used.

The smaller the average particle size of the emulsion of the present invention, the better.
3 μm or less, preferably 0.1 to 1.2 μm or less.

These average particle diameters can be measured by an analytical method such as a centrifugal sedimentation method, a light diffraction stirring method, an electric resistance method, and a photon correlation method. It can be easily measured.

The emulsion of the present invention is an emulsion having an improved stability which exists stably for a long period of time.
It shows its true value especially when additives such as preservatives, bactericides, antibacterial agents, antibacterial agents, and pH regulators are blended, and even when these additives are blended, it has excellent long-term stability.

Additives added to make the emulsions of the present invention acidic or incorporated into the emulsions of the present invention because they themselves are acidic, so that the additives that render the emulsions of the present invention acidic are: Details are described in "Commentary Standards for Cosmetic Ingredients 2nd Edition" (edited by The Japanese Official Standards Association, Yakuji Nippo Co., Ltd.), "Japanese Pharmacopoeia Commentary (edited by the Japanese Official Standards Association, Hirokawa Shoten Co., Ltd.)" Have been.

Specific examples of such additives include:
For example, citric acid, citric anhydride, benzoic acid, salicylic acid, sorbic acid, dehydroacetoic acid, ascorbic acid,
Aspartic acid, isostearic acid, isosiroaminocaproic acid, undecylenic acid, erythorbic acid, oleic acid, glycyrrhizic acid, β-glycyrrhizic acid, succinic acid, tartaric acid, stearic acid, sorbic acid, lactic acid, partimic acid, glacial acetic acid, behenic acid, Myristic acid, silicic anhydride, phosphoric acid, boric acid, hydrochloric acid, and the like.

The amount of these additives varies depending on the purpose of use and application thereof, and is not particularly limited, since an amount sufficient to exert the function is used. However, it is generally used so that the total amount of the emulsion composition is about 0.01 to 5% by weight, preferably 0.05 to 1% by weight. These additives can be used alone or in combination as appropriate.
In many cases.

Examples of cosmetics using the polyisobutylene emulsion of the present invention include, for example, spray-type hair styling, mousse-type hair styling, creams, lotions and shampoos.

The hair styling materials include cationic polymers, volatile or non-volatile silicones, silicone tetrachloride (for example, trade name: ABILOUAT, manufactured by TH Goldschmidit), perfluoropolyethers (for example, trade name:
Hair conditioning agents such as FOMBLIN, [Montefluos]), protein hydrolysates and protein tetrachloride hydrolysates; antibacterial agents; antidandruff agents such as zinc pyridinethione or Octopirox;
Preservatives; viscosity modifiers; proteins; buffers; lubricants such as polyols; herbal extracts such as tea tree, ylang-ylang, jasmine, rose, sandalwood; mink oil; And other components.

The hair styling obtained by using the emulsion of the present invention imparts firmness and styling to hair.

The cosmetics such as creams and lotions include proteins, silicone oil, squalane,
Fragrance; and the like.

Examples of medical supplies using the polyisobutylene emulsion of the present invention include haptics.
The above-mentioned haptic agent contains a polymer solution such as gelatin, gum arabic, polyvinyl alcohol, methyl cellulose, etc .; a heat absorbing agent such as kaolin and bentonite; a bactericide such as boric acid; a tackifier such as rosin and ester gum; can do. When the emulsion of the present invention is used, it has appropriate adhesion to the skin, and has less dripping,
A cataplasm having improved moisture transpiration prevention and water retention is obtained.

[0045]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples unless departing from the gist of the present invention. Example 1 1000 g of polyisobutylene having a viscosity average molecular weight of 60.000, 70 g of the following (emulsifier 1), and 10 g of the following (emulsifier 2) were placed in a 5 liter kneader, and heated to a liquid temperature of 40 ° C. Stirred for minutes. Liquid temperature 40 ° C
Water was added with stirring to produce an emulsion having an emulsion solid content of 40% by weight.

(Emulsifier 1) Polyoxyethylene polyoxypropylene block polymer Trade name: Epan U-108 (Daiichi Kogyo Seiyaku) (Emulsifier 2) Polyoxyethylene alkyl phenyl ether sulfate ammonium salt Trade name: Hytenol N-08 (Daiichi Kogyo Pharmaceutical Co., Ltd.) The results of measuring the particle size of the obtained emulsion are shown in Table 1. Table 2 shows the results of measuring the stability of the obtained emulsion by the following stability test method.

[Emulsion Stability Test Method] The prepared emulsion was subjected to 9 atmospheres at room temperature, 45 ° C. and 70 ° C.
The emulsion was allowed to stand for 0 day or more, and the state of the emulsion, such as phase separation, was visually observed. Observed results were judged according to the following stability criteria. ◎: stable for 90 days or more, ：: stable for 30 days to less than 90 days, Δ: stable for 10 days to less than 30 days, □: stable for 1 to 2 days to less than 10 days, ×: phase separation immediately or within 1 day.

Example 2 An emulsion was prepared by further adding 2 g of citric acid to the emulsion of Example 1. The concentration of citric acid is 0.07% by weight. Table 1 shows the measurement results of the particle size of the obtained emulsion.
Shown in Table 2 shows the results of measuring the stability of the obtained emulsion in the same manner as in Example 1.

Example 3 150 g of (emulsifier 1)
An emulsion (emulsified solid content: 40% by weight) was produced in the same manner as in Example 1 except that (emulsifier 2) was changed to 10 g. 2 g of citric acid was further added to the obtained emulsion.
6 g of xanthan gum was added. The concentration of citric acid is 0.07% by weight. Table 1 shows the results of measuring the particle size of the obtained emulsion. Table 2 shows the results of measuring the stability of the obtained emulsion in the same manner as in Example 1.

Example 4 2 g of citric acid and 2 g of xanthan gum were added to the emulsion obtained in Example 1.
The concentration of citric acid is 0.07% by weight. Table 1 shows the results of measuring the particle size of the obtained emulsion. Table 2 shows the results of measuring the stability of the obtained emulsion in the same manner as in Example 1.

Example 5 An emulsion was produced in the same manner as in Example 1 except that (Emulsifier 1) was mixed with water and (Emulsifier 2) was mixed with polyisobutylene, and then both were mixed. 2 g of citric acid and 2 g of xanthan gum were added to the obtained emulsion. The concentration of citric acid was 0.0
7% by weight. Table 1 shows the results of measuring the particle size of the obtained emulsion. Table 2 shows the results of measuring the stability of the obtained emulsion in the same manner as in Example 1.

Comparative Example 1 An emulsion (emulsified solid content: 40% by weight) was produced in the same manner as in Example 1 except that the amount of the emulsifier (Emulsifier 1) was changed to only 70 g. Table 1 shows the results of measuring the particle size of the obtained emulsion.

Comparative Example 2 An emulsion (emulsified solid content: 40% by weight) was prepared in the same manner as in Example 1 except that the amount of the emulsifier (Emulsifier 1) was changed to only 70 g.
g citric acid was added. The concentration of citric acid was 0.1.
07% by weight. Table 1 shows the results of measuring the particle size of the obtained emulsion.

(Comparative Example 3) An emulsion was prepared in the same manner as in Example 1 except that the emulsifier of Example 1 was changed to only 70 g of (emulsifier 1). Then, 2 g of citric acid and 6 g of xanthan gum were prepared. Each was added. The concentration of citric acid is 0.07% by weight. Table 1 shows the results of measuring the particle size of the obtained emulsion.

Comparative Example 4 An emulsion (emulsified solid content: 40% by weight) was produced in the same manner as in Example 1 except that the amount of the emulsifier (Emulsifier 2) was changed to only 150 g. Table 1 shows the results of measuring the particle size of the obtained emulsion.

(Comparative Example 5) An emulsion (emulsified solid content: 40% by weight) was prepared in the same manner as in Example 1 except that the emulsifier (Emulsifier 2) was changed to only 150 g. 6 g of xanthan gum was added. In addition,
The concentration of citric acid is 0.07% by weight. Table 1 shows the results of measuring the particle size of the obtained emulsion.

Comparative Example 6 An emulsion (emulsified solid content: 40% by weight) was produced in the same manner as in Example 1 except that the following (emulsifier 3) was used in an amount of 70 g and the following (emulsifier 4) was used in an amount of 30 g. Then, each was added so that 2 g of citric acid and 6 g of xanthan gum were obtained. In addition,
The concentration of citric acid is 0.07% by weight. Table 1 shows the results of measuring the particle size of the obtained emulsion. (Emulsifier 3) Sucrose fatty acid ester Trade name: DK ester F-160 (Daiichi Kogyo Seiyaku) (Emulsifier 4) Salt of liquid dodecylbenzenesulfonic acid with triethanolamine Trade name: Neogen T (Daiichi Kogyo Seiyaku)

[0058]

[Table 1]

[0059]

[Table 2]

From Table 1, it can be seen that the polyisobutylene emulsions of Examples 1 to 5 of the present invention have an emulsion particle size of 1.0 to 1.0.
It turns out that it is as small as 1.1 μm. On the other hand, from Table 1, the emulsion particles of the polyisobutylene emulsion of Comparative Examples 1 to 5 using (Emulsifier 1) or (Emulsifier 2) alone or the polyisobutylene emulsion of Comparative Example 6 using sucrose fatty acid ester or the like were used. All diameters are 1.4
大 き く 1.8 μm, which is expected to lower the stability when compounding various additives. Also, from Table 2, it can be seen that Example 1
It is understood that the polyisobutylene emulsions of the present invention of Nos. To 5 have good stability, and that when xanthan gum is blended as a stabilizer as in the polyisobutylene emulsions of Examples 3 to 5, the stability increases even under acidic conditions and at high temperatures.

[0061]

The emulsion of the present invention has a small particle size and good compatibility between the emulsifier used and polyisobutylene, so that the emulsion stability is excellent even when various compounding agents are blended. Further, since the emulsion of the present invention has a small particle size and is excellent in dispersing the compounding agent, it can be expected that the effect of the compounding agent is also improved. Further, since the emulsion of the present invention exists stably for a long period of time at room temperature as well as at high temperature, and also exists stably under acidic conditions, it can be used as a base for adhesives, binders, pesticides, waterproofing agents for fibers or textiles, and the like. It can be suitably used as an agent.

Claims (3)

[Claims] (A) 100 parts by weight of polyisobutylene having a viscosity average molecular weight of 10,000 to 70,000 (B) 1 to 30 parts by weight of a polyoxyethylene oxypropylene block polymer having a number average molecular weight of 1,500 to 80,000 Part (C) 0.1 to 5 parts by weight of a polyoxyethylene alkyl ether sulfate salt having a solids content of 1 to 75% by weight and a balance of water, and a polyisobutylene emulsion having improved stability. 2. (A) 100 parts by weight of polyisobutylene having a viscosity average molecular weight of 10,000 to 70,000 (B) 1 to 30 parts by weight of a polyoxyethylene oxypropylene block polymer having a number average molecular weight of 1,500 to 80,000 (C) 0.1 to 5 parts by weight of a polyoxyethylene alkyl ether sulfate salt (D) 0 to 2 parts by weight of a stabilizer. Improved polyisobutylene emulsion. 3. (A) 100 parts by weight of polyisobutylene having a viscosity average molecular weight of 10,000 to 70,000 (B) 1 to 30 parts by weight of a polyoxyethylene oxypropylene block polymer having a number average molecular weight of 1,500 to 80,000 (C) 0.1 to 5 parts by weight of a polyoxyethylene alkyl ether sulfate salt (D) 0.1 to 2 parts by weight of a stabilizer The solid content is 1 to 75% by weight, and the balance is water. Polyisobutylene emulsion with improved properties.