KR0140565B1 - Manufacturing method of anti-slip material - Google Patents

Abstract

The present invention relates to a method for producing a high efficiency slipper containing a small amount of an acrylic copolymer, and more particularly, in place of the high solids latex type slipper, which has a low solids content and its glass transition temperature ( Low T _g ) makes high-adhesive and flexible acrylic latex, and separate high relative T _g to make another rigid acrylic latex, blending them in a proportion, finally neutralizing with ammonia water and making the latex blend well It maintains the stability, and relates to a method for producing a high-efficiency acrylic non-slip agent with a low solid content to have a hardness and flexibility when drying.

Description

Manufacturing method of acrylic non-slip defense agent with low solid content

The present invention relates to a method for producing a high efficiency slipper containing a small amount of an acrylic copolymer, and more particularly, in place of the high solids latex type slipper, which has a low solids content and its glass transition temperature ( Maintain stability of latex by making flexible acrylic latex with low T _g ) and separately making another acrylic latex with relatively high T _g , blending them in proportion, finally neutralizing with ammonia water and making the latex blend well And, when drying, the present invention relates to a method for producing a high-efficiency acrylic non-slip agent with low solid content, which can have both tackiness, flexibility and hardness.

Initially, the anti-slip agent composition was applied by applying hot melt adhesive to each package box made of kraft lipids in multiple lines. However, due to the strong initial adhesion when laminating the boxes, the anti-slip effect was difficult to separate during unloading. There was a disadvantage that the packaging surface was torn or stained due to too strong adhesion after separation, thereby damaging the packaging surface (Japanese Patent Laid-Open No. 1-183596 (1989)). In order to improve this, non-slip agent compositions in inorganic and organic forms have been developed. The inorganic type is a silica hydrosol containing 20 to 30% by weight of colloidal silica having a particle diameter of 10 to 20 μm, which is a liquid, which is easy to handle, and whitened after application and drying. However, the silica sol has a drawback that the anti-slip effect is reduced because the particles are too fine to distribute the particles uniformly, or difficult to apply or dry. [Canadian Patent No. 1,156,803 (1980), Japanese Patent Laid-Open Nos. 2-245086 (1990) and 4-303653 (1992). On the other hand, the organic type includes a reaction product prepared using styrene monomer and acrylic acid ester monomer as raw materials, which have a low anti-slip effect (Japanese Patent Publication No. 57-565989 (1982)). In addition, a combination of inorganic and organic materials includes a composition in which a silica powder treated with a nonionic fiber derivative and a synthetic resin binder using poly (acrylamide) as a protective colloid are dispersed in water. Although it was excellent, the performance was poor in repeated use, and in particular, there was a problem in storage stability due to poor dispersibility of the anti-slip agent itself (Japanese Patent Publication No. 59-4460 (1984)). In this regard, some tackifier resins are branded in the ethylene-vinyl acetate copolymer emulsion and additional brands of silicas, fillers, and release agents are used.However, there is a lack of anti-skidding force or the adhesiveness is too strong. Problems such as surface peeling or contamination during repeated use have been shown [Japanese Patent Application Laid-Open No. 54-65385 (1988), No. 62-70461 (1987), No. 62-110997 (1987) and No. 4-198373 ( 1992). On the other hand, the recently developed anti-slip agent is an emulsion resin made using a nonionic surfactant. Each particle is composed of a hard part, which is a nucleus part, and a soft part, which is a keratin part. There is a technical difficulty in producing a stable latex, the content of which must be increased, and this content is broken when the content is increased (Japanese Patent Laid-Open No. 4-306273 (1992)).

Accordingly, an object of the present invention is to provide a method for preparing a high viscosity slipper made of a latex compound having a low solid content, having flexibility and warning, having excellent anti-slip properties and at the same time.

Hereinafter, the present invention will be described in detail.

The present invention (1) 20 to 80% by weight of the acrylic monomer having a glass transition temperature (T _g ) of -85 ~ -5 ℃ and 20 ~ acrylic acrylic monomer having a range of 8 ~ 153 ℃ of the glass transition temperature (T _g ) by polymerizing 80% by weight oil and relatively T _g is to prepare the acrylic latex is low, (2) separate the acrylic monomer of 10 to 60% by weight in the range of the glass transition temperature (T _g) in the container 8 ~ 153 ℃ glass Emulsion-polymerization of 40 to 90% by weight of the acrylic monomer having a transition temperature (T _g ) in the range of -85 to -5 ° C produces an acrylic latex having a relatively high T _g , and (3) the acrylic latex of (1) 100 The acrylic latex of the above (2) is mixed with 5 to 60 parts by weight with respect to parts by weight, characterized in that the production method of an acrylic anti-slip agent is neutralized using ammonia water.

Referring to the present invention in more detail as follows.

The invention T _g is lower acrylic latex and a T _g higher the acrylic latex were mixed and neutralized to a certain percentage, and then, by also adding an inorganic compound, and the mixing, dispersing agents here the content of the solid component enemy eumyeonseodo excellent slip properties It relates to a method for producing an acrylic slipper.

Referring to the manufacturing process of the acrylic anti-slip agent according to the invention in more detail as follows.

In the present invention, in order to produce a flexible acrylic latex, the glass transition temperature (T _g ) was emulsified and polymerized around acrylic monomers (viscosity: 10-30 cps) having a low -85 to -5 ° C. It acts to give adhesion. Specific examples of such acrylic monomers include ethyl acrylate, n-butyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl acrylate and One kind or two or more kinds selected from hydroxypropyl acrylate and the like can be used in combination. In producing the low T _g acrylic latex, T _g is -85 ~ -5 ℃ range of acrylic monomer is 20 to 80% by weight, and preferably contained, and if the the content is less than 20% by weight when synthetic emulsion polymer On the other hand, when the monomer content exceeds 80% by weight, the cohesive force is high due to the formation of a flexible solid substance when the monomer content exceeds 80% by weight. Lack of anti-slip effect.

In order to prepare a stable acrylic latex, a water-soluble cellulose thickener for good dispersion in a reaction solvent is used, specifically, in methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and hydroxypropyl methyl cellulose. One kind or two or more kinds selected may be used in combination, and the amount thereof is 0.05 to 20 parts by weight based on 100 parts by weight of water as a polymerization solvent.

In general, in the case of emulsion polymerization of a small amount of monomer, if the content of the thickener for dispersing is too small, it is difficult to form emulsion latex and it is difficult to form emulsion. However, when this thickener was used within the above range with respect to the reaction solvent, the reaction solution was thickened, so that the monomer in the liquid phase was dispersed well, and stable latex polymerization was shown. The acrylic crab latex thus prepared had good storage stability, and showed a good anti-slip effect even when the solid content of the latex was small. If the content of the thickener for dispersing is less than 0.05 part by weight, there is no dispersion effect due to thickening, and there is a problem in that the emulsion polymerization is not well performed. On the other hand, if the content of the thickener for dispersing is more than 20 parts by weight, the viscosity of the solution becomes high and thus dispersibility This deterioration and uniform emulsion polymerization was not well achieved.

In order to impart hardness to the anti-slip agent according to the present invention, another acrylic latex having a relatively high T _g is mixed with the acrylic latex prepared above, and the acrylic latex has a monomer having a T _g of 8 to 153 ° C. Some chain transfer agents were used to produce emulsion polymerization. Specific examples of such monomers include methyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylamide and diacetone acrylamide. , 1 or 2 or more types selected from, for example, glycidyl methacrylate, styrene, vinyl acetate and acrylonitrile can be used in combination. The T _g is in the manufacture of high acrylic latex, T _g is 8 ~ 153 ℃ range of acrylic monomer is preferably contained 10 to 60% by weight, and if, when the content is 10% by weight is less than force of the slip agent itself ( Weakness, and when the monomer content exceeds 60% by weight, the tackiness is significantly reduced, and the anti-slip property is lost.

In the present invention, the emulsion polymerization was maintained at a stirring speed of 100 to 300 rpm under a nitrogen atmosphere of 50 to 80 ° C., and a water-soluble radical initiator was used as the polymerization initiator. Specifically, ammonium persulfate, potassium persulfate, and 4 were used. , 4'-azobis-4-cyanopentanoic acid, azobisisobutiamidine, calories peroxide, hydrogen peroxide, cumene hydrofooxide, etc., and the amount thereof is 0.02 to 5 based on 100 parts by weight of the total amount of the multimer used. The parts by weight were suitable and the reaction rate was very slow when used less than the above range, and stable latex was not obtained when they were used a lot. Divinylbenzene, metal salt, butyl melamine, di- or tri-urethane acrylate, trimetholpropane trimethacrylate, N, N'-methylenebisacrylamide, and the like were used as the crosslinking agent. the total amount was 100 parts by weight of ^{0.2 × 10 -3 ~ 5 × 10} -3 parts by weight, relative to, if the amount is out of the range was reduced the viscosity of the slip agent. In addition, monomers having various carboxyl functional groups were used in the emulsion polymerization in order to impart adhesion to the non-slip agent, and the monomers used were one or two selected from acrylic acid, methacrylic acid, maleic acid and itaconic acid. The above was used together and the content is 0.05-7 weight part with respect to 100 weight part of monomer total amounts used for emulsion polymerization. At this time, when the content of the monomer having a functional group is less than 0.05 parts by weight, there is a lack of adhesion due to the lack of adhesion, and when it exceeds 7 parts by weight, the acid is added and the emulsion polymerization state becomes unstable and agglomeration occurs. The production of the antislip agent itself has been difficult.

In the present invention, the surfactant used for the emulsion polymerization was used alone or in combination with anionic and nonionic surfactants, and the stability of the latex during emulsion polymerization, storage and operation was dependent on the type and amount of the surfactant. Depends heavily Anionic surfactants include sodium alkylbenzene sulfonate, sodium alkyl sulfate, sodium alkyl sulfonate, sodium dialkyl sulfonuccinate, fatty acid soap, sodium alkyl ethoxy sulfate, alkyl phenol ethoxylate, fatty acid ethoxylate, and the like. Examples of the nonionic surfactants include polyethylene glycol nonylphenyl ether, polyethylene glycol octylphenyl ether, polyethylene glycol dodecylphenyl ether, polyethylene glycol alkylaryl ether, and polyethylene glycol oleyl having a HLB (Hydrophilic Lipophilic Balance) value of 8-18. Ether, polyethylene glycol lauryl ether, polyethylene glycol alkyl phenyl ether, polyethylene glycol olefin acid ether, polyethylene glycol distearic acid ether, polyethylene glycol sorbitan monolaurate, polyethylene glycol sorbitan monostearate, polyethylene glycol alkyl ether, polyoxyethylene Lau Aryl alcohol ether, polyoxyethylene lauryl fatty acid ester, etc., and these two types of surfactants were used alone or in combination, and the amount thereof was 0.2 × 10 ^-4 to 1 × 10 ^{-2 based} on 100 parts by weight of water, the reaction solvent used. Parts by weight were suitable. When the amount of the surfactant was less than 0.2 × 10 ^-4 parts by weight, the emulsified state tended to be easily broken, and when used in excess of 1 × 10 ^-2 parts by weight, the properties of the anti-slip agent were lowered due to the good surfactant activity. .

In the present invention, a chain transfer agent is used to control the polymerization rate and flexibility, specifically, it is carbon tetrachloride, carbon tetrabromide, dodecyl mercaptan, n-butyl mercaptan, and the like, and the amount thereof is based on 100 parts by weight of the total amount of monomers used. It was 0.005 to 5 parts by weight, and if the amount used was less than the above range, the effect of addition did not occur, and in many cases, the polymerization rate was slow and the molecular weight was too small to exhibit the characteristics of the flexible resin.

We used an aqueous ammonia of 10% concentration to mixing the pH = 2 ~ 5 range of T _g is lower acrylic latex and T _g is higher ahkeul rilgye latex prepared by emulsion polymerization as described above, the pH of the neutralization is 6 8 was appropriate, and storage stability of the mixed latex was significantly lowered at other pH ranges. The mixing ratio of T _g is will be T _g is higher acrylic latex are mixed 5 to 60 parts by weight based on the acrylic latex 100 parts by weight of a lower, appeared to be little or no back mixing ratio is less than 5 parts by weight of a thickening effect, 60 wt. When the amount was exceeded, the hardness effect became too large to reduce the slipper effect.

In addition, in the present invention, inorganic compounds were added in order to further provide an anti-slip effect to the mixed solution. For example, silica powder, silica gel, glass powder, talc, clay, calcium carbonate, magnesium carbonate, zinc oxide, barium sulfate However, when silica and glass powder are used, surface coating is performed in advance with a silane coupling agent such as γ-aminopropyltriethoxysilane, γ-gridoxy propyltrimethoxysilane, and 0.5 at 80 to 100 ° C. It was used after thermal reaction for 2 hours. The amount of the inorganic compound was 0.03 to 12 parts by weight based on 100 parts by weight of the latex prepared by mixing in the above, and the amount of the inorganic compound was less than the above range had no effect.

And these anti-slip agents are kept safe by the mixing of the carboxyl functional group and the ammonia water contained in the two types of acrylic latex during storage and storage, and also during application and drying, as shown below By reaction, some imide bridge | crosslinking (German patent 868,130 (1858)) can also be achieved, and the uniform coating effect was obtained as well as the effect of obtaining mechanical strength by crosslinking.

On the other hand, in the present invention, in order to mix the latex obtained in the above and inorganic compounds other than silica, as a dispersing thickener, casein, gelatin, ammonium polyorganic acid salt, acrylic polymer aqueous solution, sodium polyacrylate, modified polyacrylate Etc., the amount was 0.05 to 5 parts by weight based on 100 parts by weight of the slipper used, less than this range was very effective, and more than this range had a problem of lowering the cohesion of the slippery itself.

The anti-slip agent produced by the manufacturing method of the present invention as described above is used, the concentration of the solid content is adjusted to the range of 2 to 10% by weight, relative to the solids (30 to 50% by weight) of the conventional anti-slip agent product In addition, the viscosity ranges from 100 to 2,000 cps. When applied to the packaging box of kraft lipids by spray method, it has a suitable viscosity, and it is easy to work, and latex does not agglomerate on the box surface. A good anti-slip effect was obtained by uniformly dispersing, applying and drying while maintaining the appropriate hardness.

Hereinafter, the present invention will be described through the following examples, which are not intended to limit the present invention.

[Examples 1-18]

In a 250 cc round flask equipped with a dropping device with a composition as shown in Table 1 (Example 6), 0.8 g of 10% by weight of polyethylene glycol nonylphenyl ether and 10% by weight of 100 parts by weight of 0.5 parts by weight of hydroxyethyl cellulose solution were added. 1.17 g of sodium alkylbenzenesulfonate, 0.17 g of ammonium persulfate, 1.64 x 10 ^-3 g of divinylbenzene, and 0.10 g of acrylic acid were added and stirred for about 30 minutes. Meanwhile, 1.17 g of methyl methacrylate, 1.17 g of butyl acrylate, 1.67 g of ethyl acrylate, and 0.08 g of carbon tetrabromide were added to a separate beaker 50 cc, and the solution was stirred and emulsified. The emulsified solution was reacted for 4 to 5 hours while dropping 1-2 drops per second into an inert atmosphere reactor (reaction temperature: 70 ° C., stirring speed: 120 rpm) with a reflux condenser through a dropping apparatus. The reaction was cooled to room temperature and neutralized to pH = 7 by addition of 12.21 g of 10% aqueous ammonia. Thereafter, 2.20 g of another acrylic latex designed and emulsified by T _g at 37.2 ° C. and 0.50 g of silica sol surface-treated with γ-aminopropyltriethoxysilane (0.05 g) were added thereto. After stirring and mixing for ˜30 minutes, this was used as a finished product.

[Comparative Examples 1-17]

0.8 g of 10% by weight of polyethylene glycol nonylphenyl ether and 1.17 g of 10% by weight of sodium alkylbenzenesulfonate in a composition as shown in Table 1 (Comparative Example 5) in the same device as Examples 1 to 18 above. 0.17 g of ammonium persulfate and 0.05 g of acrylic acid were added thereto, followed by stirring for about 30 minutes. Meanwhile, 1.17 g of methyl methacrylate, 1.17 g of butyl acrylate, 1.67 g of ethyl acrylate, and 0.08 g of carbon tetrabromide were added to a separate beaker 50 cc, and the solution was stirred and emulsified. The emulsion solution was reacted for 4 to 5 hours while dropping 1-2 drops per second into an inert atmosphere reactor (reaction temperature: 70 ° C., stirring speed: 120 rpm) with a reflux condenser through a dropping device. Was created. It is believed that this is because a small amount of the dispersion thickener that serves as a dispersion stabilizer in the reaction solution disperses a small amount of monomers in the solution non-uniformly.

On the other hand, in Comparative Examples 2 and 3, 0.65-0.80 parts by weight of hydroxyethyl cellulose was added to distilled water to obtain a uniform emulsion polymer. However, the adhesion and reuse were not good by keeping the amount of thickener low. On the other hand, to stabilize the latex solutions were neutralized in the same manner as in Examples 1 to 18. Meanwhile, as shown in Comparative Examples 13 and 14 of Table 1, when a relatively large amount of acrylic acid was added and reacted in the monomer composition, the latexes were broken and the reactants agglomerated with each other, resulting in deterioration of overall physical properties. In addition, when a large amount of methyl methacrylate was added and reacted in the monomer composition as in Comparative Example 1, the resulting polymer was too hard and the antislip effect was bad. In addition, as in Comparative Example 8, when the amount of hydroxyethyl cellulose in the monomer composition was increased, the viscosity of the solution was increased, so that the dispersion of the monomers was not well achieved and a nonuniform emulsion polymer was obtained.

a: MMA-methyl methacrylate, BA-butyl acrylate, EA-ethyl acrylate, AA-acrylic acid, MA-methacrylic acid, DVB-divinylbenzene, HEC-hydroxyethyl cellulose, all figures are distilled water Weight of each corresponding ingredient used per 100 g.

b: 10 wt% latex having a relatively high T (= 37.2 占 폚) made of styrene, butyl acrylate, methacrylic acid, or the like.

c: 30 parts by weight of silica sol.

d: Theoretically calculated by the composition of monomers alone.

e: Reusability with respect to surface damage due to strong adhesion and contamination by adhesion.

f: After spraying anti-slip and curing for 30 minutes, measure by inclination method of friction coefficient test method of paper and cardboard of Japanese Industrial Standard (JIS) P 8147.

-The weight of the stainless steel is 60mm wide, 100mm long and 1,000g in mass

-The inclination speed of the inclined plate is less than 3 ° per second

-Raise the angle of the inclined plate to measure the angle of inclination when starting to slide further.

According to the results of Table 1, in the embodiment according to the present invention by increasing the aqueous solution to a solution of a constant viscosity using hydroxyethyl cellulose, emulsion latex polymerization around the acrylic monomers of low T to obtain a stable latex In addition, it has an anti-slip effect by itself, but in order to obtain better anti-slip properties, another acrylic latex is made around an acrylic monomer having a relatively high T, and these are mixed with the former latex and silica sol, When the additives are added, it exhibits excellent anti-slip properties, so applying this anti-slip agent to a packaging box made of kraft lipids enables stable lamination storage and lamination.

Claims (6)

(1) 20 to 80% by weight of the acrylic monomer having a glass transition temperature (T _g ) of -85 to -5 ° C and 20 to 80% by weight of the acrylic monomer having a glass transition temperature (T _g ) of 8 to 153 ° C. the emulsified polymerization relative T _g is to prepare the acrylic latex is low, (2) separate the acrylic monomer of 10 to 60% by weight and a glass transition temperature in the range of the glass transition temperature (T _g) in the container 8 ~ 153 ℃ ( T _g) by the emulsion polymerization ranges -85 ~ -5 ℃ the acrylic monomer of 40 to 90% by weight relatively to the T _g acrylic latex 100 parts by weight of the high manufacturing an acrylic latex, and (3) the above (1) The acrylic latex of (2) is mixed with 5 to 60 parts by weight, but neutralized using ammonia water, the method for producing an acrylic slipper. According to claim 1, wherein the acrylic slipper, characterized in that the addition of 0.05 to 7 parts by weight of a monomer having a carboxyl functional group with respect to 100 parts by weight of the total amount of monomers in the production of the acrylic latex of the process (1) and (2) Manufacturing method. The method of claim 2, wherein the monomer having a carboxyl functional group is one or two or more selected from acrylic acid, methacrylic acid, maleic acid and itaconic acid. The method of claim 1, wherein in the step (1), the acrylic monomer having a low T _g is ethyl acrylate, n-butyl acrylate, isopropyl acrylate, 2-ethylhexyl acrylate, n-hexyl methacrylate, A method for producing an acrylic anti-slip agent, characterized in that one or two or more selected from uryl methacrylate, 2-hydroxyethyl acrylate and hydroxypropyl acrylate are used. 2. The method of claim 1, wherein (2) the acrylic latex is high in the process of T _g of methyl acrylate, methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl A method for producing an acrylic slipper comprising at least one selected from methacrylate, acrylamide, diacetone acrylamide, glycidyl methacrylate, styrene, vinyl acetate and acrylonitrile. The method of claim 1, wherein the content of the final solid content of the acrylic latex obtained in the step (3) is adjusted to 2 to 10% by weight.