WO2010104243A1 - Transparent solid glue composition and a production method for a transparent solid glue composition - Google Patents

Abstract

Disclosed is a transparent solid glue composition which uses an acrylic emulsion as a principal component, is outstandingly transparent and adhesive, and can prevent wrinkling of the object being adhered due to contraction during adhesion. The transparent solid glue composition comprises: from 30 to 70 wt.% of an acrylic emulsion; from 1 to 20 wt.% of poly(vinyl pyrrolidone); from 5 to 40 wt.% of a filler; and from 2 to 15 wt.% of water. Moreover, the acrylic emulsion preferably comprises a copolymer having a molecular weight of from 5,000 to 90,000 obtained by the polymerisation of a (meth)acrylic acid alkyl ester monomer which has an alkyl group comprising from 1 to 2 carbon atoms, a (meth)acrylic acid monomer and an acrylic acid alkyl ester monomer which has a linear or branched alkyl group comprising from 3 to 10 carbon atoms, in a ratio of 1-98 mol.% : 1-98 mol.% : 1-98 mol.%.

Description

Transparent solid paste composition and preparation method of transparent solid paste

The present invention relates to a transparent solid paste composition, and more particularly, by using an acrylic emulsion as a main component, it is excellent in transparency and adhesiveness, and is a transparent solid paste composition which can prevent wrinkles of the adherend due to shrinkage during adhesion. And a method for producing a transparent solid pool.

Since a conventional general adhesive is a liquid having a high viscosity, when the adhesive is applied to the surface to be bonded, the adhesive is hardly applied to a certain thickness, and the adhesive flows out to a portion other than the surface to be bonded, and thus the adhesive surface is not neat. In addition, the consumption of adhesive is large. In addition, since the liquid adhesive has a solid content of 5 to 10% by weight and the remainder is composed of a liquid such as a solvent or water, it takes a long time to dry, and a small amount of the adhesive component that maintains the adhesive strength after evaporation of the solvent maintains strong adhesiveness. It is difficult to do so, and as the period elapses, there is a problem in that a solvent such as water in the liquid adhesive is evaporated and solidified so that it cannot be used. In order to rectify this problem, adhesives have been gradually developed into jelly, paste, wax, and solid, and the demand for solid, ie, solid paste, among these various forms is increasing.

Conventional solid pastes use polyvinylpyrrolidone and starch as their main raw materials to produce a white opaque color. Therefore, even if foreign matters are included in the solid pastes during the manufacturing process, they cannot be found during product inspection. There is a problem that foreign substances may appear while the consumer purchases and uses the product. Therefore, when the solid pool is transparently manufactured, foreign matter in the solid pool can be visually selected in the manufacturing process and the product inspection process, thereby preventing the solid pool containing the foreign material from being produced and sold. In addition, in the case of the existing solid paste containing starch, when pasted to the adherend such as paper and dried, there is a disadvantage that the wrinkled phenomenon of the adherend due to shrinkage appears, which contains a large amount of moisture in the solid pool Is expected to occur.

It is therefore an object of the present invention to provide a transparent solid paste composition and a method for producing a transparent solid paste which are excellent in transparency and adhesiveness.

Another object of the present invention is to provide a transparent solid paste composition and a method for producing a transparent solid paste that can prevent wrinkles of the adherend due to shrinkage during adhesion and shorten the adhesion time.

In order to achieve the above object, the present invention, 30 to 70% by weight acrylic emulsion; 1 to 20 weight percent polyvinylpyrrolidone; 5 to 40 wt% filler; And it provides a transparent solid pool composition comprising 2 to 15% by weight of water.

Here, the acrylic emulsion is a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 2 carbon atoms, (meth) acrylic acid monomer and an acrylic acid alkyl ester monomer having a linear or branched alkyl group having 3 to 10 carbon atoms 1 to 98 mol It is preferable to contain the copolymer of the molecular weight 5,000-90,000 superposed | polymerized by the ratio of%: 1-98 mol%: 1-98 mol%.

In addition, the present invention, at 15 to 30 ℃, mixing 30 to 70% by weight of the acrylic emulsion, 1 to 20% by weight of polyvinylpyrrolidone and 2 to 15% by weight of water; After raising the temperature of the mixture to 40 to 60 ° C., mixing 5 to 40 wt% of the filler and 0.5 to 10 wt% of the surfactant; And raising the temperature of the mixture to 70 to 90 ° C., and then mixing 0.1 to 5 wt% of the antifoaming agent and stirring to provide a method for preparing a transparent solid pool.

The transparent solid paste composition according to the present invention has water-soluble or water-dispersible properties by using an acrylic emulsion as a main component and using polyvinylpyrrolidone. The transparent solid paste formed from the transparent solid paste composition exhibits excellent transparency and adhesion, and has a fast adhesion time of 1 to 2 minutes, compared with a conventional solid paste requiring an adhesion time (drying time) of 3 to 4 minutes. In addition, it can exhibit more than two times the initial adhesive strength, it is possible to bond the materials that can not be bonded to the existing solid glue, such as fabric, leather, wood (but permanent bonding is impossible). In addition, when glued by glue, wrinkles due to shrinkage of the adherend such as paper is significantly reduced, pH of 9 to 14 can prevent the acidification of the solid pool and environmentally friendly, children's stationery pool, office pool, etc. Useful as

Hereinafter, the present invention will be described in detail.

The transparent solid paste composition according to the present invention comprises an acrylic emulsion, polyvinylpyrrolidone, a filler and water. As the acrylic emulsion used in the present invention, an acrylic emulsion having water-soluble or water-dispersibility may be used as the adhesive and adhesive component of the transparent solid paste, and preferably, (a) an alkyl group having 1 to 2 carbon atoms 1-98 mol% of the (meth) acrylic-acid alkyl ester monomer which has, the (b) (meth) acrylic-acid monomer, and (c) the alkyl-acid alkyl ester monomer which has a C3-C10, preferably C3-C8 linear or branched alkyl group. : 1 to 98 mol%: 1 to 98 mol% ((a): (b): (c)), preferably 5 to 90 mol%: 5 to 90 mol%: 5 to 90 mol%, more preferably Preferably 30 to 60 mol%: 20 to 40 mol%: 10 to 30 mol% of the polymerized weight average molecular weight (Mw) of 5,000 to 90,000, preferably 20,000 to 80,000, more preferably 40,000 to 70,000 air Include coalescing. In addition, the solid content of the acrylic emulsion may be 10 to 50% by weight, preferably 20 to 40% by weight. The acrylic emulsion may be formed through a common anionic polymerization method, a free radical polymerization method, or the like using the monomer and a conventional polymerization initiator, and have a liquid phase (emulsion) form and have a visible wavelength light transmittance of 90. It can be used as the main raw material of the transparent adhesive which is from 100%. If the molecular weight and the solid content of the acrylic emulsion are out of the above range, it may not have the form of the emulsion or may hinder the transparency of the transparent adhesive.

As the (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 2 carbon atoms, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate and mixtures thereof may be used. Methyl acrylate and methyl methacrylate can be used. When the content (mol%) of the (meth) acrylic acid alkyl ester monomer is out of the above range, the cohesion force of the copolymer obtained is low, and there is a fear that the adhesive force of the transparent solid paste is poor, or the synthesis of the copolymer may not be easy. As said (b) (meth) acrylic acid monomer, acrylic acid, methacrylic acid, or mixtures thereof which can introduce a carboxyl group into the molecular chain of the copolymer can be used. When the content (mol%) of the (meth) acrylic acid monomer is out of the above range, the adhesive strength of the transparent solid pool may be degraded or gelation may proceed during emulsion synthesis. As the (c) acrylic acid alkyl ester monomer having a linear or branched alkyl group having 3 to 10 carbon atoms, 2-ethylhexyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, a mixture thereof, and the like may be used. , Preferably 2-ethylhexyl acrylate can be used. When the content (mol%) of the acrylic acid alkyl ester monomer is out of the above range, the adhesiveness of the transparent solid pool may be lowered, thereby lowering the initial adhesive strength, or there may be a problem of deterioration in adhesive strength due to the decrease in cohesion.

With respect to the transparent solid paste composition according to the present invention, the content of the acrylic emulsion is 30 to 70% by weight, preferably 40 to 60% by weight, more preferably 45 to 55% by weight. When the content of the acrylic emulsion is out of the above range, there is a fear that the transparency or adhesion of the transparent solid paste is poor. If necessary, the acrylic emulsion has 1 to 20 parts by weight of lower alcohols having 1 to 4 carbon atoms, such as ethanol, preferably 100 parts by weight of the total acrylic emulsion, so as to have the form of liquid (emulsion) and the required flowability. 5 to 15 parts by weight may be mixed and used, and if the content of the alcohol is out of the range, the gelation of the acrylic emulsion may proceed and may not have the form of a liquid (emulsion). In addition, the alcohol may be removed from the transparent solid pool by evaporation or the like during the formation of the transparent solid pool.

Polyvinylpyrrolidone (PVP) used in the present invention is added to improve the adhesion of the transparent solid paste, and the content of the polyvinylpyrrolidone with respect to the transparent solid paste composition, 1 to 20% by weight, preferably 1 to 10% by weight, more preferably 2 to 8% by weight. If the content of the polyvinylpyrrolidone is less than 1 part by weight, the adhesive property of the transparent solid paste may be deteriorated. If the content of the polyvinylpyrrolidone is more than 20 parts by weight, the adhesiveness of the transparent solid paste may be improved, but the transparency may be impaired. have.

The filler used in the present invention is used to increase the specific gravity of the solid (solid content) of the transparent solid paste, and should not impair the transparency and adhesion of the transparent solid paste. The filler may be a conventional sugar (glucose), fructose (fructose), sucrose (sucrose), such as a conventional sugar (sugar) can be used, preferably glucose (glucose, pure) may be used. With respect to the transparent solid paste composition, the content of the filler is 5 to 40% by weight, preferably 10 to 30% by weight, more preferably 15 to 25% by weight. If the content of the filler is less than 5% by weight, the specific gravity of the solid content is too low, there is a fear that the formation of a transparent solid pool may be difficult, and if it exceeds 40% by weight, transparency may be impaired.

Water used in the present invention is added for effective stirring and viscosity control of the transparent solid paste composition, the content of the water, based on the transparent solid paste composition, 2 to 15% by weight, preferably 5 to 10% by weight %, More preferably 8 to 10% by weight. When the content of the water is less than 2% by weight, effective stirring of the transparent solid paste composition may be difficult, and mixing of the composition may be difficult. When the water content is more than 15% by weight, the viscosity of the transparent solid paste composition may be excessively low to inhibit solidification. There is a concern.

The transparent solid paste composition according to the present invention may further include a pH adjuster, a surfactant, a preservative, a humectant, and an antifoaming agent, as necessary.

The pH adjusting agent used in the present invention is used to maintain the pH of the transparent solid pool at 9 to 14, preferably 10 to 12 to prevent acidification of the transparent solid pool, and to activate the solidification of the transparent solid pool, As the pH adjusting agent, sodium hydroxide, 2-amino-2-methylpropanol, and the like may be used. Preferably, sodium hydroxide and 2-amino-2methylpropanol may be used alone or in combination. It can be mixed and used. The content of the pH adjusting agent is 0.5 to 5% by weight, preferably 1 to 4% by weight, based on the transparent solid paste composition. If the content of the pH regulator is less than 0.5% by weight, the amount of use is too small to have a pH control effect or the solid pool may not have sufficient hardness (solidification is weakened), if it exceeds 5% by weight, it will act as an impurity There is only a concern and there are no special advantages.

The surfactant used in the present invention is used for smooth mixing of the transparent solid paste composition. As the surfactant, a commercially available commercial surfactant may be used. For example, polyoxyethylene which is a nonionic surfactant. Polyoxyethylene alkyl aryl ethers such as lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene derivatives, oxyethylene-oxypropylene block Sodium salts of fatty acids such as copolymers, glycerin fatty acid esters, polyoxyethylene fatty acid esters, sodium stearate, sodium palmitate, sodium myristrate, and the like can be used. Preferably, polyoxyethylene octyl phenyl ether and sodium stearate It may be used alone or in combination, or may be used after being introduced under different conditions (temperature, etc.). With respect to the transparent solid paste composition, the content of the surfactant is 0.5 to 10% by weight, preferably 1 to 8% by weight. When the content of the surfactant is out of the above range, the mixing of the transparent solid paste composition may be difficult or may act as an impurity.

Preservatives used in the present invention are used to prevent the decay of the transparent solid pool, commercially available preservatives can be used, for example, isothiazolone-based preservatives, potassium sorbate, methyl paraben, ethyl Parabens and the like can be used, and preferably, ketone seed (KATHON (CG)) of Rohm and Haas can be used as an isothiazolone-based preservative. With respect to the transparent solid paste composition, the content of the preservative is 0.1 to 1% by weight, preferably 0.1 to 0.5% by weight. If the content of the preservative is out of the above range, it may not act as a preservative or may act as an impurity.

Moisturizing agent used in the present invention, which is used for the moisturizing effect of the transparent solid pool, the conventional moisturizing agent may be used as the moisturizing agent, for example, glycerin (glycerin), polyethylene glycol (PEG), Polypropylene glycol (PPG) and the like may be used, preferably glycerin may be used. With respect to the transparent solid paste composition, the content of the moisturizing agent is 5 to 20% by weight, preferably 7 to 14% by weight. If the content of the moisturizer is out of the above range, there is a fear that the moisturizer or cause the wrinkles of the adherend due to a large amount of moisture.

Antifoaming agent used in the present invention, is used to prevent or remove the formation of bubbles in the manufacturing process of the transparent solid pool, the commercially available antifoaming agent may be used as the antifoaming agent, for example, mineral oil-based, silicone oil Type, hydrocarbon type, phosphate ester type, organic ester type, amide type, organic polymer type antifoaming agent and the like can be used. Preferably, NOPCO NXZ of Sanofco may be used as the mineral oil antifoaming agent. The content of the antifoaming agent is 0.1 to 5% by weight, preferably 0.3 to 0.8% by weight based on the transparent solid paste composition. When the content of the antifoaming agent is out of the above range, a lot of bubbles are generated in the transparent solid pool or may act as impurities.

Method for producing a transparent solid pool according to the invention, (1) at 15 to 30 ℃, preferably 20 to 25 ℃, 30 to 70% by weight of acrylic emulsion, 1 to 20% by weight of polyvinylpyrrolidone and water 2 To 15% by weight and, if necessary, mixing 0.5 to 5% by weight of pH adjuster, 0.1 to 1% by weight of preservative and 5 to 20% by weight of moisturizer; (2) raising the temperature of the mixture to 40-60 ° C., preferably 45-55 ° C., then mixing 5-40% by weight of the filler and 0.5-10% by weight of the surfactant; And (3) raising the temperature of the mixture to 70 to 90 ° C., preferably 75 to 85 ° C., and then mixing 0.1 to 5% by weight of an antifoaming agent and for 20 minutes to 1 hour, preferably 25 to 40 minutes. Stirring. After completion of stirring, the mixture may be placed in a conventional plastic container for a solid pool and cooled to obtain a transparent solid pool.

If the temperature of the step (2) is out of the range, the viscosity of the mixture increases when the filler is added, there is a fear that the mixing is difficult, or the transparency may be lowered, if the temperature of the step (3) is out of the range, mixing (Stirring) may be difficult, or the grass may deteriorate.

The transparent solid paste composition according to the present invention and the transparent solid paste prepared by the method for preparing the same are used as an acrylic emulsion and polyvinylpyrrolidone as a main component. Transparency of 80 to 100%, after the paste in the container, the hardness according to ASTM D 1321 test method is 10 to 15mm, dried within 1 to 2 minutes after pasting and has an adhesive force of 90 to 110 gf (gram force) . The transparent solid paste composition according to the present invention is a water-soluble or water-dispersible material, and is characterized by not impairing transparency and adhesion. Solid content of the transparent solid pool is 30 to 60% by weight, preferably 35 to 50% by weight, there is no addition to the content over time, but the higher the test weight, the higher the content of solids may appear. The hydrogen ion concentration (pH) of the transparent solid pool is 9 to 14, which is alkaline, non-toxic, and when bonded to the transparent solid pool, can significantly reduce wrinkles due to shrinkage of the adherend, such as transparent paper, and fabric It is possible to bond materials that cannot be bonded with existing solid glue such as leather, wood, etc. (but permanent bonding is impossible).

Hereinafter, preferred examples for aiding in understanding the present invention are presented. The following examples are intended to illustrate the invention and are not intended to limit the invention.

EXAMPLES Preparation and Performance Evaluation of Transparent Solid Pools

In the reactor, methyl methacrylate monomer, methacrylic acid monomer, and 2-ethylhexyl acrylate monomer are present at a ratio of 50 mol%: 30 mol%: 20 mol%. 50% by weight of polymerized acrylic emulsion (molecular weight (Mw): 40,000 to 70,000), 8.33% by weight of water, 4.83% by weight of polyvinylpyrrolidone, and stirred, followed by 0.83% by weight of sodium hydroxide and 2-amino-2- 0.67% by weight of methyl propanol, 0.08% by weight of Ketone Cage (KATHON (CG)), 0.83% by weight of polyoxyethyleneoctylphenylether and 8.33% by weight of glycerin were added and stirred at 15 to 25 ° C. The temperature of the mixture was raised to 50 ° C., 21.67% by weight of glucose and 4% by weight of sodium stearate were added and stirred, and then the temperature of the mixture was raised to 80 ° C. and NOPCO NXZ of Sanofco. 0.43% by weight was added and stirred for 30 minutes. After stirring, the mixture was placed in a plastic container and cooled to obtain a transparent solid pool.

Performance evaluation of the prepared transparent solid pool was carried out according to the following test method, the results are shown in Table 1.

1. Adhesive test

A. Paper bonding test (Test method of KS M 7100)

1. A writing paper sheet (basis weight of 75 ~ 80g / m ³⁾ is put in a full portion of 30x30mm (60x30cm) to thin and uniform.

2. After paste uniformly on 30x30mm part, overlap and leave it for about 5 minutes and pull it out so that the force is applied almost evenly at both ends. (Criteria: There should be no change)

B. Paper Adhesion Test (TM T-515 Adhesion Test Method)

1. Acrylic plate is made 5.0mm thick, 30mm wide and 300mm long.

2. Cut A paper (Basic weight 75 ~ 80g / m ³ ) into 1cm width and 300mm length.

3. Place a weight of 300g on the top of the transparent solid paste at about 250mm and apply the paste thinly and evenly once.

4. Gently put the acrylic plate (thickness 5.0mm, width 30mm, length 300mm) in section 3.

5. Reciprocate once using rubber roll of 2kg.

6. After fixing the acrylic plate with transparent tape on the tester, attach the front paper to the tester fixture.

7. Operate the tester and move it forward and display the numerical value on the instrument panel. (Pass criteria: 100gf or more, existing solid pool 50gf)

2. pH test (pH meter: istek pH Meter)

1 pH Meter Model: Measured with an istek pH Meter at 71P.

2. Cut 2 mm of the transparent solid paste surface and attach it to the electrode of the pH meter to measure the stabilized pH value. (Pass criteria: 10.3 or more)

3. Solid content test (oven, electronic scale, tinfoil, knife, calculator, writing instrument)

1. Prepare 10 transparent solid pastes about 8g.

2. Cut 10 pieces of foil paper according to the above capacity, fold up the ends in a square shape and check the weight.

3. Put the transparent solid paste into silver foil and check the weight of 10 pieces.

4. Place 10 checked specimens into the oven.

5. Heat 5 hours at 120 degrees Celsius.

6. After heating is complete, open the oven and check the weight of each.

(Solid ratio: A: pure grass weight before drying, B: pure grass weight after drying, B / A × 100 = C weight%, acceptance criteria: 42 to 48 weight%)

4. Hardness test (ASTM D 1321 test method)

1. Place a clear solid paste 1 mm below the saliva on the penetrometer.

2. Load 50g on the needle.

3. Pull the handle and apply the load for 5 seconds.

4. After the time has elapsed, gently lower the upper handle on the circular gauge plate to read the number where the indicator hand has stopped. (Pass criteria: 10 ~ 15mm)

5. Weight test (KS G 2105: ²⁰⁰¹ According to

1. Measure the total weight of the polypropylene (PP) container.

2. Measure the total weight of the transparent paste.

3. The weight of item 2 minus 1 is the pure transparent glue weight.

4. Measure with an accuracy of 0.01g. (Pass criteria: transparent paste weight + 3wt% or more)

6. Transparency test (KS L 2514: ²⁰⁰⁴ According to

Thickness: Width: 1mm: 30mm: 30mm on a transparent glass Thickness: Width: 1mm: 10mm: 10mm After making a frame, cut the transparent solid paste and cut the top thickness: Width: 1mm: 30mm: 30mm Press to display the value obtained by transmission in%.

Table 1

From the above Table 1, the transparent solid pool according to the present invention exhibits excellent transparency and adhesiveness, and can prevent acidification of the solid pool at a pH of 12. Since the transparent solid glue has an excellent adhesive strength of 100 gf, it is possible to bond materials that are impossible to bond with conventional solid glue such as fabric, leather, and wood.

Claims (6)

30 to 70% by weight of acrylic emulsion; 1 to 20 weight percent polyvinylpyrrolidone; 5 to 40 wt% filler; And Transparent solid paste composition comprising 2 to 15% by weight of water. The acrylic emulsion of claim 1, wherein the acrylic emulsion has a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 2 carbon atoms, a (meth) acrylic acid monomer and an acrylic acid alkyl ester monomer having a linear or branched alkyl group having 3 to 10 carbon atoms. 1-98 mol%: 1-98 mol%: The transparent solid paste composition containing the copolymer of the molecular weight 5,000-90,000 polymerized by the ratio of 1-98 mol%. The transparent solid according to claim 1, further comprising 0.5 to 5% by weight of pH adjusting agent, 0.5 to 10% by weight of surfactant, 0.1 to 1% by weight of preservative, 5 to 20% by weight of moisturizer and 0.1 to 5% by weight of antifoaming agent. Pool composition. The method of claim 3, wherein the pH adjusting agent is selected from the group consisting of sodium hydroxide, 2-amino-2methylpropanol and mixtures thereof, and the filler is selected from the group consisting of glucose, fructose, sucrose and mixtures thereof. Transparent solid paste composition is selected. The transparent solid paste according to claim 1, wherein the transparent solid paste composition is water-soluble or water-dispersible, and the transparent solid paste prepared by the transparent solid paste composition has a solid content of 30 to 60% by weight and has a thickness of 1 mm. The visible solids light transmittance is 80 to 100%, hardness is 10 to 15mm, dried between 1 to 2 minutes after pasting, adhesive strength is 90 to 110gf, pH is 9 to 14 transparent solid paste composition. At 15 to 30 ° C., mixing 30 to 70 wt% of an acrylic emulsion, 1 to 20 wt% of polyvinylpyrrolidone and 2 to 15 wt% of water; After raising the temperature of the mixture to 40 to 60 ° C., mixing 5 to 40 wt% of the filler and 0.5 to 10 wt% of the surfactant; And After raising the temperature of the mixture to 70 to 90 ℃, 0.1 to 5% by weight of the defoaming agent is mixed, and the method of producing a transparent solid pool comprising the step of stirring.