JPH0227480B2 - KAMINOSUBERIBOSHIZAI - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a novel and useful anti-slip agent for paper. More specifically, the product obtained by emulsion copolymerization using a specific emulsifier and dispersant is applied onto the surface of paper or paperboard using a device such as a size press or calender, or manually using a brush or the like. The present invention relates to an anti-slip agent for paper that can prevent these slips. [Prior Art] Recently, with the diversification and specialization of the uses of paper and paperboard, various paper quality improvers have come to be used.In addition, improvements in paper making technology have improved paper strength and size. Efforts have been made to improve paper quality such as printability, smoothness, and gloss, but on the other hand, the coefficient of friction on the paper surface decreases, and there is a tendency for the paper to become more slippery. Of course, it is essential to improve the quality of paper as described above, but if the paper or paperboard is slippery, it may be difficult to operate it during the process of winding it up from a paper machine, printing process, or even manufacturing process of corrugated boxes. Trouble occurs. In addition, there is a problem in that problems such as damage to the contents due to the paper product becoming unbalanced or the cardboard box being unbalanced during loading may occur. Therefore, it is strongly desired to improve the paper quality and to make the paper less slippery. [Problem to be solved by the invention] Conventionally, methods have been used to make the paper surface less slippery, such as roughening the surface of paper or coating paper or paperboard with inorganic substances such as alumina sol or silica gel. This method is not only problematic in terms of operation, as the size press roll causes significant wear on the carrier roll and requires constant maintenance and inspection of the equipment. This anti-slip method by applying an inorganic substance is not preferable, as the wear of the render roll will eventually lead to a decline in paper quality.Therefore, there is a strong need for the development of a rational anti-slip agent. ing. In order to solve these problems,
Various anti-slip agents have been proposed in Japanese Patent Application Laid-open No. 56598 and Japanese Patent Application Laid-Open No. 171796/1984. However, its performance is still insufficient, and there is a need for an anti-slip agent with better properties. An object of the present invention is to provide an anti-slip agent for paper that can prevent paper from slipping without damaging the quality of the paper or using inorganic materials that pose problems in mechanical operation. [Means for Solving the Problems] Therefore, the present inventors have made extensive studies in order to meet these actual circumstances, and as a result, we have developed an emulsification dispersion of a specific vinyl copolymer that has been cationized using a quaternizing agent. Emulsifying (co)using specific vinyl monomers as an agent
When an emulsified (co)polymer dispersion obtained by polymerization is applied to the surface of paper or paperboard, a paper base material with reduced slipperiness and a large coefficient of friction can be obtained without any deterioration of paper quality. This discovery led to the completion of the present invention. That is, the present invention provides (1) 20 to 60 parts by weight of an emulsifying dispersant obtained by cationizing a copolymer obtained by copolymerizing monomers having the following composition (A) or (B), and this emulsifying dispersant. At least one of the following (a), (b), (c), and (d) in the presence of 20 to 60 parts by weight of the agent.
The present invention provides an anti-slip agent for paper containing an emulsion containing 80 to 40 parts by weight of a polymer or copolymer obtained by emulsion polymerization of monomers having two compositions. (b) Only (a) below (b) Only (d) below (c) 80 to 2 mol% of (e) below, one or two selected from each of the groups (a) or (d) below. 20 to 98 mol% or more (d) 80 to 2 mol% of the following (e), 20 to 98 mol% of two or more selected from the following groups (a) and (d) (A) 95 of the following (a) ~50 mol%, below (b) 5-50 mol% (B) Below (a) 94-30 mol%, below (b) 5-50 mol%
and the following (c) 1 to 20 mol% (a) General formula [However, R ₁ in the formula represents a hydrogen atom or a methyl group, and R ₂ represents a hydrogen or chlorine atom, or a methyl group, an ethyl group, or a monochloromethyl group. ] Styrene and/or styrene derivative (b) General formula [However, in the formula, R ₁ represents a hydrogen atom or a methyl group, R ₃ represents a methyl group or an ethyl group, and n is an integer of 2 or 3. ] Acrylic ester and/or methacrylic ester represented by (c) Other vinyl monomers having copolymerizability with (a) and (b) above (d) General formula [However, R ₁ in the formula represents a hydrogen atom or a methyl group, and R ₄ represents an alkyl group having 1 to 18 carbon atoms. ] Acrylic acid ester and/or methacrylic acid ester (e) Bifunctional crosslinkable monomer having copolymerizability with the above (a) and (b) Next, the present invention will be explained in detail. Styrene represented by the general formula [ ] and/
Typical styrene derivatives (a) include styrene, α-methylstyrene, vinyltoluene, ethylvinylbenzene, chlorostyrene, and chloromethylstyrene; on the other hand, acrylic acid represented by the general formula [] Representative esters and/or methacrylates (b) include dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminoethyl (meth)acrylate or diethylaminopropyl (meth)acrylate. ) dialkylaminoalkyl esters of acrylic acid. In addition, typical examples of other vinyl monomers (c) that are copolymerizable with the monomer (a) of the general formula [] and the monomer (b) of the general formula [] include methyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, lauryl (meth)acrylate or stearyl (meth)acrylate ( Meth)acrylic acid esters; esters of maleic acid or fumaric acid such as dibutyl maleate, dibutyl fumarate or dioctyl maleate; vinyl acetate or acrylonitrile. The above monomers (a), (b), and (c) are (a) 95 to 50 mol%, (b)
Monomer of composition (A) consisting of 5 to 50 mol% or (a)
94-30 mol%, (b) 5-50 mol%, (c) 1-20 mol%
A copolymer is obtained by copolymerizing the monomers having the composition (B) consisting of: This copolymer is cationized, and as the quaternizing agent used in this cationization reaction, any commonly used quaternizing agent can be used, but typical examples include dimethyl sulfate, methyl Examples include chloride, allyl chloride, ethylene chlorohydrin, and epichlorohydrin, and the reaction using such quaternizing agents can be carried out according to known and commonly used methods. On the other hand, acrylic ester and/or methacrylic ester (d) represented by the general formula []
Typical examples include methyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, or stearyl (meth)acrylate. ) Acrylic acid esters. Further, examples of the above-mentioned difunctional crosslinkable monomer (e) include diallyl phthalate, ethylene glycol dimethacrylate, divinylbenzene, and the like. (b) with only the above monomer (a), only with the above monomer (d)
(b) Consists of 80 to 2 mol% of the above monomer (e) and 20 to 98 mol% of one or more selected from each of the above monomers (a) or (d). , the above monomer (e) 80-2
mol%, consisting of 20 to 98 mol% of two or more monomers selected from both groups of monomers (a) and (d) above, is reacted in the presence of the cationized copolymer obtained above. A polymer or copolymer is thus obtained. The quaternary cationized copolymer of (A) or (B) used as the milk dispersant is prepared by a known solution polymerization or bulk polymerization method in the presence of a radical polymerization initiator. can get. In this case, the above-mentioned (meth)acrylic acid ester (b) is 5 to 50 mol%.
However, if it is outside this range, there will be no sufficient emulsifying and dispersing effect, and the anti-slip effect of the final product will be poor. The reason why the amount of the copolymerizable vinyl monomer (c) used is limited to 1 to 20 mol% is also the same. The emulsifying and dispersing agent obtained by cationizing a copolymer obtained by copolymerizing the above (A) or (B) is used in an amount of 20 to 60 parts by weight, preferably 33 to 51 parts by weight, and the monomer (A), (b), (c), and (d) are emulsified (co)polymerized.
Note that even if the emulsifying dispersant is in a range of 10 to 70 parts by weight, which is wider than the above range, a pre-emulsifying (co)polymerization product can be obtained. If the amount of the emulsifying dispersant is less than 10 parts by weight, the emulsion polymerization will not be completed sufficiently and an emulsifying (co)polymer will not be obtained, and if the amount is more than 70 parts by weight, the final product will be in the form of the emulsifying and dispersing agent itself. There is little difference from
Furthermore, the anti-slip effect of the final product cannot be improved. A quaternary cationized copolymer of the above copolymer (A) or (B) is used as an emulsifying dispersant, and various monomers a and/or (d) listed above are used.
alone, or an appropriate combination of these and the bifunctional crosslinking monomer (e) listed above ((a), (b), (c), (ni)).
))
The emulsion (co)polymer obtained from is obtained using a known emulsion polymerization method in an aqueous solution in the presence of a radical polymerization initiator. Bifunctional crosslinking monomer (e) is 2 to 80
Although it is limited within a range of mol %, if it is outside this range, a sufficient anti-slip effect cannot be obtained. In this way, in the presence of a cationized copolymer of (A) or (B), (a), (b),
The anti-slip agent of the present invention is obtained by polymerizing or copolymerizing (c) and (d). When applying the thus obtained anti-slip agent of the present invention to paper or paperboard, the anti-slip agent itself may be used alone, or the anti-slip agent may be combined with polyvinyl alcohol, starch, polyvinyl acetate or Of course, it may be used in combination with other conventional paper quality improvers such as carboxymethylcellulose. Further, when the anti-slip agent of the present invention is used as a coating liquid, there is no problem in controlling the pH as appropriate within the range of 3 to 11. Furthermore, the amount of the anti-slip agent applied is usually 0.1~
The amount is approximately 1.0 g (solid content)/m ² , but this amount may be increased or decreased as appropriate depending on the purpose of application. The anti-slip agent of the present invention not only exhibits a sufficient anti-slip effect when applied to paper or paperboard, but also has the function of imparting sizing properties to paper. [Examples] Next, the present invention will be specifically explained using Examples and Comparative Examples. All percentages refer to percentages by weight unless otherwise specified. Example 1 83.2 g of styrene, 37.1 g of dimethylaminoethyl methacrylate and 51.5 g of toluene are placed in a 4-necked flask equipped with a stirrer, thermometer and reflux condenser.
was charged, and 2.0 g of azobisisobutyronitrile was added as a polymerization initiator, and a polymerization reaction was carried out at a reaction temperature of 90° C. for 4 hours. Next, 12.0g of acetic acid
and 261.9 g of water were added, heated to 90-100°C, and distilled off by azeotropic action of toluene and water. After that, epichlorohydrin was added to the obtained copolymer.
18.5 g was added to make the copolymer a quaternary cation, and the required amount of water was further added to adjust the solid content to 25%. After cooling to room temperature, 104.1 g of styrene, 100.1 g of methyl methacrylate and 76.5 g of diallyl phthalate were added to the quaternary cationized copolymer, followed by 720.3 g of water and 2.0 g of potassium persulfate.
g was added thereto, and a polymerization reaction was carried out at a reaction temperature of 70°C for 4 hours. A necessary amount of water was added to the resulting emulsion copolymer to adjust the solids content to 25%. The ratio of the emulsifying dispersant to the monomer (solid content) at this time was 33 to 67. Example 2 A four-necked flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 78.0 g of styrene, 31.4 g of dimethylaminoethyl methacrylate, 9.9 g of 2-ethylhexyl acrylate, and 51.1 g of toluene, and further azo was added as a polymerization initiator. 2.0 g of bisisobutyronitrile was added and a polymerization reaction was carried out at a reaction temperature of 80° C. for 6 hours. Next, 12.0g of acetic acid and water
259.9 g of the mixture was added, and the mixture was heated to 90 to 100°C to distill off toluene by azeotropic action with water. Thereafter, 25.2 g of dimethyl sulfate was added to the obtained copolymer to make the copolymer a quaternary cation, and the required amount of water was further added to adjust the solid content to 25%. After cooling to room temperature, 124.8 g of styrene, 19.6 g of ethyl methacrylate, and 67.9 g of diethylene glycol dimethacrylate were added to the quaternary cationized copolymer, followed by 532.0 g of water and 2.
1.5 g of 2'-azobis(2-aminodinopropane) dihydrochloride was added, and a polymerization reaction was carried out at a reaction temperature of 70°C for 4 hours. Thereafter, the required amount of water was added to the obtained emulsion copolymer to adjust the solid content to 25%. The ratio of the emulsifying dispersant to the monomer (solid content) at this time was 40 to 60. Example 3 A four-neck flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 90.5 g of styrene, 37.1 g of diethylaminoethyl acrylate, 10.2 g of stearyl methacrylate, and 59.1 g of toluene, and azobisisobutylene was added as a polymerization initiator. Lonitrile
2.0g was added and a polymerization reaction was carried out at a reaction temperature of 90°C for 4 hours. Next, 12.0 g of acetic acid and 295.1 g of water were added, and the mixture was heated to 90 to 100°C to distill off toluene by azeotropic action with water. Thereafter, 18.5 g of epichlorohydrin was added to the obtained copolymer to make the copolymer a quaternary cation, and the required amount of water was further added to adjust the solid content to 25%. After cooling to room temperature, 101.8 g of α-methylstyrene, 19.8 g of stearyl methacrylate, and 30.5 g of commercially available divinylbenzene (a mixture of divinylbenzene and ethylbenzene) were added to the quaternary cationized copolymer, followed by 366.4 g of water. g and 15.0 g of 30% hydrogen peroxide solution, and the reaction temperature was 80.
The polymerization reaction was carried out at ℃ for 3 hours. Then, add the required amount of water to the obtained emulsion copolymer to remove the solid content.
Adjusted to 25%. The ratio of emulsifying dispersant to monomer (solid content) at this time was 51/49. Comparative Example 1 Commercially available anti-slip agent (SiO ₂ type) Comparative Example 1
And so. Comparative Example 2 Comparative Example 2 was an aqueous solution of an anti-slip agent with a solid content of 20% obtained according to Reference Example 5 described in JP-A No. 57-56598. Application test example 1 Anti-slip agents obtained in Examples 1 to 3 and commercially available anti-slip agent of Comparative Example 1 (SiO ₂ type)
0.2g each on kraft paper (basis weight 65g/m ² )
(solid content)/m ² was applied with a brush and dried at room temperature. 24 in a constant temperature and humidity room at 20℃ and 65% relative humidity.
After holding for a period of time, the slip angle of each of these coated papers was measured. The sliding angle is determined by the inclination method (Japan Tappi No.31−
79), and the sliding angles obtained when sliding was repeated 1, 5, and 10 times are listed in Table 1.

[Table] Application test example 2 0.2 g (solid content) of each of the anti-slip agents obtained in Examples 1 to 3 and the commercially available anti-slip agent of Comparative Example 1 was added to a C-class liner (basis weight 180 g/m ² ). / ^m2
Apply the amount using a roll applying a linear pressure of 50 kg/cm,
It was dried at 100°C for 1 minute. After being kept in a constant temperature and humidity room at 20°C and 65% relative humidity for 24 hours, the slip angle of each coated paper was measured. The slip angle was measured in the same manner as in Application Test Example 1, and the slip angles obtained when sliding was repeated 1, 5, and 10 times are listed in Table 2.

[Table] Application test example 3 The anti-slip agent obtained in Example 3 and the commercially available anti-slip agent of Comparative Example 2 were added to a C-class liner (basis weight 180 g/m ² ) at 0.05 g (solid content)/m. ² ,
Amounts of 0.1 g (solid content)/m ² and 0.25 g (solid content)/m ² were applied using a laboratory size press device at a nip pressure of 50 kg/cm and a coating speed of 100 mg/min. ,
Dry at 100°C for 30 seconds. This coated paper is heated at 20℃.
After conditioning the humidity in a constant temperature and humidity room at 65% relative humidity for 24 hours, the slip angle of each coated paper was measured using the method described above, and the results are shown in Table 3.

[Table] Application test example 4 The anti-slip agents of Example 3 and Comparative Example 2 were applied to high-quality paper (basis weight 65 g/m ² , calcium carbonate content 14%), and 0.5 g (solid content)/m ² 1.5 at 110°C using a laboratory roll coater.
Let dry for a minute. The slip angles of these coated papers were measured by the method described above, and the results are shown in Table 4.

[Table] Of the results in Tables 1 to 4, especially Table 3 shows that the product of the present invention (Example 3) achieved the same or higher level of anti-slip properties with a coating amount of 1/5 of that of Comparative Example 2. It is known to have an anti-slip effect. That is, the anti-slip agent of Example 3 was added at 0.05 g/m ²
(Solid content) The slip angle obtained when applying the anti-slip agent of Comparative Example 2 at 0.25 g/m ^{2 (solid content) was equal to or higher than the slip angle obtained when applying the anti-slip agent of Comparative Example 2 at 0.25 g/m 2} (solid content). There is. [Effects of the Invention] According to the present invention, it is possible to provide an anti-slip agent for paper containing an emulsion obtained by obtaining an emulsion polymer having the above composition in the presence of a cationized copolymer having the above composition. There are no problems with mechanical operation, and there is no damage to the paper quality.

Claims (1)

[Claims] 1. An emulsifying dispersant obtained by cationizing a copolymer obtained by copolymerizing monomers having the following composition (A) or (B):
obtained by emulsion polymerization of 20 to 60 parts by weight of monomers having at least one of the following compositions (a), (b), (c), and (d) in the presence of 20 to 60 parts by weight of this emulsifying and dispersing agent. An anti-slip agent for paper, characterized in that it contains an emulsion containing 80 to 40 parts by weight of a polymer or copolymer. (b) Only (a) below (b) Only (d) below (c) Below (e) 80 to 2 mol%, one or two selected from the following groups (a) or (d): More than 20
~98 mol% (d) 80-2 mol% of the following (e), 20-98 mol% of two or more selected from both groups (a) and (d) below (A) 95-50 of the following (a) Mol%, below (b) 5 to 50 mol% (B) following (a) 94 to 30 mol%, following (b) 5 to 50 mol%, and following (c) 1 to 20 mol% (a) General formula [However, R ₁ in the formula represents a hydrogen atom or a methyl group, and R ₂ represents a hydrogen atom, a chlorine atom, or a methyl group, an ethyl group, or a monochloromethyl group. ] Styrene and/or styrene derivative (b) General formula [However, in the formula, R ₁ represents a hydrogen atom or a methyl group, R ₃ represents a methyl group or an ethyl group, and n is an integer of 2 or 3. ] Acrylic ester and/or methacrylic ester represented by (c) Other vinyl monomers having copolymerizability with (a) and (b) above (d) General formula [However, R ₁ in the formula represents a hydrogen atom or a methyl group, and R ₄ represents an alkyl group having 1 to 18 carbon atoms. ] Acrylic ester and/or methacrylic ester (e) Bifunctional crosslinkable monomer 2 having copolymerizability with the above (a) and (b) 33 to 51 parts by weight of an emulsifying dispersant, emulsion polymerization The anti-slip agent for paper according to claim 1, characterized in that the amount of the polymer or copolymer obtained is 67 to 49 parts by weight. 3. The anti-slip agent for paper according to claim 1 or 2, wherein the paper is paperboard.