KR100385816B1 - Manufactur method of dampproof covering material for paper and it's used dampproof paper - Google Patents

Abstract

The present invention relates to a method for producing a moisture-proof (waterproof) coating material for paper and a moisture-proof paper using the same, and to maintain the viscosity stability and to reduce the amount of gum generated, good moisture-proof, and to prevent the blocking phenomenon of the moisture-proof paper. .

The present invention is the first water-soluble synthetic resin by emulsifying and copolymerizing 5 to 20 parts by weight of acrylonitrile, 80 to 95 parts by weight of two or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid alkyl esters, methacrylic acid alkyl esters and aromatic unsaturated monomers. To obtain 100 parts by weight of the first water-soluble synthetic resin, 5-30 parts by weight of acrylic acid alkyl ester or methacrylic acid alkyl ester, 5-30 parts by weight of acrylonitrile and 70-95 parts by weight of acrylamide or methacrylamide 0.5-20 weight part of 2nd water-soluble synthetic resin solid content obtained by copolymerization, and 25-100 weight part of wax emulsion zone solids are mixed, and a coating material is manufactured, and it heat-drys after apply | coating the coating material to the surface of paper.

Description

Manufacturing method of moisture-proof film material for paper and moisture-proof paper using the film material {MANUFACTUR METHOD OF DAMPPROOF COVERING MATERIAL FOR PAPER AND IT'S USED DAMPPROOF PAPER}

The present invention relates to a method for producing a moisture-proof and waterproof coating material for paper bags or containers used for packaging industrial and industrial products, and a moisture-proof paper using the coating material.

As is well known, a bag or container used for packaging industrial and industrial products may contain a polyolefin-based polymer compound such as polyethylene or polypropylene having excellent moisture resistance and water resistance to prevent moisture absorption or absorption of its contents. Laminated polyolefin-based laminating paper is used.

However, the above-mentioned polyolefin-based laminating paper is hard to dissociate due to its strong coating layer and is recovered as high paper to be used as a raw material of pulp, so that the coating layer remains in a sheet form or the three-layer coating is mixed in a papermaking process and fused to a dryer. Since it is not possible to use it as a notice because it causes a problem such as, and is incinerated after use, it is uneconomical in consideration of resource saving and pollution prevention.

In view of the above circumstances, a coating layer of a wax-based emulsion zone is formed on the surface of paper as a moisture-proof and waterproof paper that can be used as high paper, and is disclosed in Japanese Patent Application Publication No. 6339022. When the product is destroyed by the mechanical impact and dried at a high temperature during manufacturing, moisture resistance is deteriorated, and other problems occur such as slippage or blocking when the laminate is stacked.

In addition, a mixture of a wax-based emulsion zone and a synthetic rubber latex is disclosed in Japanese Patent Application Publication No. 5522597, which is improved in moisture resistance compared to the wax-based emulsion zone coating layer. Due to the thickening, slippage, mechanical damage and blocking did not improve.

And the resin composition for moisture proof and waterproof coating of the paper which improved the fault of the said wax type emulsion zone and the synthetic rubber latex type mixed film layer is disclosed by Unexamined-Japanese-Patent No. 3 279492. The dosage resin composition comprises 70 to 98 parts by weight of hydrophobic α.β monoethylenically unsaturated monomers selected from the group consisting of acrylic acid alkyl esters, methacrylic acid alkyl esters and aromatic unsaturated monomers and acrylamide and / or methacrylamide 2 Emulsion copolymerization of the monomer mixture of ˜30 parts by weight yields a synthetic resin aqueous dispersion, and 20 to 200 parts by weight of a wax-based emulsion zone solid is added to 100 parts by weight of the synthetic resin aqueous dispersion solids.

However, the moisture-proof and waterproof coating resin composition is a mixture of hydrophobic α.β monoethylenically unsaturated monomer and hydrophilic acrylamide, which is emulsified and copolymerized only once to obtain a synthetic resin aqueous component, and then mixed with a wax emulsion. When a large amount of gum (gum) is generated at the time of purification, not only the filtration is difficult, but also difficult to control the viscosity and work efficiency is reduced. In addition, after the waterproof and moisture-proof coating composition is prepared, the copolymerization proceeds, the viscosity increases, and the coagulation is difficult to apply to the paper, or the problem of blocking occurs after the coating.

The present invention is to correct the above problems, while maintaining the viscosity stability, while reducing the amount of gum generation, good moisture resistance, to provide a method for producing a moisture-proof film material for paper and a moisture-proof paper using the same that can prevent the blocking phenomenon of the moisture-proof paper. It aims to do it.

In order to achieve the above object, the present invention provides 5 to 20 parts by weight of acrylonitrile and 80 to 95 parts by weight of two or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid alkyl esters, methacrylic acid alkyl esters and aromatic unsaturated monomers. To obtain a first water-soluble synthetic resin, to 100 parts by weight of the first water-soluble synthetic resin, 5 to 30 parts by weight of acrylic acid alkyl ester or methacrylic acid alkyl ester, 5 to 30 parts by weight of acrylonitrile and acrylamide or It is characterized by the manufacturing method of the moisture proof film material for papers which mix | blended 0.5-20 weight part of 2nd water-soluble synthetic resin solid content obtained by copolymerizing 70-95 weight part of methacrylamide, and 25-100 weight part of wax emulsion zone solids.

Moreover, this invention is characterized by the moisture-proof paper which apply | coated the said coating material on the surface of paper, and heat-dried.

The production method of the present invention is obtained by emulsion co-polymerizing acrylonitrile and two or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid alkyl esters, methacrylic acid alkyl esters and aromatic unsaturated monomers to obtain a first water-soluble synthetic resin, 2-30 water-soluble synthetic resin solids obtained by copolymerizing 5-30 weight part of acrylic acid alkyl esters or methacrylic acid alkyl esters with water-soluble synthetic resin solids, 5-30 weight part of acrylonitrile, and acrylamide or methacrylamide, and wax emulsion zone solids To prepare a coating material.

And the moisture proof paper of this invention apply | coats the said coating material to the surface of paper, and heat-drys.

The first and the second water-soluble synthetic resin of the present invention is to prevent the blocking phenomenon when the coating material is applied to the paper by adjusting the adhesiveness by emulsion copolymerization or copolymerization of acrylonitrile having a low adhesiveness to a highly adhesive ethylenically unsaturated monomer Bar, the mixed amount of acrylonitrile is 5 to 20 parts by weight is appropriate, if less than 5 parts by weight of the coating material does not lower the adhesion phenomenon of the moisture-proof paper, and if it exceeds 20 parts by weight, the adhesion of the coating material is inferior.

In the present invention, the first water-soluble synthetic resin is prepared by emulsion copolymerization, and as the emulsion copolymerization method, a monomer mixture is mixed with water mixed with a surfactant to use a radical polymerization initiator (persulfate, peroxy compound, azobis compound, etc.). It heat-polymerizes or copolymerizes in a conventional method using a redox-type polymerization initiator (a mixture of a persulfate or peroxy compound and a reducing agent such as sulfite and ferrous sulfate).

In the present invention, acrylic acid alkyl esters and methacrylic acid alkyl esters which are hydrophobic ethylenically unsaturated monomers which are co-polymerized or copolymerized to the first and second water-soluble synthetic resins are methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate. Esters of alkyl groups having 10 to 18 carbon atoms of methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, other acrylic acid or methacrylic acid. Moreover, styrene, (alpha) -methyl styrene, vinyl styrene, etc. are used as an aromatic unsaturated monomer. It is suitable to mix 80-95 weight part of said ethylenically unsaturated monomers, and can mix and use 2 or more types.

In the present invention, the wax emulsion zone mixed in the first water-soluble synthetic resin solid content 100 is a mixture of 25 to 100 parts by weight based on solids, mainly composed of a wax having a melting point of 40 to 80 ° C., and a mixture of modified rosin and marinated petroleum resin. If less than 25 parts by weight, the moisture resistance is lowered, if more than 100 parts by weight damage to the coating layer during mechanical contact, the moisture resistance is reduced, the slip phenomenon occurs during loading, it is difficult to transport and store the damp paper .

The present invention is a second water-soluble synthetic resin by emulsion copolymerization of the first water-soluble synthetic resin, copolymerization of 5 to 30 parts by weight of acrylic acid alkyl ester or methacrylic acid alkyl ester, 5 to 30 parts by weight of acrylonitrile and acrylamide or methacrylamide. After preparing the coating material by mixing the second water-soluble synthetic resin and the wax emulsion zone to the first water-soluble synthetic resin, the second water-soluble synthetic resin containing hydrophilic acrylamide or methacrylamide has already been emulsion copolymerized When the mixture is mixed with the first water-soluble synthetic resin, acrylamide and the like have low adhesiveness, so that the viscosity is easily controlled, the viscosity does not change, the viscosity is maintained, and the viscosity is not solidified. In addition, the blocking phenomenon can be prevented when the coating material is applied to the paper while maintaining the viscosity safety.

When copolymerizing the second water-soluble synthetic resin in the present invention, acryl amide or methacryl amide is mixed 70 to 95 parts by weight, if less than 70 parts by weight is poor dissociation, and if it exceeds 95 parts by weight is less moisture-proof. Acrylamide or methacrylamide may also be used alone or in combination.

The second water-soluble synthetic resin may be a copolymer of 70 to 95 parts by weight of commercial acrylamide, 5 to 30 parts by weight of acrylonitrile, and 5 to 30 parts by weight of an acrylic acid alkyl ester or a methacrylic acid alkyl ester.

Example 1

350.0 parts by weight of water, 8.8 parts by weight of dialkyl sulfate, 7.9 parts by weight of dodecyl benzene sulfate, 39.9 parts by weight of acrylonitrile, 194.1 parts by weight of methacrylic methyl, 14.0 parts by weight of acrylic Nbutyl, acryl 160.0 parts by weight of 2ethyl hexyl, 23.0 parts by weight of methacrylic acid and 24.0 parts by weight of styrene are added thereto, and when heated to 40 ° C., 20 parts by weight of 10% persulfate is added thereto, followed by emulsification copolymerization at 85 ° C. for 3 hours. After cooling, the mixture is neutralized with ammonia water to bring the pH to 7 ± 0.5, and then water is added to form a first water-soluble synthetic resin having a solid content of 45%.

Next, the first water-soluble synthetic resin solid content 100 parts by weight, the second water-soluble synthetic resin solid content [Hyunil Synthetic Industry Co., Ltd. brand name H1201, acryl amide 85 parts by weight, acrylonitrile 7 parts by weight, acrylic acid alkyl ester and methacrylic acid alkyl ester 8 parts by weight of a solid content of 10%] 3 parts by weight of a wax emulsion zone (A wax manufactured by Heung Il Synthetic Industry Co., Ltd., 50% of solid content) 70 parts by weight of solid content is added, and water is added to form a coating material having a solid content of 40%. Was prepared.

Example 2

350.0 parts by weight of water, 8.8 parts by weight of dialkyl sulfate, 7.9 parts by weight of dodecyl benzene sulfate, 45.0 parts by weight of acrylonitrile, 15.0 parts by weight of acrylic Nbutyl, 150.0 parts by weight of acrylic 2ethyl hexyl, 160.0 parts by weight of methacrylic methyl, 15.0 parts by weight of methacrylic acid and 70.0 parts by weight of styrene are added thereto, and when heated to 40 ° C., 20 parts by weight of 10% persulfate is added thereto, followed by emulsion copolymerization at 85 ° C. for 3 hours. After cooling, the mixture is neutralized with ammonia water to bring the pH to 7 ± 0.5, and then water is added to form a first water-soluble synthetic resin having a solid content of 45%.

Next, 100 parts by weight of the first water-soluble synthetic resin solid content, 2 parts by weight of the second water-soluble synthetic resin [trade name H1201 manufactured by Heungil Synthetic Industry Co., Ltd.] and wax emulsion (trade name A wax, solid content of 50% by Heungil Synthetic Industry Co., Ltd.) 70 parts by weight of water was mixed and water was added to prepare a coating material having a solid content of 40%.

Example 3

3 parts by weight of the second water-soluble synthetic resin solid [H1201] and 100 parts by weight of the wax-emulsion solid (Hungil Synthetic Industry Co., Ltd. product name A) in 100 parts by weight of the first water-soluble synthetic resin solid content emulsion-polymerized in Example 2. Wax, solid content of 50%]] 100 parts by weight of water and water was added to prepare a coating material of 40% solids.

Comparative Example 1

560 parts by weight of water, 9 parts by weight of dodecyl benzene sulfate, 124 parts by weight of acrylic Nbutyl, 56 parts by weight of acrylic 2ethyl hexyl, 82 parts by weight of methacrylic methyl, 70 parts by weight of 40% acrylamide in a reactor (stirrer and thermometer installation) Add 110 parts by weight of styrene, and when heated to 40 ° C., add 5 parts by weight of 10% potassium persulfate and 3 parts by weight of 10% bisulfate and emulsify and copolymerize at 90 ° C. for 4 hours to form a synthetic resin aqueous product, which is then cooled and cooled to 40% of solids. Obtain a synthetic resin product. 70 parts by weight of the wax emulsion zone solids (manufactured by Heung-Il Synthetic Industry Co., Ltd., trade name A wax) was mixed with 100 parts by weight of the synthetic resin aqueous product solid content to prepare a coating material having a solid content of 40%.

Comparative Example 2

Styrene butadiene-based latex (Ulsan Pacific Co., Ltd., brand name DL620, 50%) solids content of 100 parts by weight of wax emulsion zone solids (Hexil Synthetic Industry Co., Ltd., brand name A wax) 40% of the coating material was produced.

The coating materials prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were directly coated on a grade B kraft paper having a basis weight of 80 g / m 2 and dried at 100 ° C. for 1 hour to prepare a moisture resistant paper having a coating amount of 20 g / m 2.

Test Methods

1. Permeability: According to KSM 7019­95.

2. Blocking resistance: 10cm square sample was coated with coating material and uncoated surface at 40 ℃ 12㎏ / ㎠ for 30 minutes, left for 1 hour, and then separated. The adhesive side is easily separated, B is the adhesive side separated without damage, and C is the damaged state when the adhesive side is separated.

3. Dissociation: Cut the sample into squares of 1cm 1cm, and dissociate it for 2 minutes at a concentration of 1.6% 500㏄ for 2 minutes in a home mixer, make a sheet of 80 g / m2 of basis weight in a laboratory paper machine and dry it at 120 ℃ for 20 minutes. Judging by the presence or absence of dissociation material, ○ is a state in which there is no undissociated material in the sheet, △ is a state in which undissociated material remains.

4. Viscosity of coating material: Brookfield BL type viscometer irradiated at 25 ° C

Test results of Examples 1 to 3 and Comparative Examples 1 and 2 are shown in Table 1 and Table 2.

Coating amount (g / ㎡) Moisture permeability (g / ㎡24hr) Blocking resistance Dissociation Example 1 20 28.5 C ○ Example 2 20 29.1 A ○ Example 3 20 28.8 A ○ Comparative Example 1 20 59.8 A ○ Comparative Example 2 20 97.0 C △

Viscosity (CPS) After manufacture 10 days later 20 days later 30 days later 45 days later 60 days later Example 1 450 ← ← ← ← 455 Example 2 515 ← ← ← ← 520 Example 3 320 ← ← ← ← ← Comparative Example 1 980 990 1,270 1,325 1,538 2,239 Comparative Example 2 280 ← ← ← ← 285

As described above, the present invention emulsifies and co-polymerizes the first water-soluble synthetic resin, copolymerizes the second water-soluble synthetic resin including acrylamide or methacrylamide, and mixes the first water-soluble synthetic resin with the wax emulsion, and the first and second water-soluble synthetic resin Since acrylonitrile is mixed in the film, it is possible to control the viscosity of the coating material, thereby preventing the blocking phenomenon when the coating material is applied to the paper, and the moisture resistance does not decrease even when bending, and also maintains the viscosity stability and the amount of gum generation Since it is reduced, the production of the coating material is simple and quick, and the productivity can be improved upon application to paper, and the performance does not change even after long-term storage.

Claims (2)

5 to 20 parts by weight of acrylonitrile and 80 to 90 parts by weight of two or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid alkyl esters, methacrylic acid alkyl esters and aromatic unsaturated monomers are obtained to obtain a first water-soluble synthetic resin, Obtained by copolymerizing 5-30 weight part of acrylic acid alkyl ester or methacrylic acid alkyl ester with 5-30 weight part of acrylonitrile, and 70-95 weight part of acryl amide or methacrylamide in 100 weight part of said 1st water-soluble synthetic resin solid content The manufacturing method of the moisture proof coating material for papers which mix | blended 0.5-20 weight part of 2nd water-soluble synthetic resin solid content, and 25-100 weight part of wax emulsion zone solid content. On the surface of the paper, 5 to 20 parts by weight of acrylonitrile and 80 to 90 parts by weight of two or more ethylenically unsaturated monomers selected from the group consisting of acrylic acid alkyl esters, methacrylic acid alkyl esters and aromatic unsaturated monomers are emulsified and co-polymerized. Obtaining a water-soluble synthetic resin, 5 to 30 parts by weight of acrylic acid alkyl ester or methacrylic acid alkyl ester, 5 to 30 parts by weight of acrylonitrile and acrylamide or methacrylamide 70 to 95 parts by weight of the first water-soluble synthetic resin solid content The moisture-proof paper which apply | coats the coating material which mixed 0.5-20 weight part of 2nd water-soluble synthetic resin solid content obtained by copolymerization by weight part, and 25-100 weight part of wax emulsion zone solids.