TW201934846A - Surface emulsion sizing agent for papermaking, manufacturing method thereof and coating paper capable of exhibiting excellent mechanical stability, producing little foaming, and exerting extremely excellent sizing effect - Google Patents

Abstract

The present invention provides a surface emulsion sizing agent for papermaking that exhibits excellent mechanical stability, produces little foaming, and exerts extremely excellent sizing effect, and also provides a manufacturing method of the surface emulsion type sizing agent for papermaking, and a coating paper. The surface emulsion sizing agent for papermaking in accordance with the present invention is characterized in including a shell part containing a surfactant (A); and a core part containing a polymer (B) of monomer components, and a rosin (C), wherein the polymer (B) of monomer components contains styrene (b1). Furthermore, the amount of the surfactant (A) to be used is 20 to 200 parts by weight per 100 parts by weight of the polymer (B) and the rosin (C) in terms of weight of solidcontents. The surfactant (A) includes a polymer containing a monomer component of styrene (a1) and/or [alpha]-olefin (a2) or starch. The monomer component constituting the polymer (B) further includes (meth)acrylic acid ester (b2).

Description

Surface emulsion type sizing agent for paper making, manufacturing method of surface emulsion type sizing agent for paper making, and coated paper

The present invention relates to a surface emulsion type sizing agent for papermaking, a method for producing a surface emulsion type sizing agent for papermaking, and coated paper.

Generally speaking, sizing agents for papermaking are roughly divided into aqueous solution type and emulsion type, but the latter has relatively low viscosity even if the solid content (non-volatile content) is set to a relatively high level. It has good operability and foaming properties of the coating liquid. Also relatively small advantages.

However, since the surface emulsion type sizing agent for papermaking is unstable to mechanical shearing, when the coating is applied to paper by a coating method that applies a strong shearing force such as a sizing pressing method, the emulsion is broken and dross is generated. Or foaming may cause uneven coating and decrease workability. As a result, there are problems such as reduction in sizing effect. This problem is particularly significant in the case of using hard water in which metal ions are dissolved, such as industrial water.

As a method for improving mechanical stability, for example, in conjunction with anionic or nonionic emulsifiers, the use of high molecular weight compounds as protective colloids can be considered, and a surface sizing agent is proposed, which is based on a specific molecular weight benzene An emulsion containing a hydrophobic unsaturated monomer such as an emulsion polymerized styrene in the presence of an ethylene-maleic acid copolymer salt (Patent Document 1). However, the surface emulsion type sizing agent has insufficient sizing effect and mechanical stability.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 08-246391

The invention provides a surface emulsion type sizing agent for papermaking, which has excellent mechanical stability and less foaming, and exerts a better sizing effect; and provides a method for manufacturing a surface emulsion type sizing agent for papermaking and a coating method thereof. Cloth paper.

The inventors expected to focus on improving the sizing effect and using rosin, or the mechanical stability would be deteriorated due to the use of rosin. When reviewing various conditions, they found a surface emulsion sizing agent for papermaking to solve the aforementioned problems. The subject has a shell part containing a surfactant, a core part containing a polymer containing a specific monomer component, and a rosin type, and the present invention has been completed. That is, this invention relates to the following surface emulsion type sizing agent for papermaking, the manufacturing method of the surface emulsion type sizing agent for papermaking, and coated paper.

A surface emulsion type sizing agent for paper making, comprising: a shell portion containing a surfactant (A); and a core portion containing a monomer-containing polymer (B) and a rosin (C) ; And the polymer (B) containing the monomer component contains a styrene (b1).

2. The surface emulsion type sizing agent for papermaking as described in the preceding paragraph 1, wherein the amount of the component (A) used is 100 parts by weight based on the solid content relative to the total weight of the components (B) and (C), It is 20 to 200 parts by weight.

3. The surface emulsion type sizing agent for papermaking as described in the above item 1 or 2, wherein the component (A) contains a polymer containing a monomer component of a styrene (a1) and / or an α-olefin (a2) , Or starch.

4. The surface emulsion type sizing agent for papermaking according to any one of the preceding paragraphs 1 to 3, wherein the monomer component forming the component (B) further comprises a (meth) acrylate (b2).

5. The surface emulsion type sizing agent for papermaking according to any one of the preceding paragraphs 1 to 4, wherein the monomer component forming the component (B) further contains an unsaturated monomer (b3) having a hydrophilic group.

6. The surface emulsion type sizing agent for papermaking according to any one of the preceding paragraphs 1 to 5, wherein the component (C) is selected from the group consisting of undenatured rosin, α, β-unsaturated carboxylic acid modified rosin, and unmodified rosin. At least one of the groups of esters.

7. The surface emulsion type sizing agent for papermaking according to any one of the preceding paragraphs 1 to 6, wherein the proportion of the component (B) and component (C) is based on the weight of the solid component, (B) / (C ) = 20/80 ~ 95/5.

8. The surface emulsion type sizing agent for papermaking according to any one of the foregoing paragraphs 1 to 7, wherein the volume average particle diameter is 50 to 300 nm.

9. A method for producing a surface emulsion type sizing agent for papermaking according to any one of the preceding paragraphs 1 to 8, characterized in that, in the component (A), a monomer component that forms the component (B) and (C) ) Ingredients and emulsion polymerization.

10. A coated paper comprising the surface emulsion type sizing agent for papermaking as described in any one of items 1 to 8 above.

The surface emulsion type sizing agent for papermaking according to the present invention has excellent mechanical stability, less foaming, and exhibits an excellent sizing effect during papermaking.

The surface emulsion type sizing agent for papermaking of the present invention (hereinafter, also referred to simply as "emulsion type sizing agent") has a shell portion containing a surfactant (A) (hereinafter, referred to as (A) component) ; And a core part containing a monomer-containing polymer (B) (hereinafter, referred to as (B) component) and rosin (C) (hereinafter, referred to as (C) component); and the aforementioned monomer-containing component The polymer (B) contains a styrene (b1) (hereinafter, referred to as (b1) component). Hereinafter, each component is demonstrated in detail.

The component (A) is a component that forms the shell portion of the emulsion-type sizing agent. By functioning as a protective colloid, it has excellent mechanical stability and also has the effect of reducing foaming. The type is not particularly limited. In the present invention, for example, from the viewpoint of emulsification with the component (B) and the component (C), a styrene (a1) (hereinafter referred to as (a1) component) and / A polymer of a monomer component of α-olefin (a2) (hereinafter, referred to as (a2) component) or starch is preferred.

(a1) The component is not particularly limited, and examples thereof include styrene, α-methylstyrene, tert-butylstyrene, dimethylstyrene, ethoxylated styrene, hydroxystyrene, and vinyl. Toluene, vinyl chloride, etc. These can be used alone or in combination of two or more.

(a1) The amount of the component used is not particularly limited. From a viewpoint, the total of the total monomer components forming the component (A) is 100% by weight, usually about 20 to 90% by weight, and preferably about 40 to 80% by weight.

(a2) The component is not particularly limited, and examples thereof include diisobutylene (2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, 2,4 , 4-trimethyl-1-pentene and a mixture of 2,4,4-trimethyl-2-pentene), 3-methyl-1-butene, 3-methyl-1-pentene, Branched α-olefins such as 4-methyl-1-pentene; 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-decene Linear alpha-olefins of hexadecene, 1-octadecene, 1-eicosene, 1-tetracosene, 1-tetradecene, etc .; cyclohexene, methylcyclohexene Cyclic α-olefins such as vinylcyclohexane, 4-vinylcyclohexene, cyclopentene, methylcyclopentene and the like. These can be used alone or in combination of two or more. Among them, from the viewpoint of the sizing effect of coated paper, branched α-olefins are preferred, and diisobutylene is more preferred.

(a2) The use amount of the component is not particularly limited. From the viewpoint of the effect of coating paper sizing, the total amount of all monomer components forming the component (A) is 100% by weight, which usually accounts for about 0 to 60% by weight. , Preferably about 0 to 50% by weight.

From the viewpoint of the emulsifiability of the component (B) and the component (C), the monomer component forming the component (A) is further combined with an unsaturated monomer (a3) having a carboxyl group (hereinafter referred to as (a3) component), ( Dialkylaminoalkyl (meth) acrylate (a4) (hereinafter, referred to as (a4) component), N, N-dialkylaminoalkyl (meth) acrylamidoamine (a5) (hereinafter, It is preferably called (a5) component).

(a3) The component is not particularly limited, and examples thereof include (anhydrous) acrylic acid (referred to as anhydrous acrylic acid or acrylic acid, the same applies hereinafter), (anhydrous) methacrylic acid, (anhydrous) maleic acid, and (anhydrous) itaconic acid. Acid, (anhydrous) citraconic acid, or these neutralizing salts, half esters, half ester neutralizing salts, and the like. These can be used alone or in combination of two or more. Among them, acrylic acid, maleic acid, and anhydrous maleic acid are preferred from the viewpoint of polymerizability with the component (a1) or (a2).

(a3) The amount of the component used is not particularly limited. From the viewpoint of emulsification with the components (B) and (C), the total amount of all monomer components forming the component (A) is 100% by weight, which usually accounts for About 10 to 80% by weight, preferably about 20 to 50% by weight.

(a4) The component is not particularly limited, and examples thereof include (N) N-dimethylaminoethyl (meth) acrylate, -N, N-diethylaminoethyl (meth) acrylate, (Meth) acrylic-N, N-dimethylaminopropyl, (meth) acrylic-N, N-dimethylaminobutyl, (meth) acrylic-N, N-dipropylamine Ethyl ester, -N, N-dibutylaminoethyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.

(a4) The amount of the component used is not particularly limited. From the viewpoint of emulsification with the components (B) and (C), the total amount of all monomer components forming the component (A) is 100% by weight, usually accounting for 100% by weight. About 0 to 40% by weight, preferably about 5 to 30% by weight.

(a5) The component is not particularly limited, and examples thereof include N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamine Amine, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-dipropylaminoethyl (Meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide. These can be used alone or in combination of two or more.

(a5) The amount of the component used is not particularly limited. From the viewpoint of emulsification with the components (B) and (C), the total amount of all monomer components forming the component (A) is 100% by weight, which usually accounts for About 0 to 20% by weight, preferably about 1 to 10% by weight.

In the case of using the (a4) component and (a5) component, a part or all of the amine groups derived from the (a4) component and the (a5) component are graded in four stages from the (B) component and the (C) component. The emulsification viewpoint is preferable. The degree of gradation is not particularly limited, but the (a4) component and / Or at least about 10 mole% of the amine group of (a5) component is more preferable, and about 50 to 100 mole% is more preferable. Various grades can be used as the grade 4 chemical agent for grade 4, for example, chlorotoluene, methyl chloride, dimethyl sulfate, glycidol, vinyl chloride, allyl chloride, styrene oxide, ring Oxypropane, epichlorohydrin, etc. The four-stage system is usually at a temperature of about 50 to 90 ° C., preferably for 1 to 4 hours. It is usually performed after the polymer is prepared, but it can also be performed before or during the polymerization.

Further, in the monomer component, an unsaturated monomer (a6) (hereinafter, referred to as (a6) component) other than (a1) to (a5) component may be appropriately used in combination. (a6) The component is not particularly limited, and examples thereof include (meth) acrylates, unsaturated monomers having a sulfofluorenyl group, (meth) acrylamide, and the like.

The (meth) acrylate is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, (n) -propyl (meth) acrylate, and n-butyl (meth) acrylate Ester, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and dodecyl (meth) acrylate.

The unsaturated monomer having a sulfonyl group is not particularly limited, and examples thereof include vinylsulfonic acid, sodium styrenesulfonate, and sodium (meth) allylsulfonate.

(Meth) acrylamide includes acrylamide and methacrylamide.

These (a6) components can be used individually or in combination of 2 or more types. The amount of the (a6) component to be used is not particularly limited, but the total amount of all the monomer components forming the (A) component is 100% by weight, preferably about 1 to 10% by weight.

The component (A) of the present invention is obtained by appropriately combining the aforementioned monomer components and polymerizing them in the presence of a polymerization initiator. The polymerization method is not particularly limited, and a known method can be adopted. In the case of solution polymerization, aromatic hydrocarbons such as benzene and toluene; ketones such as acetone and methyl ethyl ketone; alcohols such as n-propanol and isopropyl alcohol can be used as the solvent.

The polymerization initiator is not particularly limited. For example, azo-based compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis-2,4-dimethylvaleronitrile may be used. ; Or benzamidine peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, tert-butyl peroxy-2-ethylhexanoate, dicumyl peroxide, ten Organic peroxides such as dialkyl peroxides; any of other redox catalysts. The amount of the polymerization initiator used is not particularly limited, and may be about 0.1 to 5 parts by weight based on 100 parts by weight of the total monomer components forming the component (A).

In addition, during polymerization, mercaptans such as 2-mercaptoethanol, n-dodecyl mercaptan; alcohols such as ethanol, isopropanol or pentanol; carbon tetrachloride, ethylbenzene, isopropyl Chain transfer agents for benzene, cumene, α-methylstyrene dimer, 2,4-diphenyl-4-methyl-1-pentene, etc. The use amount of the chain transfer agent is not particularly limited, and may be about 0.01 to 5 parts by weight based on 100 parts by weight of the entire monomer component forming the component (A).

The conditions of the polymerization reaction are generally carried out at a reaction temperature of about 70 to 140 ° C and a reaction time of about 1 to 10 hours.

The physical properties of the component (A) obtained by the aforementioned method are not particularly limited. For example, the weight-average molecular weight (value of polystyrene converted by gel permeation chromatography) from the viewpoint of the effect of sizing on coated paper In the case of 5,000 ~ 40,000, it is better.

For polymers, the pH can also be adjusted during or after polymerization. Regarding the adjustment, various conventional pH adjusting agents can be used. Examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; and alkaline earth metals such as calcium hydroxide. Hydroxides; amines such as monomethylamine, dimethylamine, monoethylamine, diethylamine, triethylamine; ammonia, etc. The pH value is not particularly limited, but it is preferably adjusted to about 4 to 10.

Starches are not particularly limited, for example, corn starch, potato, tapioca Unmodified starch of wheat flour, wheat starch, rice starch, sago starch, etc .; cationized starch, oxidized starch, phosphate modified starch, carboxymethylated starch, hydroxyethylated starch, carbamate ethylated starch, cyanoethyl Processed starch such as basic starch, dialdehyde starch, acetic acid modified starch; denatured unmodified starch or processed starch (hereinafter also referred to as "raw starch") with inorganic peroxide, enzymes, inorganic acids, etc. Modified starch and so on.

The inorganic peroxide is not particularly limited, for example, hypochlorite; ammonium persulfate (hereinafter, also referred to as APS), potassium persulfate (hereinafter, also referred to as KPS), sodium persulfate (hereinafter, referred to as SPS) ), Etc. peroxodisulfate; hydrogen peroxide, etc. These can be used alone or in combination of two or more. Furthermore, iron sulfate or copper sulfate may be combined with hydrogen peroxide.

The enzyme is not particularly limited, and examples thereof include α-amylase produced by various bacteria, animals and plants.

The inorganic acid is not particularly limited, and examples thereof include hydrochloric acid, sulfuric acid, and phosphoric acid. These can be used alone or in combination of two or more.

The use amount of the aforementioned treatment agent is not particularly limited. From the viewpoint of reactivity with the raw material starch, it is preferably about 0.01 to 10 parts by weight based on 100 parts by weight of the raw material starch, based on the solid content, and is preferably 0.1. ~ 6 parts by weight is more preferred.

The method for producing modified starch is not particularly limited, and examples thereof include heating an aqueous solution composed of starches and a treating agent at a temperature of about 60 to 100 ° C. and about 30 to 60 minutes.

The physical properties of the modified starch obtained by the aforementioned manufacturing method are not particularly limited. For example, the Brookfield viscosity of an aqueous solution having a solid concentration of 15% by weight is 5 to 1000 mPa at a temperature of 25 ° C. s, preferably 10 ~ 200mPa. s around.

(A) The amount of the component used is based on the weight of the solid component relative to the component (B) and (C) The total of the ingredients is 100 parts by weight, generally about 20 to 200 parts by weight, and preferably about 30 to 100 parts by weight. By forming the aforementioned numerical range, the dispersion stability of the surface emulsion type sizing agent and the sizing effect of the coated paper can be improved.

In addition, as the component (A), in addition to the aforementioned polymer, a cationic surfactant, a nonionic surfactant, or an anionic surfactant can be used.

The cationic surfactant is not particularly limited. For example, dodecyltrimethylammonium chloride, cetyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetradecyl Alkyl dimethyl benzyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, and the like. As these commercially available products, for example, CATIOGEN H, CATIOGEN L, manufactured by Daiichi Industries Pharmaceutical Co., Ltd., QUARTAMIN24P, QUARTAMIN86P CONC, QUARTAMIN60W, QUARTAMIN86W, etc., manufactured by Kao Corporation can be purchased.

The nonionic surfactant is not particularly limited, and examples thereof include polyethylene glycol, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene styrylphenyl ether, and polyoxyethylene Sorbitan fatty acid esters, nonionic surfactants having reactive functional groups in the molecule, and the like.

The anionic active agent is not particularly limited, and examples thereof include dialkyl sulfosuccinate, alkane sulfonate, α-olefin sulfonate, polyoxyethylene alkyl ether sulfosuccinate, and Oxyethylene styrylphenyl ether sulfosuccinate salt, naphthalenesulfonic acid formaldehyde condensate, polyoxyethylene alkyl ether sulfate salt, polyoxyethylene alkylphenyl ether sulfate salt, and the like.

These other surfactants may be used alone or in combination of two or more kinds.

(B) component is a polymer containing a monomer component containing (b1) component, and is formed A component of the shell part of the emulsion sizing agent, which helps to coat the sizing effect of paper.

The component (b1) is not particularly limited, and examples thereof include those exemplified for the component (a1). These can be used alone or in combination of two or more.

(b1) The use amount of the component is not particularly limited, and from the viewpoint of the sizing effect of the coated paper, the total amount of all monomer components forming the (B) component is 100% by weight, and generally 10 to 80% by weight. %, Preferably about 20 to 70% by weight.

The monomer component forming the component (B) is not particularly limited. For example, a (meth) acrylate (b2) (hereinafter, referred to as (b2) component) and an unsaturated monomer (b3) having a hydrophilic group may be used in combination. (Hereinafter, referred to as (b3) component) and the like.

(b2) The component is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, (n) -propyl (meth) acrylate, and n-butyl (meth) acrylate Ester, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and dodecyl (meth) acrylate. These can be used alone or in combination of two or more. Among them, isobutyl (meth) acrylate is preferred from the viewpoint of the sizing effect of the coated paper.

(b2) The amount of the component to be used is not particularly limited. From the viewpoint of the sizing effect of the coated paper, the total amount of all monomer components forming the component (B) is 100% by weight, and generally 10 to 80% by weight. %, Preferably about 20 to 70% by weight.

(b3) The component is not particularly limited as long as it does not belong to the components (b1) and (b2). Examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; itaconic acid, Unsaturated itaconic acid, maleic acid, anhydrous maleic acid, fumaric acid, muconic acid, citraconic acid and other unsaturated dicarboxylic acids; 2-hydroxymethyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxyalkyl (meth) acrylates such as hydroxyethyl, hydroxy n-propyl (meth) acrylate, hydroxyisopropyl (meth) acrylate, etc .; Unsaturated monoalcohols such as propanol, methallyl alcohol; diethylene glycol (meth) acrylate, triethylene glycol (meth) acrylate, tetraethylene glycol (meth) acrylate, (meth) acrylic acid Polypropylene glycol-based unsaturated vinyl monomers such as dipropylene glycol, tripropylene glycol (meth) acrylate, and tetrapropylene glycol (meth) acrylate. These can be used alone or in combination of two or more. Among them, acrylic acid is preferred.

(b3) The amount of the component to be used is not particularly limited. From the standpoint of dispersion stability of the emulsion sizing agent and the sizing effect of the coated paper, the total of all monomer components forming the component (B) is 100% by weight, generally about 10-20% by weight, preferably about 5-20% by weight.

In addition, other monomer components (b4) (b4) (hereinafter, referred to as (b4) component) other than (b2) component and (b3) component may be used in combination with diethyl maleate and di-n-butyl maleate as required. Ester, isobutyl maleate, di-n-octyl maleate, di-n-decyl maleate, di-n-dodecyl maleate, di-n-hexadecyl maleate, etc. Unsaturated dicarboxylic acid dialkyl esters; -N, N-diethylaminoethyl (meth) acrylate, -N, N-diethylaminopropyl (meth) acrylate, (methyl ) Dialkylamino (meth) acrylates such as -N, N-diethylaminobutyl acrylate; vinyl esters such as vinyl propionate and vinyl acetate; acrylonitrile and methacrylonitrile Nitriles such as N, N-diethyl (meth) acrylamide, N, N-dipropyl (meth) acrylamide, etc., N, N-dialkyl (meth) acrylamide; N, N'-Methylene bis (meth) acrylamide, N, N'-propylene bis (meth) acrylamide, bisacrylamide dimethyl ether, etc .; vinyl Unsaturated monomers having a sulfonyl group, such as sulfonic acid, sodium styrene sulfonate, sodium (meth) allyl sulfonate, and the like. These can be used alone or in combination of two or more. The amount of the component (b4) used is not particularly limited, and the total amount of all monomer components forming the component (B) is 100% by weight, and preferably about 1 to 20% by weight.

Further, if necessary, mercaptans such as 2-mercaptoethanol, n-dodecyl mercaptan; alcohols such as ethanol, isopropanol or pentanol; carbon tetrachloride, ethylbenzene, cumene, isopropyl alcohol Propylbenzene, α- Methylstyrene dimer, 2,4-diphenyl-4-methyl-1-pentene and other chain transfer agents. The use amount of the chain transfer agent may be about 0.01 to 5 parts by weight based on 100 parts by weight of the entire monomer component forming the component (B).

The component (C), which is the same as the component (B), is a component that forms the shell portion of the emulsion sizing agent, and contributes to the sizing effect of the coated paper. In addition, due to the affinity with the component (A), the mechanical stability of the emulsified sizing agent is also improved, and contamination of coating equipment and the like can be reduced. (C) The component is not particularly limited, and examples thereof include gum rosin, wood rosin, tall oil rosin, Nanyang rosin (rosin containing dihydroagathic acid), and wetland rosin (containing cypress Unsaturated rosin, such as acid rosin); hydrogenated rosin, α, β-unsaturated carboxylic acid modified rosin, disproportionated rosin, or esterified products thereof (unmodified rosin ester, α, β-unsaturated carboxylic acid modified rosin ester) , Disproportionated rosin ester)). These can be used alone or in combination of two or more. Among them, from the viewpoint of the sizing effect of coated paper, it is preferable to contain at least one selected from the group consisting of undenatured rosin, α, β-unsaturated carboxylic acid modified rosin, and unmodified rosin esters. At least one of the group consisting of gum rosin, maleic rosin, and gum rosin ester is more preferred.

The component (C) may be purified by a conventional vacuum distillation method, steam distillation method, extraction method, recrystallization method, or the like.

α, β-unsaturated carboxylic acid denatured rosin is based on the addition of α, β-unsaturated carboxylic acid to undenatured rosin. The α, β-unsaturated carboxylic acid is not particularly limited, and examples thereof include α, β-unsaturated dicarboxylic acids such as maleic acid, anhydrous maleic acid, and fumaric acid; and α, such as acrylic acid and methacrylic acid. , Β-unsaturated monocarboxylic acid and the like. The amount of the α, β-unsaturated carboxylic acid is not particularly limited, and it is generally about 1 to 30 parts by weight relative to 100 parts by weight of the undenatured rosin.

The method for producing α, β-unsaturated carboxylic acid denatured rosin components is not particularly limited, For example, after mixing undenatured rosin and α, β-unsaturated carboxylic acid in an appropriate reaction vessel, heating and melting, and performing Diels-Alder at about 190 to 230 ° C for about 1 to 3 hours. Method of reaction.

The physical properties of α, β-unsaturated carboxylic acid-denatured rosin are not particularly limited. From the viewpoint of sizing effect of coated paper, generally, the softening point is about 85 to 140 ° C, and the acid value is 195 to 320 mgKOH / g. About about, preferably, the softening point is about 95 to 130 ° C, and the acid value is about 240 to 295 mgKOH / g.

Undenatured rosin ester is a reaction product of undenatured rosin and polyol.

The polyhydric alcohol is not particularly limited, and a trihydric alcohol and / or a tetrahydric alcohol are preferred. The former is exemplified by trimethylolethane, trimethylolpropane, and 3-methylpentane-1,3. , 5-triol, etc .; or the latter, for example, pentaerythritol and diglycerol may be mentioned.

The undenatured rosin ester can be produced by various conventional methods. For example, it is obtained by subjecting an undenatured rosin and a polyol to an esterification reaction at a temperature of generally 200 to 350 ° C for 6 to 20 hours. The reaction can be performed under any of normal pressure, reduced pressure, and increased pressure. In addition, the usage ratio of undenatured rosin and polyol is also not particularly limited. Generally, the equivalent ratio [OH _(eq) / COOH _(eq) ] of the former carboxyl group to the latter hydroxyl group is about 0.2 to 1.5, preferably 0.4. ~ 1.2 or so. In the reaction, an esterification catalyst such as p-toluenesulfonic acid or various antioxidants may be used. The reaction may be carried out under a nitrogen stream.

The physical properties of the undenatured rosin ester are not particularly limited. From the viewpoint of sizing effect of coated paper, generally, the softening point is about 80 to 100 ° C, the acid value is about 0 to 25 mgKOH / g, and the hydroxyl value is 0. It is preferably about 30 mgKOH / g, preferably a softening point of about 85 to 95 ° C, an acid value of about 10 to 20 mgKOH / g, and a hydroxyl value of about 0 to 10 mgKOH / g.

The ratio of (B) and (C) components [(B) / (C)], from the viewpoint of the mechanical stability of the emulsion type sizing agent, is generally 20/80 ~ 95 in terms of solid content by weight About / 5, preferably about 50/50 to 90/10.

The surface emulsion type sizing agent for papermaking of this invention can be obtained by various conventional manufacturing methods. The manufacturing method is not particularly limited, and examples thereof include mixing monomer components (A) and (B) and monomer components (C), and performing solution polymerization, emulsion polymerization in the presence of a polymerization initiator, A method of suspension polymerization and the like, but from the viewpoint of the polymerizable properties of the monomer component forming the (B) component and the (C) component, the monomer component forming the (B) component and (C) A method for emulsification polymerization of the component. More specifically, in the presence of the (A) component and a polymerization initiator, the method for dripping the (B) component and the (C) component for emulsification polymerization is preferred. In particular, if a mixed solution of the monomer component (B) component and the (C) component is added, the obtained emulsion sizing agent is excellent in mechanical stability and sizing effect. The conditions of the emulsion polymerization are not particularly limited, and the temperature is generally about 40 to 150 ° C (preferably about 60 to 100 ° C), and the time is generally about 1 to 10 hours (preferably about 1 to 3 hours).

The polymerization initiator is not particularly limited, and examples thereof include peroxides such as hydrogen peroxide, ammonium persulfate, and potassium persulfate; tert-butyl peroxybenzoate, tert-butyl peroxy-2- Organic peroxides such as ethylhexanoate, dicumyl peroxide, dodecyl peroxide; 2,2'-azobisisobutyronitrile and dimethyl-2,2'- The azo-based compounds such as azobisisobutyl ester and the like may be used alone or in combination of two or more kinds. In addition, the amount of the polymerization initiator used is also not particularly limited, and it is generally about 0.1 to 10 parts by weight, and preferably about 1 to 5 parts by weight, relative to 100 parts by weight of all the monomer components forming the component (B).

Also, sulfites such as sodium sulfite, and sulfites such as sodium bisulfite can be used. A hydrogen salt, triethanolamine, cuprous sulfate, or the like is used in combination with the aforementioned polymerization initiator.

In addition, when manufacturing a surface emulsion type sizing agent for papermaking, a solvent may be used as necessary.

The solvent is not particularly limited, and examples thereof include alcohols such as ethanol and isopropanol; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and benzene; ethyl acetate, chloroform, and dimethylformamide And other organic solvents, or water, and mixed solvents of the foregoing organic solvents and water.

In addition, the pH of the surface emulsion type sizing agent for papermaking may be adjusted with various conventional pH adjusting agents during or after production. The pH adjusting agent is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; Monomethylamine, dimethylamine, monoethylamine, diethylamine, triethylamine, etc .; ammonia, etc.

The physical properties of the surface-emulsion sizing agent for papermaking of the present invention are not particularly limited. For example, the volume average particle diameter measured by the light scattering method is generally about 50 to 300 nm, preferably about 50 to 150 nm, and more preferably It is about 50 ~ 80nm. By such a value range, the mechanical stability of the emulsion sizing agent and the sizing effect of the coated paper can be balanced.

In addition, the Brookfield (Brookfield) viscosity at a solids concentration of 25% by weight and a temperature of 25 ° C is generally 10 to 200 mPa. s, preferably 30 ~ 80mPa. s around.

In addition, the pH value at a temperature of 25 ° C. is generally about 7 to 11, preferably about 7.5 to 9.5.

The surface emulsion type sizing agent for papermaking of the present invention can also be added with additives such as antioxidants, defoaming agents, preservatives, chelating agents, water-soluble aluminum compounds, etc., as required.

As a coating liquid containing the surface emulsion type sizing agent for papermaking of the present invention, The aforementioned emulsion sizing agent may be used directly or diluted with water or the like, and various additives may be mixed according to requirements. Examples of the additive include starches such as oxidized starch, phosphated starch, home (modified) starch, cationized starch, and amphoteric starch; celluloses such as carboxymethyl cellulose; polyvinyl alcohols, and polymers Paper strength enhancers, anti-slip agents, preservatives, rust inhibitors, pH adjusters, defoamers, thickeners, fillers, antioxidants, waterproof Additives, film-forming aids, pigments, dyes, etc.

The solid content concentration of the coating liquid is not particularly limited, but is generally about 0.5 to 30% by weight, and preferably in the range of 1 to 20% by weight for practical use.

The present invention relates to those who coat paper. Coated paper refers to those containing a surface emulsion type sizing agent for papermaking, and specifically refers to those obtained by applying the coating solution to the surface of a base paper.

The base paper is not particularly limited. Generally, uncoated paper and paperboard using wood cellulose fibers as raw materials can be used. The base paper is obtained from papermaking pulp. Examples of the papermaking pulp include chemical pulp such as LBKP and NBKP, mechanical pulp such as GP and TMP, and recycled pulp. In addition, various medicines such as fillers, sizing agents, and paper strength enhancers can be added to the base paper.

In addition, the coating means of the coating liquid is not particularly limited, and for example, various conventional methods such as a dipping method, a slurry method, a door roll method, a bar coating method, a calendering method, and a spraying method can be applied. In addition, the coating amount (concentration) of the coating liquid is also not particularly limited, but is generally about 0.005 to 1 g / m ² , and preferably about 0.01 to 0.5 g / m ² .

The coated paper obtained by the aforementioned means is not particularly limited, and examples thereof include recording papers such as report paper, PPC paper, and thermal recording paper; coating of art paper, cast coated paper, and high-quality coated paper. Paper; kraft paper, pure white roll paper, packaging paper; note paper, books Various papers (foreign paper) such as tissue paper, printing paper, newsprint paper, etc .; Manila chipboard, white chipboard, recycled chipboard, etc. Paperboard board and liner or core board paper.

[Example]

Hereinafter, the present invention will be described with examples, but the present invention is not limited thereto. In addition, the parts and% of Examples and Comparative Examples are based on weight unless otherwise specified.

(Viscosity)

The viscosity of the sample adjusted to 25 ° C was measured using a B-type viscosity agent (manufactured by Toki Sangyo Co., Ltd.).

(pH)

A commercially available measuring machine (product name "pH METER F-14", manufactured by Horiba, Ltd.) was used to measure the pH value of the sample (solid content concentration: 25%) adjusted to 25 ° C.

(Softening Point)

Measured by the ring and ball method of JIS K 2531.

(Acid value)

Measured in accordance with JIS K 0070.

(Hydroxy value)

Measured in accordance with JIS K 0070.

(Volume average particle diameter)

Measurement was performed using a light scattering particle size analyzer (product name "ELSZ-2", manufactured by Otsuka Electronics Co., Ltd.).

Production Example 1-1 (Manufacture of Polymer (A-1))

In a flask equipped with a stirrer, a cooling tube, a nitrogen introduction tube, and a thermometer, stir 85 parts of isopropanol, 43 parts of ion-exchanged water, 125.9 parts of styrene (70% of the total monomer content), and 80% acrylic acid under a nitrogen gas stream. 67.5 parts (30% of the total monomer content) of the mixed solution, while heating to 70 ° C, and mixing 7.3 parts of tert-butylperoxy-2-ethylhexanoate (trade name "PERBUTYL® O") Company). The temperature was further increased to 80 to 90 ° C, and the polymer was obtained by holding for 4 hours. Then, 200 parts of ion-exchanged water, 0.045 part of hydroquinone, and 51.0 parts of 48% potassium hydroxide aqueous solution were mixed (equivalent to the anionic group in the polymer). At 50 mol%), after neutralization, isopropanol was evaporated. Further, 29.7 parts of ammonia water (corresponding to 50 mol% with respect to the anionic group in the copolymer) was added and dissolved to obtain a polymer (A-1) having a solid content concentration of 25%.

Production Example 1-2 (Manufacture of Polymer (A-2))

Diisobutene (2,4,4-trimethyl-1-pentene; 76% purity) is stirred in a reaction vessel equipped with a stirrer, a cooling tube, two dropping funnels, a nitrogen introduction tube, and a thermometer under a stream of nitrogen. A mixed solution of 70.3 parts (53.4% of the total monomer component), 46.6 parts of anhydrous maleic acid (46.6% of the total monomer component), and 180 parts of toluene, while heating to 70 ° C, and mixing 7.3 parts of tert-butyl peroxide Oxidized 2-ethylhexanoate (trade name "PERBUTYL® O" manufactured by Japan Oil & Fat Corporation). The temperature was further raised to 80 to 90 ° C, and the polymer was held for 4 hours to obtain a polymer. Then, 200 parts of ion-exchanged water, 0.045 part of hydroquinone, and 35.0 parts of 48% potassium hydroxide aqueous solution were mixed (equivalent to anionic groups in the polymer). At 100 mol%), after neutralization, toluene was evaporated to obtain a polymer (A-2) having a solid content concentration of 20%.

Production Example 1-3 (Manufacture of Polymer (A-3))

In a flask equipped with a stirrer, a cooling tube, a dropping funnel, a nitrogen introduction tube, and a thermometer, 70 parts of styrene, 30 parts of dimethylaminoethyl methacrylate, 42.9 parts of isopropyl alcohol, and 2,2'- 2.5 parts of azobisisobutyronitrile, polymerized at 80-85 ° C for 5 hours while stirring under a nitrogen stream reaction. Next, after adding 11.5 parts of acetic acid and 300 parts of water, 17.7 parts of epichlorohydrin was added, and the temperature was maintained at 80 ° C for 2 hours. Further, a predetermined amount of water was added to adjust the solid content concentration to 20% to obtain a polymer (A-3). .

Manufacturing Example 1-4 (manufacturing of APS modified starch (A-7))

In a flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube, add 100 parts of corn starch (trade name: "Prince ACE A", manufactured by Oji Corn Starch Co., Ltd., solid content concentration: 88%), 5 parts of APS, and water. 300 parts, and it heated up to 90 degreeC, and stirred for 1 hour. after that. After adding water to adjust the solid content concentration to 15%, it was cooled to 40 ° C to obtain APS modified starch (A-7).

Production Example 1-5 (Production of Enzyme Modified Starch (A-8))

In a flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube, 100 parts of corn starch ("Prince Ace A", manufactured by Oji Corn Starch Co., Ltd., solid content concentration 88%), KLEISTASE L1 (Amano enzyme Co., Ltd.) 0.1 parts and 300 parts of water, and the temperature was raised to 75 ° C, and after stirring for 40 minutes, the temperature was raised to 90 ° C and further stirred for 10 minutes. Thereafter, water was added to adjust the solid content concentration to 15%, and then cooled to 40 ° C to obtain enzyme-modified starch (A-8).

Production Example 1-6 (Sulfuric acid modified starch) (Production of A-9)

In a flask equipped with a stirrer, a cooling tube, a thermometer, and a nitrogen introduction tube, 250.0 parts of corn starch (trade name: "Oji Ace A", manufactured by Oji Corn Starch Co., Ltd., solid content concentration 88%), 20% sulfuric acid aqueous solution 11 (2.2 parts of solid content) and 300 parts of water, the temperature was raised to 90 ° C, and the mixture was stirred for 1 hour. Thereafter, water was added to adjust the solid content concentration to 15%, and the mixture was cooled to 40 ° C to obtain sulfate-modified starch (A-9).

Manufacturing Example 2-1 (Manufacture of Malay Rosin (C-2))

In a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube and cooling tube, mixing 600.0 g of domestic melted rosin melt at about 160 ° C and 42.0 g of anhydrous maleic acid were reacted at 200 ° C for 2 hours while stirring under a nitrogen stream, thereby obtaining a horse with a softening point of 97.4 ° C and an acid value of 234.5 mgKOH / g Come with rosin (C-2).

Manufacturing Example 2-2 (Production of Fumar Rosin (C-3))

In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a cooling tube, 600.0 g of a melt of about 160 ° C and 42.0 g of fumaric acid produced from Chinese gum rosin were mixed, and reacted at 200 ° C while stirring under a stream of nitrogen. 2 Hours, thereby obtaining a fumaric rosin (C-3) having a softening point of 104.5 ° C and an acid value of 219.5 mgKOH / g.

Production Example 2-3 (Production of Gum Rosin Ester (C-4))

In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube and a cooling tube, 663.2 parts of Chinese rosin and 55.6 parts of glycerol (equivalent ratio [OH (eq) / COOH (eq)] = 0.91) were added, and an antioxidant was added. 10 parts of NOCRAC300 (manufactured by Daichi Shinko Chemical Industry Co., Ltd.) and 0.1 part of p-toluenesulfonic acid of the catalyst, and reacted at 270 ° C for 15 hours while stirring under a nitrogen gas flow, thereby obtaining a softening point of 90.8 ° C and an acid value of 8.1 mgKOH / g of gum rosin ester (C-4).

Example 1

In a reaction vessel equipped with a stirrer, a cooling tube, a nitrogen introduction tube, a thermometer, and two dropping funnels, 50 parts of polymer (A-1) (solid content), 200 parts of ion-exchanged water, and anionic surfactant ( Product name: "HITENOL LA10" manufactured by Daiichi Kogyo Co., Ltd.) 2 parts, 0.08 parts by weight of iron (II) sulfate heptahydrate, and after fully replacing the oxygen in the reaction vessel with nitrogen, the inside of the system is stirred while being stirred The temperature was raised to 80 ° C. Next, separately mix the liquid in which 20 parts of Chinese rosin produced in the dropping funnel (I) is dissolved in a monomer mixture of 56 parts of styrene and 24 parts of acrylic acid, and the solid content concentration in the dropping funnel (II) is 35%. 10 parts of hydrogen peroxide water (3.5 parts by weight with respect to the monomer component) The solution was dissolved in 100 parts of water, and the solution was dripped into the system for about 2 hours. The reaction was further maintained for 2 hours to complete the reaction, and a paper emulsion surface sizing agent with a solid concentration of 25.5% was obtained. The viscosity, pH, and volume average particle diameter of the obtained surface emulsion type sizing agent for papermaking are shown in Table 1 (the same applies hereinafter).

Examples 2 to 21, Comparative Examples 1 to 3

The components and amounts shown in Table 1 were changed, and the same synthesis was performed as in Example 1 to individually obtain a surface emulsion type sizing agent for papermaking.

(Mechanical stability)

50g of a surface emulsion type sizing agent for paper was taken from a container scale of a Maron-type stability tester (manufactured by Shinsei Industry Co., Ltd.), and the mixture was stirred vigorously for 5 minutes at a temperature of 25 ° C, a load of 10kg, and a rotation speed of 1000rpm. Filter the agglomerates with a 350-mesh wire mesh that has been weighed beforehand. After drying at 105 ° C for 3 hours, the weights of the steel wire mesh and the aggregates were measured to obtain the solid weight of the aggregates. The value was calculated according to Equation 1, and judged by the following evaluation criteria.

(Formula 1) Mechanical stability (%) = (solid weight (g) of aggregates / solid weight (g) of surface emulsion sizing agent for papermaking) x 100

(Evaluation criteria)

◎: The calculated value above is less than 0.5%

○: Above calculated value is 0.5% or more and less than 1.0%

△: Above calculated value is 1.0% or more and less than 5.0%

×: Above calculated value is 5.0% or more

(Preparation of coating liquid)

Corn starch (trade name: "Prince ACE A", manufactured by Prince Corn Starch Co., Ltd.) Ionized water was diluted to a solid content concentration of 12%, and ammonium persulfate (hereinafter, referred to as APS) was added to the solid content of starch by 1.6%, and the temperature was maintained at 90 ° C for 20 minutes. Diluted with deionized water to a solid content concentration of 7.5%, and adjusted to pH 5.0 with a 48% aqueous sodium hydroxide solution to obtain APS modified starch. To 50 parts of the aforementioned APS modified starch, 1.47 parts of the surface emulsion type sizing agent for papermaking of Example 1 were mixed to prepare a coating solution. Moreover, the solid content concentration of the surface emulsion type sizing agent for papermaking in a coating liquid was 0.88%. In addition, the surface emulsion type sizing agents for papermaking of Examples 2 to 21 and Comparative Examples 1 to 3 were also carried out in the same manner to prepare coating liquids.

(Foaming property of coating liquid)

After each coating solution was heated to 50 ° C. and treated with a household mixer for 2 minutes, the height of the liquid surface immediately after the treatment was measured (the initial liquid surface height was 60 mm).

(Production of coated paper and evaluation of sizing effect)

Using a bar coater, each side of each coating liquid adjusted to a liquid temperature of 50 ° C was coated on the surface of high-quality neutral paper (water resistance: 0.5 seconds, basis weight: 70g / m ² ), and then at 105 ° C. The spin dryer was dried for 1 minute to prepare coated paper. In addition, the adhesion amount of the surface emulsion type sizing agent for papermaking of the base paper was about 0.08 g / m ² in terms of solid content, and the adhesion amount of starch was about 2 g / m ² in terms of solid content. The water resistance of the obtained coated paper was measured in accordance with JIS P 8122. The larger the value, the better the sizing effect.

<(A) component>

． A-1: Polymer of Production Example 1-1

． A-2: Polymer of Production Example 1-2

． A-3: Polymer of Production Example 1-3

． A-4: Corn starch (trade name: "Prince ACE A", manufactured by Prince Corn Starch Corporation)

． A-5: Tapioca starch

． A-6: Potato

． A-7: APS modified starch of manufacturing example 1-4

． A-8: Enzyme-modified starch of Production Example 1-5

． A-9: Sulfate-modified starch of Production Example 1-6

<(B) component>

． B-1: St / BA = 70/30 (weight ratio (conversion of solid content))

． B-2: St / IBMA = 70/30 (weight ratio (solid content conversion))

． B-3: St / BA / AA = 65/20/15 (weight ratio (solid content conversion))

． B-4: St / BA / DM = 65/20/15 (weight ratio (solid content conversion))

※ St-styrene, BA-acrylic-n-butyl, IBMA-isobutyl methacrylate, AA-acrylic, DM-N, N-dimethylaminoethyl methacrylate

<(C) component>

． C-1: Rosin from China

． C-2: Malay Rosin of Production Example 2-1

． C-3: Fumar rosin of Production Example 2-2

． C-4: Gum Rosin Ester of Production Example 2-3

Claims (10)

A surface emulsion sizing agent for papermaking, which is characterized in that it has a shell portion containing a surfactant (A), and a core portion containing a monomer-containing polymer (B) and a rosin (C); and The monomer-containing polymer (B) contains a styrene (b1). The surface emulsion type sizing agent for papermaking as described in the first patent application scope, wherein the use amount of the component (A) is based on the solid content weight relative to 100 parts by weight of the total of the components (B) and (C) 20 to 200 parts by weight. The surface emulsion type sizing agent for papermaking according to item 1 or 2 of the scope of patent application, wherein the component (A) contains: Polymers, or starches. The surface emulsion type sizing agent for papermaking as described in any one of claims 1 to 3, wherein the monomer component forming the component (B) further includes a (meth) acrylate (b2). The surface emulsion type sizing agent for papermaking as described in any one of claims 1 to 4, wherein the monomer component forming the component (B) further contains an unsaturated monomer (b3) having a hydrophilic group. The surface emulsion type sizing agent for papermaking as described in any one of claims 1 to 5, wherein the component (C) is selected from undenatured rosin, α, β-unsaturated carboxylic acid modified rosin, and unmodified At least one of the groups of denatured rosin esters. The surface emulsion type sizing agent for papermaking as described in any one of the claims 1 to 6, wherein the proportion of the component (B) and the component (C) is based on the solid content weight, (C) = 20/80 ~ 95/5. The surface emulsion type sizing agent for paper making as described in any of claims 1 to 7 of the scope of patent application, Among them, the volume average particle diameter is 50 to 300 nm. A method for producing a surface emulsion type sizing agent for paper making as described in any one of claims 1 to 8 of the scope of patent application, characterized in that, in the component (A), a monomer component that forms the component (B) is dropped. And (C) component and emulsification polymerization. A coated paper characterized in that it comprises a surface emulsion type sizing agent for papermaking as described in any one of claims 1 to 8 of the scope of patent application.