JP2003049398A - Synthetic resin emulsion for moisture-proof processing, resin composition for moisture-proof processing, and moisture-proof material - Google Patents

Abstract

(57) [Summary] PROBLEM TO BE SOLVED: To provide high moisture proof performance and to reproduce
Excellent disintegration between resin layer and paper, and anti-blocking
Moisture proof material with good water resistance and slip resistance
Obtained Resin Composition for Moistureproofing, Resin Group for Moistureproofing
Synthetic resin emulsion for moisture-proof processing
Material obtained by applying a resin composition for moisture-proof processing on a substrate
I will provide a. SOLUTION: The aliphatic conjugated diene monomer is 0.5 to 2
0% by weight, the alkyl group having 3 to 10 carbon atoms
(T) 30 to 80 acrylic acid alkyl ester monomers
% By weight, 1 to 40% of the carboxyl group-containing vinyl monomer
Moisture proof by emulsion polymerization of monomer mixture containing weight%
Processing synthetic resin emulsion, synthetic resin for moisture-proof processing
Contains emulsion, wax and hydrophobic powder
Resin composition for moisture-proof processing and resin composition for moisture-proof processing
The product is 10 to 50 g / m in terms of solid content. ^Two With the application amount
Moisture proof material applied on the substrate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a moisture-proof synthetic resin emulsion, a moisture-proof resin composition containing the emulsion, and a moisture-proof resin composition coated on a substrate. It relates to a moistureproof material. More specifically, a moisture-proof resin composition for forming a moisture-proof layer by coating or impregnating paper, a non-woven fabric, a fiber base material, wood, etc. The resin composition and the synthetic resin emulsion for moisture proofing used therein are particularly applied to the field of wrapping paper, and the moisture proof material is particularly moisture proof paper.

[0002]

2. Description of the Related Art Conventionally, as moisture-proof paper, there are polyethylene-laminated paper and moisture-proof coated paper in which vinylidene chloride resin is coated on base paper. Has been done.

However, in recent years, from the viewpoint of effective use of resources and measures against pollution, there is a problem in whether or not it is easy to recycle waste paper or waste paper into paper. From this point of view, in the case of polyethylene laminated paper, there is a problem that it is difficult to separate the resin layer from the paper and it is difficult to recycle the waste paper or the damaged paper. In addition, when a vinylidene chloride resin is applied, the generation of halogen-based toxic gas has become an environmental problem recently when the coated paper is incinerated and discarded. As described above, the moisture-proof paper has a problem, and development of alternative moisture-proof paper is strongly required.

As an alternative technique, there is a technique for obtaining a moisture-proof paper by blending 100 parts by weight of butadiene latex with 5 to 200 parts by weight of wax and coating the mixture.
No. 2259 is proposed.

However, since this technique uses wax, the coated surface is slippery, and even if a slip preventive agent is used,
It does not satisfy the sliding resistance. Also, the moisture-proof performance is rather deteriorated due to the wax falling off due to abrasion of the coated surface. Furthermore, the pressure at the time of winding the coated paper causes problems such as blocking of the coated paper.

[0006] Further, a technique of blending an acrylic emulsion with wax and coating it on a dumbbell has been proposed (Japanese Patent Publication No. 2-1671). However, the moisture-proof paper obtained by this technique has satisfactory sliding resistance, but its moisture-proof property is inferior to that of the above vinylidene chloride resin-coated paper and polyethylene laminated paper.

Further, there is a technique in which a wax emulsion containing a paraffin wax, an esterified product of a specific maleated or fumarized rosin and a polyhydric alcohol, and polybutene is used as a moisture-proof composition (Japanese Patent Publication No. 3-10759). Issue). However, the moisture-proof paper obtained by coating the substrate with this moisture-proof composition has a problem that the wax is removed by abrasion of the coated surface and the moisture-proof property is lowered.

Further, there is a technique relating to a moisture-proof paper in which a coating layer containing an acrylic emulsion and a wax emulsion and an inorganic pigment is provided on the surface of a paper substrate (JP-A-8-226096). However, although this technique is excellent in disaggregation, it does not provide sufficiently satisfactory performance in moisture resistance.

A moisture-proof paper having a moisture-proof layer containing a wax and a synthetic resin latex formed on at least one surface of a paper support, wherein the moisture-proof layer has a flat plate shape having an aspect ratio of 5 or more and a particle diameter of 5 to 50 μm. It contains a pigment and has an n-paraffin component ratio of 0.5 to 5.
There is a technology relating to a moisture-proof paper with 0% by weight (Japanese Patent Laid-Open No. 9-29138).
-111696 gazette). However, in this technique, it is difficult to lower the viscosity due to the pigment dispersibility in producing the composition and the thickening in the pigment blending, and there is a problem in coating suitability in a coating machine that requires low viscosity. Further, the glossiness (whiteness) and the friction coefficient of the coated paper cannot be sufficiently satisfactory.

Further, there is a technique relating to a moisture-proof processed paper obtained by coating a moisture-proofing agent containing a synthetic resin latex such as styrene-butadiene latex as a main component with aluminum hydroxide fine powder, preferably a coating liquid containing wax. (JP-A-11-335999). However, this technique provides moisture resistance comparable to that of polyethylene laminated paper, but it is difficult to obtain more moisture resistance. Also,
The coating liquid used here has a drawback that the aluminum hydroxide fine powder is liable to settle and the storage stability is poor.

Therefore, for the moisture-proof processing of an emulsion type, which can impart moisture resistance higher than that of polyethylene laminated paper, and can easily collect and recycle waste paper and broke, that is, excellent releasability between the resin layer and the paper upon regeneration. Development of a resin composition is desired.

[0012]

The problem to be solved by the present invention is to provide a high moistureproof performance (JIS Z-0208) superior to that of polyethylene laminated paper, and to recycle the resin layer and the paper during recycling. A resin composition for moisture-proof processing, which has excellent disaggregation properties, good blocking resistance, good sliding resistance, and a moisture-proof material with no wax falling off, a moisture-proof processing synthetic resin emulsion contained in the moisture-proof processing resin composition, It is intended to provide a moisture-proof material obtained by applying a resin composition for moisture-proof processing onto a substrate.

[0013]

Means for Solving the Problems Aliphatic conjugated diene monomer (a1) and alkyl group (meth) acrylic acid alkyl ester monomer (a2) having 3 to 10 carbon atoms
And a carboxyl group-containing vinyl monomer (a3),
A moisture-proof synthetic resin emulsion, characterized by being emulsion-polymerized in the following specific ratios, is used as a moisture-proof synthetic resin emulsion (A), a wax (B) and a hydrophobic powder ( The resin composition for moisture-proofing containing C) and C) has a high moisture-proofing performance (J) higher than that of polyethylene laminate paper by coating the resin composition on a substrate.
IS Z-0208) can be imparted, excellent releasability between the resin layer and paper at the time of recycling, good blocking resistance and slip resistance, and a moisture-proof material that prevents wax from falling off have been found. The present invention has been completed.

That is, according to the present invention, 0.5 to 20% by weight of the aliphatic conjugated diene monomer (a1) and a (meth) acrylic acid alkyl ester monomer having an alkyl group having 3 to 10 carbon atoms are used. 30 to 80% by weight of the body (a2) and 1 to 40% by weight of the carboxyl group-containing vinyl monomer (a3),
The present invention provides a synthetic resin emulsion for moisture-proofing, which is characterized by being emulsion-polymerized.

The present invention also provides a moisture-proofing resin composition comprising the above-mentioned moisture-proofing synthetic resin emulsion (A), wax (B), and hydrophobic powder (C). It is provided.

Furthermore, the present invention provides the moisture-proof synthetic resin emulsion (A), the wax (B), and the hydrophobic powder (C) containing the moisture-proof synthetic resin composition in an amount of 10 to 10 in terms of solid content. The present invention provides a moisture-proof material, characterized in that the moisture-proof material is applied on a substrate at an application amount of 50 g / m ² .

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The synthetic resin emulsion for moisture-proof processing of the present invention comprises an aliphatic conjugated diene monomer (a1) 0.5
˜20% by weight, and a (meth) acrylic acid alkyl ester-based monomer (a2) having an alkyl group having 3 to 10 carbon atoms
Emulsion polymerization of 30 to 80% by weight, 1 to 40% by weight of a carboxyl group-containing vinyl monomer (a3), and optionally another copolymerizable vinyl monomer (a5). It is essential that when the content of the aliphatic conjugated diene-based monomer (a1) is less than 0.5% by weight, the moisture resistance after abrasion is increased, and when it exceeds 20% by weight, the disaggregation is performed. Is not preferable, because the
When the content of the acrylic acid ester-based monomer (a2) is less than 30% by weight, the disintegration property is decreased, and when it exceeds 80% by weight, the moisture resistance is decreased, which is not preferable. Vinyl monomer (a3)
When the content of s is less than 5% by weight, the disintegration property is 30
If it exceeds 5% by weight, moisture resistance is lowered, which is not preferable.

Among the synthetic resin emulsions of the present invention, the aliphatic conjugated diene-based monomer (a1) is preferably used from the viewpoint of increasing the molecular weight, improving the resistance to blocking and moisture, and maintaining good disaggregation. The content is 2 to 15% by weight, the content of the (meth) acrylic acid alkyl ester-based monomer (a2) is 30 to 80% by weight, and the disintegration property is from the viewpoint of improving the disintegration property without lowering the moisture resistance. The content of the carboxyl group-containing vinyl-based monomer (a3) is 5 to 30% by weight from the viewpoint of achieving a good balance between the improvement in moisture resistance and the moisture resistance.
The synthetic resin emulsions of are respectively preferred. Furthermore, the glass transition temperature (Tg) of the resin solid content is 5 to 3 from the viewpoint of excellent blocking resistance and moisture resistance due to film-forming property.
A synthetic resin emulsion at 0 ° C. is particularly preferred. further,
Among the synthetic resin emulsions of the above invention, when importance is attached to the disintegration property, it is preferable to adopt a formulation in which the carboxyl group-containing vinyl monomer (a3) is unevenly distributed on the emulsion particle surface as much as possible by two-step polymerization. That is, in the first-stage polymerization, the carboxyl group-containing vinyl-based monomer (a
After a part of the monomers used for the polymerization of the emulsion containing the whole amount of 3) is polymerized, the rest of the monomers used for the polymerization of the emulsion is polymerized in the second stage to In the two-step polymerization, polymerization occurs in the particles polymerized in the first step, and the carboxyl group-containing vinyl-based monomer (a3) used in the first step polymerization is likely to be unevenly distributed on the particle surface.

Examples of the aliphatic conjugated diene-based monomer (a1) used here include 1,2-butadiene, 1,
3-Butadiene, isoprene, chloroprene and the like can be mentioned, and among them, 1,2-Butagen and 1,3-Butagen are preferable.

The alkyl group has 3 to 10 carbon atoms.
(Meth) acrylic acid alkyl ester-based monomer (a
As 2), for example, propyl (meth) acrylate,
Examples include butyl (meth) allylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, octadecyl (meth) acrylate, and the like, among which the number of carbon atoms of the alkyl group is 4 to 7 (meth) acrylic acid alkyl ester-based monomer is preferable,
2-Ethylhexyl acrylate is particularly preferable from the viewpoint of obtaining high moisture-proof performance and disintegration property.

Further, as the carboxyl group-containing vinyl monomer (a3), for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid and its anhydride, fumaric acid, itaconic acid, unsaturated dicarboxylic acid monoalkyl ester. (For example, monomethyl maleate, monoethyl fumarate, mononormal butyl itaconate).

Further, as the other copolymerizable vinyl-based monomer (a4), which is optionally used in combination, there may be mentioned, for example,
Methyl (meth) acrylate, ethyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene,
Ethylenically unsaturated aromatic monomers such as chlorostyrene and 2,4-dibromostyrene; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; vinylidene chloride, vinylidene bromide, etc. Vinylidene halide; (meth) acrylic acid-2-hydroxyethylene, (meth) acrylic acid-2
Hydroxyalkyl esters of ethylenically unsaturated carboxylic acids such as hydroxypropyl; glycidyl esters of ethylenically unsaturated carboxylic acids such as glycidyl (meth) acrylate; (meth) acrylamide, N-methylol (meth) acrylamide, butoxymethyl (meth ) Acrylamide, diacetone acryl amide and the like.

The synthetic resin emulsion of the present invention comprises 0.5 to 20% by weight of the above aliphatic conjugated diene monomer (a1),
30-80% by weight of a (meth) acrylic acid alkyl ester-based monomer (a2) having an alkyl group having 3 to 10 carbon atoms, and a carboxyl group-containing vinyl-based monomer (a3) 1 to 4
It is obtained by emulsion polymerization of 0% by weight, and optionally other copolymerizable vinyl-based monomer (a4).

As the emulsifier used in the emulsion polymerization, various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc. can be used. Of these, it is preferable to use a reactive emulsifier in order to further improve the moisture resistance. A soap-free type synthetic resin emulsion can be obtained by using this reactive emulsifier.

Examples of the above reactive emulsifiers include sodium styrene sulfonate, sodium vinyl sulfonate, soda vinyl sulfonate, and emulsifiers having various ethylenically unsaturated groups.

In the synthetic resin emulsion of the present invention, the ionic and nonionic properties of the emulsifier are the same as those of the wax (B) because of its good compatibility with the emulsion of the wax (B) described later. Preferably. For example, if an anionic surfactant is used in the emulsion of wax (B), the synthetic resin emulsion preferably uses an anionic surfactant.

The amount of the emulsifier to be used is 0.1 to 3 parts by weight of the active ingredient of the emulsifier per 100 parts by weight of the synthetic resin emulsion in terms of solid content, since high emulsifying property can be exhibited. Ranges are preferred.

In producing the synthetic resin emulsion of the present invention, the above-mentioned monomer mixture is mixed with a free radical generating catalyst such as potassium persulfate (K ₂ S ₂ O ₈ ) and sodium persulfate (Na ₂ S _2). O ₈ ), ammonium persulfate [(NH ₄ ) ₂ S ₂ O ₈ ], aqueous catalysts such as hydrogen peroxide, tert.
-Emulsion polymerization may be carried out in the presence of an oil catalyst such as -butyl hydroxide-cumene or cumene hydroperoxide. The same applies to the production of synthetic resin emulsion by two-step polymerization.

Additives usually used in radical polymerization, such as chain transfer agents, ethylenediaminetetraacetic acid, p
An alkaline substance or the like for adjusting H can be used if necessary.

The synthetic resin emulsion of the present invention is preferably used after being concentrated to a required solid content by, for example, a method such as stripping in order to reduce the odor of unreacted monomers.

Minimum film forming temperature of synthetic resin emulsion (M
The FT) is not particularly limited, but is preferably 50 ° C. or lower in consideration of the film forming property.

The moisture-proof resin composition of the present invention comprises the above-mentioned synthetic resin emulsion (A), wax (B),
A resin composition containing a hydrophobic powder (C).

As the wax (B) used here, various waxes can be used, and examples thereof include paraffin wax, polyethylene wax, montan wax, microcrystalline wax, carnauba wax, and the like, but paraffin wax is preferable.

The above-mentioned paraffin wax is crystalline paraffin separated from petroleum and refined, and mainly has a structure of normal paraffin, isoparaffin, cycloparaffin, etc., but contains 90% by weight or more of normal paraffin, for example. , 90 normal paraffin
It is preferable that the content of the isoparaffin and the cycloparaffin be 10% by weight or less and the moisture resistance is excellent. The number of carbon atoms in the paraffin wax is not particularly limited, but is preferably 20 to 35. The melting point of paraffin wax usually changes in the range of 40 to 70 ° C., but the wax does not soak into the base material in the drying step after the resin composition for moisture-proof processing of the present invention is applied to the base material, and the wax does not penetrate the surface of the coating film. The melting point is preferably 45 to 65 ° C. in order to bleed out and exhibit high moisture resistance. Furthermore, the molecular weight of the paraffin wax is not particularly limited, but a number average molecular weight of 330 to 480 is preferable for exhibiting moisture resistance.

Examples of the form of the paraffin wax include a solid form and an emulsion form obtained by emulsifying and dispersing this solid form. Any form can be used, but it is compatible with a synthetic resin emulsion or the like. From the point of view, an emulsion is preferable.

Commercially available products of paraffin wax are, for example, 115, 120, 125, 130, 135, 14
Solid paraffin waxes such as 0 and 150 [above, manufactured by Nippon Seiro Co., Ltd.]; EMUSTER 0135 and 0136;
0384 [above, manufactured by Nippon Seiro Co., Ltd.], Harricks WE
200 [manufactured by Harima Kasei Co., Ltd.], Cerosol 428, B
Emulsion paraffin wax such as -460, B-608, B-982, 686 [above, manufactured by Chukyo Yushi Co., Ltd.] and the like.

The amount of the paraffin wax used is preferably 0.3 to 150 parts by weight with respect to 100 parts by weight of the resin solid content of the synthetic resin emulsion (A), but above all, the melting point is 45 to 65 ° C. It is preferable to use the paraffin wax in the range of 0.3 to 150 parts by weight with respect to 100 parts by weight of the resin solid content of the synthetic resin emulsion (A) in terms of excellent moisture resistance and slip resistance.

As the hydrophobic powder (C) used in the moisture-proof resin composition of the present invention, various hydrophobic powders can be used. For example, as the inorganic substance, calcium carbonate, magnesium carbonate, aluminum hydroxide, Powders of talc, kaolin, mica, titanium oxide, zinc oxide, silica, etc.
Examples of the organic substance include powders of polyester resin, petroleum-based rosin, rosin ester, etc. Among them, a blocking agent, a film-forming property, a moisture-proof property are excellent, and a moisture-proof material having a good surface condition can be obtained. Therefore, the average particle size is 6
~ 60 μm calcium carbonate powder and average particle size 6 ~
Aluminum hydroxide powder of 60 μm is preferred.

The amount of the hydrophobic powder (C) used is 5 to 250 with respect to 100 parts by weight of the resin solid content of the synthetic resin emulsion because of its excellent blocking resistance and film-forming property.
A range of parts by weight is preferable, and a range of 10 to 150 parts by weight is particularly preferable.

The method for combining the synthetic resin emulsion (A), the wax (B) and the hydrophobic powder (C) to obtain the moisture-proof processing resin composition of the present invention is not particularly limited, and examples thereof include synthetic methods. The resin emulsion (A) may be mixed with the wax (B) and the hydrophobic powder (C), or a monomer mixture for the synthetic resin emulsion in the presence of the wax (B) and the hydrophobic powder (C). May be emulsion polymerized.

The moisture-proof resin composition of the present invention contains, if necessary, a surfactant and a polyhydric alcohol in addition to the above components.
And thickeners can be added.

The surfactant and the polyhydric alcohol are used to improve the disintegration property when the moisture-proof paper is recycled.

As this surfactant, for example, commercially available products, Emulgen 105, 108, 109P, 12
0, 123P, 705, 707, 709, Emer, Emerr 2F, Neoperex F25 [above, Kao Corporation
Manufactured], Neugen EA-80, 120, 140, 142,
160, 170, 190D, Neocor YSK, P [above, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] and the like.

As the polyvalent alcohol, for example,
Examples thereof include ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol.

Examples of the thickener include polyvinyl alcohol, polyacrylic acid soda salt, ammonium salt, polyethylene-based thickener and the like.

A moisture-proof material can be obtained by applying or impregnating a substrate with the moisture-proof resin composition of the present invention.

Examples of the substrate include paper, non-woven fabric, fiber substrate and wood. As a method for coating or impregnating the substrate, various processing methods such as coating with various coaters, impregnation with an impregnating machine, and processing with a size press can be used.

The coating amount on the substrate is preferably 10 to 50 g / m ^{2 in} terms of solid content in terms of obtaining dryness and high moisture resistance, and a more preferable coating amount. Two
It is 0 to 30 g / m ² .

[0049]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. All parts and% in the examples are based on weight.

Example 1 120 parts of water, 0.1 part of sodium hydroxide, and a reactive emulsifier S-180 [Kao] were placed in a pressure resistant polymerization vessel equipped with a stirrer.
Unsaturated alkyl sulphate manufactured by KK] 1.2 parts, ethylenediaminetetraacetic acid 0.1 part, butadiene 5 parts, acrylic acid 2-
When 35 parts of ethylhexyl, 53 parts of styrene, 7 parts of methacrylic acid and 0.1 part of t-dodecyl mercaptan were charged, stirring was started, the reaction temperature was raised to 60 ° C, and the temperature in the polymerization vessel reached 60 ° C. Then, 0.1 part of ammonium persulfate was added to start the reaction. After 7 hours, when the polymerization rate reached 98%, cooling was performed to obtain a synthetic resin emulsion. The obtained synthetic resin emulsion had a polymerization rate of 98.6%. Next, the pH was adjusted to 9.0 with 25% aqueous ammonia, and then steam distillation was performed to synthesize a synthetic resin emulsion having a solid content of 50.1% (hereinafter, referred to as Em-A).
I got).

Example 2 In a pressure-resistant polymerization vessel equipped with a stirrer, 120 parts of water, 0.1 part of sodium hydroxide and an emulsifier Neoperex F-25 were used.
[Kao Corporation alkylbenzene sulfonic acid soda salt] 2
Part, ethylenediaminetetraacetic acid 0.1 part, butadiene 12
Parts, 34 parts of 2-ethylhexyl acrylate, 44 parts of methyl methacrylate, 10 parts of acrylic acid and 0.1 part of t-dodecyl mercaptan are charged, stirring is started, the reaction temperature is raised to 60 ° C., and the temperature in the polymerization vessel is increased. When the temperature reached 60 ° C, 0.1 part of ammonium persulfate was added to start the reaction. After 7 hours, when the polymerization rate reached 98%, cooling was performed to obtain a synthetic resin emulsion. The obtained synthetic resin emulsion had a polymerization rate of 98.6%. Then, the pH was adjusted to 9.0 with 25% aqueous ammonia, and the content of the emulsifier active ingredient was reduced to 1% by steam distillation.
The following synthetic resin emulsion having a solid content of 50.1% (hereinafter, referred to as Em-B) was obtained.

Example 3 In a pressure resistant polymerization vessel equipped with a stirrer, 120 parts of water and a reactive emulsifying agent S-180 [unsaturated alkylsulfate manufactured by Kao Corporation]
2.4 parts, ethylenediaminetetraacetic acid 0.1 part, butadiene 5 parts, 2-ethylhexyl acrylate 50 parts, methyl methacrylate 20 parts and methacrylic acid 20 parts were charged, stirring was started, and the reaction temperature was raised to 60 ° C. Then, when the temperature in the polymerization vessel reached 60 ° C., 0.1 part of ammonium persulfate was added to start the reaction. After 7 hours, when the polymerization rate reached 98%, cooling was performed to obtain a synthetic resin emulsion. The obtained synthetic resin emulsion had a polymerization rate of 98.6%. Then, the pH was adjusted to 9.0 with 25% aqueous ammonia, and then steam distillation was performed to synthesize a synthetic resin emulsion having a solid content of 45.4% (hereinafter, referred to as Em-C).
I got). Example 4 In a pressure-resistant polymerization vessel equipped with a stirrer, 405 parts of water and a reactive emulsifier S-180 (unsaturated alkylsulfate manufactured by Kao Corporation)
2.0 parts, 0.15 parts of ethylenediaminetetraacetic acid, 8 parts of butadiene, 44 parts of styrene and 48 parts of methacrylic acid were charged, stirring was started, and the temperature was raised to 70 in the polymerization vessel.
When reached ° C, 0.2 parts of potassium persulfate was added to start the reaction. After 8 hours, the temperature was raised to 80 ° C., and after 5 hours, cooling was carried out to obtain a first-stage synthetic resin emulsion. Then, add water 40 to a pressure resistant polymerization vessel equipped with a stirrer.
3 parts, Newcol 271A [manufactured by Nippon Emulsifier Co., Ltd.]
0 parts, 0.15 parts of ethylenediaminetetraacetic acid, 4 parts of butadiene, 20 parts of styrene and 76 parts of 2-ethylhexyl acrylate, the synthetic resin emulsion 22 of the first stage
5 parts were charged, stirring was started, the temperature was raised, and when the temperature in the polymerization vessel reached 70 ° C., 0.2 part of potassium persulfate was added to start the reaction. After 8 hours, the temperature was raised to 80 ° C. and 5
After a lapse of time, cooling was performed to obtain a second stage synthetic resin emulsion. The obtained synthetic resin emulsion has a polymerization rate of 9
It was 8.2%. Then pH with 25% ammonia water
Was adjusted to 9.0 and then the solids content of 4 by steam distillation.
A 0.3% synthetic resin emulsion (hereinafter referred to as Em-D) was obtained.

Comparative Example 1 In a pressure resistant polymerization vessel equipped with a stirrer, 120 parts of water, 0.1 part of sodium hydroxide, reactive emulsifier S-180 [Kao]
Unsaturated alkyl sulphate manufactured by KK] 1.2 parts, ethylenediaminetetraacetic acid 0.1 part, butadiene 29 parts, styrene 68
Parts, acrylic acid 3 parts and t-dodecyl mercaptan 0.1 part were charged, stirring was started, the reaction temperature was raised to 60 ° C., and when the temperature in the polymerization vessel reached 60 ° C., ammonium persulfate 0.1 Parts were added to start the reaction. 7
After a lapse of time, when the polymerization rate reached 98%, cooling was performed to obtain a synthetic resin emulsion. The obtained synthetic resin emulsion had a polymerization rate of 98.6%. Next, the pH was adjusted to 9.0 with 25% aqueous ammonia, and then steam distillation was performed to obtain a synthetic resin emulsion having a solid content of 50.1% (hereinafter referred to as Em-e).

Comparative Example 2 In a pressure resistant polymerization vessel equipped with a stirrer, 120 parts of water, 0.1 part of sodium hydroxide, and an emulsifier Neoperex F-25 were used.
[Kao Corporation alkylbenzene sulfonic acid soda salt] 2
Part, ethylenediaminetetraacetic acid 0.1 part, butadiene 12
Part, 2-ethylhexyl acrylate 32 parts, styrene 1
Charge 5 parts and 41 parts of acrylic acid, start stirring,
The reaction temperature was raised to 60 ° C., and when the temperature in the polymerization vessel reached 60 ° C., 0.1 part of ammonium persulfate was added to start the reaction. After 7 hours, when the polymerization rate reached 98%, cooling was performed to obtain a synthetic resin emulsion. The obtained synthetic resin emulsion had a polymerization rate of 98.6%. Then, the pH was adjusted to 9.0 with 25% ammonia water, and then steam distillation was performed to obtain a synthetic resin emulsion having a solid content of 50.1% (hereinafter referred to as Em-f).

Examples 4 to 15 and Comparative Examples 3 to 4 A synthetic resin emulsion Em- was placed in a container equipped with a stirrer.
A, Em-B, Em-C, Em-D, Em-e or E
paraffin wax emulsion having a melting point of 60 ° C., aluminum hydroxide B103, B153, B303
Alternatively, B53 and calcium carbonate SS30 were blended so as to have respective solid weights shown in Tables 1 to 3 to obtain a moisture-proofing composition of the present invention and a comparative control.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

(Footnotes in Tables 1 to 3) Paraffin wax emulsion; E manufactured by Nippon Seiro Co., Ltd.
-0136 (containing paraffin wax having a softening point of 60 ° C.,
Solid content 40%)-Aluminum hydroxide B103; Aluminum hydroxide powder manufactured by Nippon Light Metal Co., Ltd., average particle diameter 8 µm. -Aluminum hydroxide B153; aluminum hydroxide powder manufactured by Nippon Light Metal Co., Ltd., average particle diameter 15 µm. Aluminum hydroxide B303; aluminum hydroxide powder manufactured by Nippon Light Metal Co., Ltd., average particle diameter 30 μm. -Aluminum hydroxide B53; aluminum hydroxide powder manufactured by Nippon Light Metal Co., Ltd., average particle size 50 µm. -Calcium carbonate SS30; calcium carbonate powder manufactured by Nitto Koka Co., Ltd., average particle diameter 7.4 μm.

The obtained moisture-proofing resin composition of the present invention and a comparative control were respectively applied to commercially available high-quality paper (grammage 70 g / m 2).
² ) was coated by a Mayer lot so that the coating amount of the solid content would be about 25 g / m ^2, and dried at 120 ° C. for 1 minute with a hot air dryer. A moisture-proof coated paper was obtained.

With respect to the moisture-proof coated paper of the present invention thus obtained and for comparison and comparison, and the commercially available polyethylene laminated paper, the coating amount, moisture permeability, moisture permeability after abrasion, and friction were measured by the following methods. The coefficient, disaggregation property, blocking property, glossiness (whiteness), powder dispersibility and surface condition were evaluated. The results are shown in Tables 4 to 6.

From the results of Tables 4 to 6, Comparative Example 3
It can be seen that the moisture-proof processed paper of No. 1 has a low moisture permeability and is close to the moisture permeability of the moisture-proof processed papers of Examples 4 to 15, but is inferior in the moisture permeability after abrasion and the disintegration property. Further, the moisture-proof processed paper of Comparative Example 4 has a higher moisture permeability than the values of the moisture-proof processed papers of Examples 4 to 15, and in view of moisture resistance, polyethylene laminated paper (hereinafter abbreviated as "polylaminated paper"). It can be seen that it cannot be an alternative moisture-proof paper of.

The physical properties shown in Tables 4 to 6 were measured and evaluated by the following test methods. <Evaluation method> -Coating amount: The weight difference per 1 m ² between the moisture-proof processed paper and the high-quality paper before coating of the resin composition for moisture-proof processing was determined and defined as the coating amount.

Water vapor transmission rate (g / m ² · 24 hr); JIS
40 ° C, 90, under constant temperature and humidity conditions according to Z-0208
It was measured by the cup method at% RH.

Water vapor permeability after wear (g / m ² · 24 h
r); The coated surface of the moisture-proof coated paper is matched with the uncoated surface, and the load is 1
After applying 0 kg and shaking the shaker left and right for 2 minutes using a shaker, the coated surface was abraded, and then the water vapor transmission rate was changed to JIS as above.
It measured according to Z-0208.

Friction coefficient; friction coefficient test method JIS P
It measured according to -8147 (horizontal method).

Degradability: 500 ml of hot water at 50 ° C. and 3 c
10 g of the coated paper cut into m-squares was placed in a domestic mixer pot, stirred for 5 minutes, and the disintegration property between the resin and the paper was visually determined according to the following criteria. ◯: There is disaggregation, Δ: There is no disaggregation, X: No disaggregation.

Blocking property; moisture-proof coated paper 10 × 10
cm coated surface and black paper, press temperature 40 ℃,
Press for 15 minutes at a pressing pressure of 10 kg / cm ² ,
The state in which the black drawing paper was transferred to the coated surface was visually determined according to the following criteria. ○: No blocking, △: Some blocking,
X: There is blocking.

Gloss (whiteness); JIS P-813
8 (paper opacity test method).

Powder dispersibility: The moisture-proof resin composition was coated on a glass plate with an applicator (bar coater), and the dispersion state of the hydrophobic powder was visually determined according to the following criteria. ◯: Evenly dispersed, Δ: Uniform but insufficiently dispersed,
X: There is a lump and it is not dispersed.

-Surface condition: A solvent (toluene) colored with a red dye is brush-coated on the coated surface of the moisture-proof coated paper, and the state of penetration of the solvent into the back surface of the coated paper is visually and visually touched according to the following criteria. It was judged. ◯: Not permeated, Δ: A little bleeding, ×: Permeated completely.

[0072]

[Table 4]

[0073]

[Table 5]

[0074]

[Table 6]

[0075]

The moisture-proof material obtained by using the moisture-proof resin composition containing the moisture-proof synthetic resin emulsion of the present invention together with the wax and the hydrophobic powder is the conventional polymer. Compared with the conventional moisture-proof coated paper, it is superior in moisture-proof property, anti-broking property and anti-slip property, less wax falls off after abrasion, and good disaggregation between resin and paper and easy repulping.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) D06M 15/263 D06M 15/263 D21H 17/37 D21H 17/37 // (C08F 220/18 C08F 220: 06 220: 06 236: 04 236: 04) C08F 222: 00 (C08F 220/18 222: 00 236: 04) F term (reference) 4J002 AE03X AF023 BG04W BG05W BH02W CF003 DE106 DE136 DE146 DE236 DJ016 DJ036 DJ046 DJ056 FD013 FD016 GG02 GH00 GK02 GK04 HA06 HA07 4J100 AJ01Q AJ02Q AJ08Q AJ09Q AK32Q AL03P AL04P AL05P AL36Q AS02R AS03R AS07R CA05 DA25 DA37 EA06 FA20 JA01 JA11 JA13 4L033 AB01 AB63 AC02 AC07 AC07B07 AH AH BE08 EA14 EA16 EA20 EA32 FA11 FA19 FA20 FA30 GA47

Claims (11)

[Claims] 1. An aliphatic conjugated diene monomer (a1) 0.
5 to 20% by weight, and the number of carbon atoms in the alkyl group is 3 to 10
(Meth) acrylic acid alkyl ester-based monomer (a
2) A synthetic resin emulsion for moisture proofing, which is obtained by emulsion polymerization of 30 to 80% by weight and 1 to 40% by weight of a vinyl monomer (a3) containing a carboxyl group. 2. The aliphatic conjugated diene-based monomer (a1)
˜15% by weight, (meth) acrylic acid alkyl ester monomer (a2) having an alkyl group with 3 to 10 carbon atoms
The synthetic resin emulsion for moisture-proof processing according to claim 1, which comprises 30 to 80% by weight and 5 to 30% by weight of the vinyl monomer (a3) containing a carboxyl group. 3. Glass transition temperature (Tg) of resin solid content
Is 5 to 30 ° C. 3. The synthetic resin emulsion for moisture-proof processing according to claim 1 or 2. 4. A moisture-proof processing resin comprising the synthetic resin emulsion (A) for moisture-proof processing according to claim 1, 2 or 3, a wax (B) and a hydrophobic powder (C). Composition. 5. A wax (B) having a melting point of 45 to 6
The moisture-proof resin composition according to claim 4, wherein the paraffin wax at 5 ° C. is contained in an amount of 0.3 to 150 parts by weight based on 100 parts by weight of the resin solid content of the synthetic resin emulsion (A) for moisture-proof processing in terms of solid content. object 6. The moisture-proof resin composition according to claim 5, wherein the paraffin wax contains 90% by weight or more of normal paraffin wax. 7. A resin solid content of the hydrophobic powder (C), calculated as solid content, of the synthetic resin emulsion (A) for moisture-proof processing is 100.
5 to 250 parts by weight based on parts by weight, 5.
The resin composition for moisture-proof processing according to 5 or 6. 8. The hydrophobic powder (C) has an average particle size of 6 to
60 μm calcium carbonate powder or average particle size of 6 ~
The aluminum hydroxide powder having a particle size of 60 μm.
7. The resin composition for moisture-proof processing according to any one of 7. 9. A moisture-proofing resin composition containing the moisture-proofing synthetic resin emulsion (A) according to claim 1, 2 or 3 and a wax (B) and a hydrophobic powder (C) is a solid content. A moisture-proof material, characterized in that the moisture-proof material is applied on a substrate at an application amount of 10 to 50 g / m ^{2 in} terms of conversion. 10. The moisture-proof material according to claim 9, wherein the base material is paper. 11. A moisture-proofing resin composition, wherein the wax (B) is paraffin wax having a melting point of 45 to 65 ° C., and the resin solid content of the moisture-proof synthetic resin emulsion (A) is 100 parts by weight in terms of solid content. For 0.3 to 15
10 parts by weight, and 5 to 250 parts by weight of the hydrophobic powder (C) in terms of solid content based on 100 parts by weight of the resin solid content of the synthetic resin emulsion (A) for moistureproof processing. Alternatively, the moisture-proof resin composition according to the item 10.