JPH1095893A - Moistureproofing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a moistureproofing composition which, when applied to paper, can give highly moistureproof paper which can be reclaimed even when wasted by mixing a copolymer resin emulsion prepared by using an emulsifier with a fatty acid ester, a rosin acid ester and a polyhydric alcohol. SOLUTION: This composition comprises a copolymer resin emulsion (A) obtained by using an emulsifier, a fatty acid ester (B), a rosin acid ester compound (C) prepared from maleinized or fumaric mohipied rosin and an alcohol, and a polyhydric alcohol (D). Component A is desirably a latex (especially of SBR or MBR) obtained by emulsion-polymerizing butadiene and an ethylenically unsaturated monomer in the presence of a reactive emulsifier in an aqueous phase. Component B is desirably a stearic ester which is desirably dispersed in water for convenience in use. Component C desirably has a softening point of 80-140 deg.C and an acid value of 35 or above. Component C may be used in the form of a solution in an alcohol or may be made water- salable with n alkali. Coated paper prepared by using this composition has moistureproofness equivalent to that of polyethylene-laminated paper.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for moisture-proof processing, and more particularly, to a composition for moisture-proof processing in which a paper or nonwoven fabric is coated or impregnated to form a moisture-proof layer. The present invention relates to a moisture-proof and waterproof composition that facilitates recovery and recycling of waste paper and waste paper, and is applied to the field of wrapping paper.

[0002]

2. Description of the Related Art Conventionally, as a moisture-proof paper, there are a moisture-proof coat paper in which a base paper is coated with a vinylidene chloride resin and a polyethylene laminate paper.

[0003] These moisture-proof papers have been applied to the field of wrapping paper because of their good moisture-proof performance. In recent years, from the viewpoint of effective use of resources and measures against pollution, there is a problem as to whether it is easy to recycle paper when collecting waste paper or waste paper.

[0004] From this viewpoint, in the case of polyethylene laminated paper, there is a problem that it is difficult to disintegrate the resin layer and the paper, and it is difficult to recycle even if the waste paper or the waste paper is collected. Further, when a vinylidene chloride resin is applied, the generation of toxic gas of halogen when incinerating the coated paper has recently become an environmental problem.

[0005] As described above, all moisture-proof papers have problems, and the development of alternative moisture-proof papers is strongly demanded. As an alternative technique, a technique of obtaining a moisture-proof paper by applying a composition obtained by mixing 5-200 parts by weight of a wax with 100 parts by weight of a copolymer resin emulsion is disclosed in Japanese Patent Publication No. 55-2259.
In the publication.

However, in this technique, since a wax is used, the coated surface is slippery, and a slip preventive agent or the like is used, but the slip resistance is not satisfied. Also,
Moisture-proof performance is reduced due to the loss of wax due to abrasion of the coated surface. Further, problems such as blocking of the coated paper occur due to the pressure at the time of winding the coated paper.

[0007] As an alternative technique, a wax is blended with an acrylic emulsion, and the mixture is applied to a cardboard.
A technology for manufacturing moisture-proof paper has also been proposed (Japanese Patent Publication No. 2-1).
No. 671).

[0008] However, the moisture-proofing properties of the moisture-proof paper obtained by this technique are inferior to those of vinylidene chloride resin coated paper and polyethylene laminated paper.

Therefore, at present, the paper industry and processing agent manufacturers can provide an emulsion-type moisture-proof resin capable of imparting moisture-proof properties comparable to polyethylene-laminated paper and recovering waste paper and waste paper. Is desired.

[0010]

DISCLOSURE OF THE INVENTION The present invention relates to a high moisture-proof performance (JIS Z-020) comparable to that of polyethylene laminated paper.
It is an object of the present invention to provide a moisture-proof composition capable of imparting 8) and recovering waste paper and waste paper.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a copolymer resin emulsion, a fatty acid ester compound, a rosin acid ester compound and a polyhydric alcohol are used. By coating a paper with a resin emulsion composition blended at a specific ratio of
Demonstrates the same high moisture-proof performance as polyethylene laminate,
In addition, the inventors have found that a moisture-proof paper which can easily recover waste paper and waste paper and has excellent blocking resistance can be obtained, and have completed the present invention.

That is, the present invention relates to a method for preparing a copolymer resin emulsion (A) obtained by using an emulsifier, a fatty acid ester (B) obtained by reacting a fatty acid with an alcohol, and maleating or fumarating the emulsion. An object of the present invention is to provide a moisture-proof resin composition comprising a rosin ester compound (C) and a polyvalent alcohol (D) obtained by reacting rosin and alcohol.

Also preferably, the fatty acid of the fatty acid ester (B) is stearic acid, preferably the emulsifier is a reactive emulsifier, and preferably the copolymer resin emulsion (A) is a mixture of butadiene and It is a butadiene-based latex obtained by emulsion-polymerizing a copolymerizable ethylenically unsaturated monomer and a fatty acid ester in an aqueous medium, and more preferably the copolymer resin emulsion (A) has an acid value of 30 to 100, preferably a rosin acid ester compound (C) having a softening point of 80 ° C to 140 ° C,
Provided is a moisture-proof resin composition having an acid value of 35 or more.

More preferably, the weight ratio of the copolymer resin emulsion (A) to the fatty acid ester (B), the rosin acid ester compound (C) and the polyhydric alcohol (D) is 100: 3 to 100: The present invention provides a moisture-proof resin composition having a ratio of 1 to 100: 5 to 30.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION

The copolymer resin emulsion (A) is an emulsion comprising a copolymer obtained by copolymerizing two or more types of ethylenically unsaturated monomers shown below.

Examples of the ethylenically unsaturated monomer include a conjugated diene monomer and an ethylenically unsaturated monomer copolymerizable therewith. Examples of the conjugated diene monomer include 1.3-butadiene and isoprene. Of these, 1,3-butadiene is preferred.

Examples of the ethylenically unsaturated monomer copolymerizable with the conjugated diene monomer include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl metalcurate, acryl Butyl acrylate, metal butyl acrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate,
Alkyl acrylates and alkyl methacrylates exemplified by heptyl methacrylate, octyl acrylate, octyl methacrylate, octadecyl acrylate, octadecyl methacrylate; styrene;
Ethylenically unsaturated aromatic monomers represented by α-methylstyrene, vinyltoluene, chlorostyrene, 2,4-dibromostyrene and the like; unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, crotonic acid , Maleic acid and anhydrides thereof, fumaric acid, itaconic acid and unsaturated dicarboxylic acid monoalkyl esters, for example, ethylenically unsaturated carboxylic acids such as monomethyl maleate, monoethyl fumarate and mono-n-butyl itaconate; vinyl acetate, propion Vinyl esters such as vinyl acid; vinylidene halides such as vinylidene chloride and vinylidene bromide; ethylenic compounds such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and 2-hydroxyethyl methacrylate Unsaturated carboxylic acid Hydroxyalkyl esters; grilledyl esters of ethylenically unsaturated carboxylic acids such as glysilyl acrylate and grilsil methacrylate, and acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, N-butoxymethylacrylamide Polymerization of ethylene, diacetone acrylamide, etc.

When an ethylenically unsaturated carboxylic acid is used as the ethylenically unsaturated monomer copolymerizable with the conjugated diene monomer, the copolymer resin emulsion (A) has an acid value of 30 to 100. Preferably, there is.

These compounds are important compounds generally used for imparting appropriate hardness to the emulsion film and for improving adhesion, dispersibility, mechanical stability and freezing stability. The minimum film forming temperature (MFT) of the latex is preferably 50 ° C. or less in consideration of film forming properties.
It is not restricted to these conditions.

As described above, the copolymer resin emulsion of the present invention is preferably a butadiene-based latex. Examples of the butadiene-based latex include SBR,
All polymer aqueous dispersions containing butadiene such as MBR and NBR are included. Among them, SBR and MBR are preferable in order to obtain high moisture proof performance.

In producing the copolymer resin emulsion used in the present invention, an emulsifier is used. As such emulsifiers, commercially available anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like can be used. Preferably, an emulsifier is used. Examples of the reactive emulsifier include commercially available soda styrenesulfonate, soda vinylsulfonate, and emulsifiers having various ethylenically unsaturated groups. Among them, Japanese Patent Application Laid-Open No.
Compounds having the following structural formula shown in JP 203960 are most preferred.

[0023]

[Formula 1]

(Wherein, R is an alkyl group having 12 carbon atoms, or 18 carbon atoms in which one hydrogen atom is substituted by a fluorine atom)
And M represents Na or NH ₄ . The amount of the emulsifier is not particularly limited, but is preferably 0.1 to 3 parts by weight based on 100 parts by weight of the copolymer emulsion. If the amount of the emulsifier exceeds 3 parts by weight, it is difficult to use a butadiene-based latex as a copolymer emulsion and combine it with a fatty acid ester compound to develop high moisture-proof properties.

Production of the copolymer resin emulsion of the present invention
When mixing, the above-mentioned ethylenically unsaturated monomer
Free radical generation under the condition of using emulsifier
The polymerization may be carried out at 40 ° C. to 80 ° C. by adding a medium. H
Examples of the free radical generating catalyst include potassium sulfate.
(K_TwoS_TwoO), ammonium sulfate [(NH_Four)_TwoS
_TwoO ₉], An aqueous catalyst such as hydrogen peroxide, tert-butyl
Idoperoxide, cumene hydroperoxide, etc.
Oil-based catalyst.

Further, additives usually used for radical polymerization, for example, a chain transfer agent, ethylenediaminetetraacetic acid, pH
An alkali substance for adjustment can be used if necessary. The obtained copolymer emulsion is used after being concentrated to a required solid content by a method such as stripping.

The fatty acid constituting the fatty acid ester (B) used in the present invention is preferably a higher fatty acid having 6 or more carbon atoms, and the alcohol is preferably a higher alcohol, and having 16 carbon atoms in consideration of water resistance. Above
Particularly, stearic acid is more preferable.

The fatty acid ester may be in the form of powder, water-dispersed type, etc., but the water-dispersed type is preferred in view of the workability of compounding.

The amount of the fatty acid ester compound used is as follows:
Although not particularly limited, copolymer resin emulsion 100
It is preferable to use 3 to 100 parts by weight based on parts by weight. When the amount of the fatty acid ester is less than 3 parts by weight, it is difficult to obtain moisture-proof performance, and when the amount of the fatty acid ester exceeds 100 parts by weight, the durability of the coated surface becomes poor. The use amount of the fatty acid ester compound is more preferably 5 to 50 parts by weight.

The rosin acid ester compound (C) used in the present invention is obtained by reacting a maleated or fumarated rosin with an alcohol. The softening point and acid value of the rosin ester compound are not particularly limited, but a rosin ester compound having a softening point of 80 ° C to 140 ° C and an acid value of 35 or more is preferable, and 150 to 250 is more preferable in terms of disintegration.

When the rosin acid ester compound is used, it is used by dissolving it in methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol or the like. Alternatively, an alkali solution such as aqueous ammonia, sodium hydroxide, potassium hydroxide, ethylamine, triethylamine, dimethylethanolamine, methyldiethanolamine, triethanolamine or the like may be added to form an aqueous solution. Further, a material which has been dispersed in water in advance may be used. The use amount of the rosin acid ester is not particularly limited, but it is preferable to use 1 to 100 parts by weight based on 100 parts by weight of the copolymer emulsion. If the amount of the rosin acid ester is less than 1 part by weight, the disintegration of the coated paper is difficult, and if it exceeds 100 parts by weight, it is difficult to obtain high moisture-proof performance.

The polyhydric alcohol used in the present invention includes
For example, ethylene glycol, propylene glycol,
1,4-butanediol, 1,6-hexanediol,
Neoventil glycol, glycerin, polyethylene glycol (molecular weight: 200 to 1500), polypropylene glycol (molecular weight: 400 to 3000) and the like. The amount of the polyhydric alcohol is not particularly limited, but is preferably 5 to 30 parts by weight based on 100 parts by weight of the copolymer resin emulsion. When the amount is less than 5 parts by weight, the disintegration property is insufficient, and when the amount is more than 30 parts by weight, the moisture-proof property decreases.

As a method of combining the fatty acid ester compound, the rosin acid ester compound and the copolymer emulsion, the fatty acid ester compound and / or the rosin acid ester compound may be blended with the copolymer resin emulsion, or the fatty acid ester compound and the rosin acid ester compound may be blended. An ethylenic monomer mixture copolymerizable with butadiene may be emulsion-polymerized in the presence of a rosin acid ester.

The copolymer resin emulsion obtained by the above method can reduce the amount of the fatty acid ester compound and the rosin acid ester compound to obtain the same moisture-proof property, and furthermore, the resulting moisture-proof paper is free from bleeding. There is an advantage that the printability is not deteriorated because the amount is small.

The resin composition for moisture-proof processing of the present invention is applied directly to a substrate as it is, or by blending various fillers with the composition, or impregnating the substrate with an impregnating machine, and pressing by size. A wide variety of processing methods such as adhesion to paper can be applied.

As a method for processing the moisture-proofing composition of the present invention into paper or nonwoven fabric, various methods such as coating with various coaters, impregnation with an impregnating machine, or processing with a size press can be used. The composition for moisture-proof processing may be used as it is, or various fillers may be blended if necessary.

The coating amount of the moisture-proofing resin composition of the present invention is preferably 20 g / m ² or less with respect to the substrate in view of cost and recovery of waste paper and waste paper.
If it is 5 g / m ² or less, it is difficult to exhibit high moisture-proof properties. The coating amount is preferably from 10 to 15 g / m ² .

As the base material, paper, paperboard, nonwoven fabric,
It can be used as a fiber base material.

[0039]

The present invention will be described below with reference to Synthesis Examples and Examples. All parts and percentages in the examples are based on weight.

Synthesis Examples 1-7 120 parts of water, 0.1 part of sodium hydroxide, and 0 parts of reactive emulsifier S-180 [unsaturated alkyl sulfate, manufactured by Kao Corporation] were placed in a high-pressure polymerization vessel equipped with a stirrer. .5 parts, ethylenediaminetetraacetic acid 0.1 parts, styrene 45 parts, butadiene 52
Part, acrylic acid 3.0, t-dodecyl mercaptan 0.
One part was charged, stirring was started, and when the temperature in the polymerization vessel raised to the reaction temperature of 60 ° C. reached 60 ° C., 0.1 part of ammonium persulfate was added to start the reaction. After 7 hours, cooling was performed when the conversion reached 98%. The obtained copolymer resin emulsion had a polymerization rate of 98.6%. Then, the pH of the emulsion was adjusted to 9.0 with 25% aqueous ammonia, and then steam distillation was performed to obtain a copolymer resin emulsion having a solid content of 50.1% and an emulsifier content of 1% or less.

Synthesis Examples 8 to 9 In a high-pressure polymerization vessel equipped with a stirrer, 120 parts of water, 0.1 part of sodium hydroxide, and a reactive emulsifier S-180 [unsaturated alkyl sulfate, manufactured by Kao Corporation] were added. 0.5 part, 0.1 part of ethylenediaminetetraacetic acid, 45 parts of styrene, 52 parts of butadiene, 3 parts of acrylic acid, and 0.1 part of t-dodecylmercaptan were charged, stirring was started, and the reaction temperature was raised to 60 ° C.
When the temperature inside the polymerization vessel reached 60 ° C., 0.1 part of ammonium persulfate was added to start the reaction.
After 7 hours, cooling was performed when the conversion reached 98%. The obtained copolymer resin emulsion had a conversion of 98.
6%. Next, the pH of the emulsion was adjusted to 9.0 with 25% aqueous ammonia, followed by steam distillation, and the solid content of the emulsifier was 1% or less and the fatty acid ester compound and the rosin acid ester compound were mixed to 4% each.
9.9% and 50.1% copolymer resin emulsions were obtained.

Examples 1 to 9 Using the copolymer resin emulsions obtained in Synthesis Examples 1 to 9, resin compositions for moisture-proof processing having the formulations shown in Table 1 were obtained.
This composition was applied to commercially available high-quality paper (basis weight 70 m ² ).
About 12 g / m ² of coating amount is applied by wire lot,
The coated paper was dried at 120 ° C. for 1 minute using a hot air drier to process the moisture-proof coated paper.

Synthesis Examples 10 to 12 In a high-pressure polymerization vessel equipped with a stirrer, 120 parts of water, 0.1 part of sodium hydroxide, and 0 emulsifier Neoperex F-25 [sodium salt of alkylbenzenesulfonic acid, manufactured by Kao Corporation] were added in an amount of 0 parts. 0.5 part, ethylenediaminetetraacetic acid 0.1 part, styrene 45 parts, butadiene 52 parts, acrylic acid 3.0, t-dodecylmercaptan 0.1 part, and stirring was started.
When the temperature in the polymerization vessel, which was raised to 60 ° C., reached 60 ° C., 0.1 part of ammonium persulfate was added to start the reaction. After 7 hours, cooling was performed when the conversion reached 98%. The obtained copolymer resin emulsion had a polymerization rate of 98.6%. Next, the pH of the emulsion was adjusted to 9.0 with 25% aqueous ammonia, and thereafter, a copolymer resin emulsion having an emulsifier content of 1% or less and a solid content of 50.1% was obtained by steam distillation.

Synthesis Examples 10 to 14 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 added.
[Alkalibenzene sulfonic acid sodium salt, manufactured by Kao Corporation],
0.5 part, ethylenediaminetetraacetic acid 0.1 part, styrene 45 parts, butadiene 52 parts, acrylic acid 3 parts
And 0.1 part of t-dodecyl mercaptan, and stirring was started to raise the reaction temperature to 60 ° C. 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, the conversion is 98%
When cooling was achieved, cooling was performed. The obtained emulsion had a polymerization rate of 98.6%. Next, the pH of the emulsion was adjusted to 9.0 with 25% aqueous ammonia, followed by steam distillation to obtain solids containing an emulsifier of 1% or less and containing a fatty acid ester compound at 49.9% and 59.9%, respectively.
A 0.1% copolymer resin emulsion was obtained.

Comparative Examples 1 to 10 The copolymer resin emulsions obtained in Synthesis Examples 10 to 14 and a commercial SBR (solid content: 50.0%,
An emulsifier amount of at least 1 part by weight) and a commercially available acrylic emulsion (solid content of 45.1%, emulsifier amount of at least 1 part by weight) were wire-bonded to a commercially available high-quality paper (basis weight: 70 g / m ² ). -A coating amount of about 12 g / m < ² > was applied according to lot and dried in a hot air dryer at 120 [deg.] C. for 1 minute. The coating amount and the JISZ0208 for the processed paper thus obtained are described.
Was measured (cup method at 40 ° C. and 90% humidity under constant temperature and humidity conditions). As Comparative Example 10, a commercially available polyethylene laminated paper was used. Tables 4 and 5 show the results.

According to Tables 4 and 5, the moisture-proof value of the emulsion containing no fatty acid ester compound was as shown in Example 1.
The values are higher than the values obtained in Nos. 1 to 9 and indicate that they cannot be used as a substitute for polyethylene-laminated paper in terms of moisture-proof properties. It is also understood that the effect of the fatty acid ester compound on the moisture resistance is better in the emulsion. It can be seen that the moisture-proof paper of the composition containing no polyhydric alcohol has poor disintegration properties, and the moisture-proof paper of the composition containing no rosin acid ester has poor disintegration properties and blocking properties.

Table 3 shows the measurement results of the physical properties of the moisture-proof coated paper.
4 and Table 5. Each physical property in the table was measured and evaluated by the following methods. 1. Moisture Permeability (g / m ² , 24 hr) 20 ° C., 9 under constant temperature and humidity conditions according to JIS 0208
It was measured by the cup method at 0% RH.

2. Disintegration 535 ml of warm water in a household mixer pot at 40 ° C.
0.8 g of 5% sodium hydroxide is added, 1 g of coated paper cut into a 3 cm square is added, and defibration is performed for 3 minutes, and the defibration property between the resin and the paper is visually determined.

3. Blocking Coated paper 10 × 10c at a press temperature of 40 ° C of a small press machine
m coated surface and black paper, press pressure 10kg / c
Pressing is performed for 15 minutes at m ^2, and the state of transfer to the black paper coated surface is visually determined.

[0050]

[Table 1]

In the table, the rosin acid ester is Beckasite P-896 [softening point 100-115, acid value 185-20.
5 Dainippon Ink and Chemicals, Inc.] was used. As the fatty acid ester, Nopco LB-550 [stearic acid ester manufactured by San Nopco Co., Ltd.] was used.

PEG 600; polyethylene glycol Number average molecular weight 600 [manufactured by Nisso Oil Chemical Co., Ltd.] PPG400; polypropylene glycol 400 (manufactured by Nisso Oil Chemical Co., Ltd.) PPG700; PPG1000; 〃 1000 (manufactured by Nisso Yuka Co., Ltd.)

[0053]

[Table 2]

[0054]

[Table 3]

[0055]

[Table 4]

[0056]

[Table 5]

[0057]

The coated paper using the resin composition for moisture-proof processing of the present invention has better moisture-proof performance than the conventional moisture-proof coated paper using a polymer. Further, it is easy to repulp coated paper and has extremely excellent blocking resistance, so that it is very useful as moisture-proof paper.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C09D 133/12 C09D 133/12

Claims (6)

[Claims] 1. A copolymer resin emulsion (A) obtained by using an emulsifier, a fatty acid ester (B) obtained by reacting a fatty acid and an alcohol, and a maleated or fumarated rosin and an alcohol. And a rosin acid ester compound (C) obtained by reacting the compound with a polyhydric alcohol (D). 2. The composition according to claim 1, wherein the fatty acid of the fatty acid ester (B) is stearic acid. 3. The composition according to claim 1, wherein the emulsifier is a reactive emulsifier. 4. A copolymer resin emulsion (A) obtained by emulsion-polymerizing butadiene, an ethylenically unsaturated monomer copolymerizable therewith, and a fatty acid ester in an aqueous medium in the presence of an emulsifier. The composition according to any one of claims 1 to 3, wherein the composition is a butadiene-based latex. 5. The composition according to claim 1, wherein the rosin acid ester compound (C) has a softening point of 80 ° C. to 140 ° C. and an acid value of 35 or more. 6. The weight ratio of the copolymer resin emulsion (A), the fatty acid ester (B), the rosin acid ester compound (C) and the polyhydric alcohol (D) is 100: 3-1.
The composition according to any one of claims 1 to 5, wherein the ratio is from 00: 1 to 100: 5 to 30.