TW201728690A - Rosin-based emulsion sizing agent and paper obtained by using the sizing agent - Google Patents

Abstract

To provide a rosin-based emulsion sizing agent good in storage stability and mechanical stability, and paper excellent in size effect by using the sizing agent. This invention relates to a rosin-based emulsion sizing agent by emulsifying at least one kind of article to be emulsified selected from (B1) reinforced rosins which is an addition product of (b1) rosins containing communic acid of 0.1 to 8 wt.%, pimaric acids of 15 to 34.9 wt.% and abietic acids of 65 to 84.9 wt,% and (b2) [alpha],[beta]-unsaturated carboxylic acid and (B2) rosin esters which are a reaction product of the (b1) component and polyalcohols (b3) in a presence of a macromolecular dispersant (A); and paper obtained by using the sizing agent.

Description

Rosin emulsion sizing agent and paper obtained by using the sizing agent

The present invention relates to a rosin-based emulsion sizing agent and a paper obtained by using the sizing agent.

The rosin-based emulsion sizing agent refers to a composition obtained by emulsifying a rosin-based substance in the presence of various emulsifiers and water; paper obtained by using the sizing agent, due to emulsion particles fixed on pulp fibers And shows a good sizing effect.

As a rosin-based substance, conventionally, the so-called reinforced turpentine or its esterified product is appreciated and used because of its excellent sizing property, and the reinforced rosin or its esterified product is excellent in sizing property and maleic acid. The α,β-unsaturated carboxylic acid is obtained by modifying a raw material rosin such as gum rosin, tall oil rosin or wood rosin (see, for example, Patent Documents 1 to 3).

However, rosin-based emulsion sizing agents are thermodynamically unstable non-equilibrium systems. Therefore, even if it is a rosin type emulsion sizing agent which is stable at normal temperature, if it is left for a long time, the emulsion particle may aggregate and generate a deposit. This problem is easily made remarkable, for example, in the case where the papermaking system is at a high temperature or a high hardness. Further, when the rosin-based emulsion sizing agent is pumped by pumping, or when the papermaking system including the rosin-based emulsion sizing agent is subjected to high-speed stirring, the emulsion particles are subjected to shear stress, and sometimes There will be dirt or sediment residue. Therefore, in general, rosin-based emulsion sizing agents are required to have chemical stability, storage stability, and mechanical stability. [Previous Technical Literature] (Patent Literature)

Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei.

[Problem to be Solved by the Invention] A problem of the present invention is to provide a rosin-based emulsion sizing agent which is excellent in storage stability and mechanical stability, and also excellent in sizing effect.

[Means for Solving the Problem] The rosin-based emulsion sizing agent capable of solving the above problems was repeatedly examined, and as a result, it was found that the target-based slurry can be obtained by using a rosin containing a specific amount of a specific resin acid. That is, the present invention relates to the following rosin emulsion sizing agent and paper obtained using the sizing agent.

A rosin-based emulsion sizing agent which is obtained by emulsifying an emulsion (B) in the presence of a polymer dispersant (A), and the emulsified product (B) is selected from the group consisting of At least one of the group: a fortified rosin (B1) which is an addition product of a rosin (b1) and an α,β-unsaturated carboxylic acid (b2), and the rosin (b1) contains 0.1 to 8% by weight. Berberic acid, 15 to 34.9 wt% of sea pine acid and 65 to 84.9% by weight of rosin acid; and, rosin ester (B2), which is a reaction product of (b1) component and polyol (b3)

2. The rosin-based emulsion sizing agent according to the above item 1, wherein the component (A) is an anionic copolymer and/or a salt thereof (A1).

3. The rosin-based emulsion sizing agent according to the above item 2, wherein the (A1) component is an anionic unsaturated monomer (a1), a hydrophobic unsaturated monomer (a2), and a chain transfer property. A saturated monomer (a3) is used as a copolymer of a reaction component or a salt thereof.

4. The rosin-based emulsion sizing agent according to the above item 3, wherein the component (a1) comprises a component selected from the group consisting of a carboxyl group-containing unsaturated monomer, a sulfonic acid group-containing unsaturated monomer, and the like. At least one of the groups.

5. The rosin-based emulsion sizing agent according to the above item 3, wherein the component (a2) comprises styrenes and/or alkyl (meth)acrylates.

The rosin-based emulsion sizing agent according to any one of the items 3 to 5, wherein the component (a3) comprises (meth)allylsulfonic acid and/or a salt thereof.

The rosin-based emulsion sizing agent according to any one of the above-mentioned item, wherein the component (A1) is further selected from the group consisting of acrylamide (a4) and a hydroxyl group-containing unsaturated monomer. At least one of the group consisting of (a5) and the crosslinkable unsaturated monomer (a6) is used as a reaction component.

The rosin-based emulsion sizing agent according to any one of the above-mentioned items, wherein the (A1) component has a weight average molecular weight of 4,000 to 100,000.

9. The rosin-based emulsion sizing agent according to the above item 1, wherein the component (A) is a cationic polyamine polyamine (A2).

10. The rosin-based emulsion sizing agent according to the above item 9, wherein the component (A2) is a mixture of an aliphatic dibasic acid and a polyalkylene polyamine by a cationizing agent (β). The condensate (α) is obtained by upgrading.

The rosin-based emulsion sizing agent according to the above item 10, wherein the (α) component has a viscosity of 200 to 1,000 mPa·s at a solid concentration of 50% by weight and a temperature of 25°C.

12. The rosin-based emulsion sizing agent according to the above item 10, wherein the (β) component comprises an epihalohydrin and/or an inorganic acid.

The rosin-based emulsion sizing agent according to any one of the items 1 to 12, wherein the component (b3) comprises a triol and/or a tetrahydric alcohol.

The rosin-based emulsion sizing agent according to any one of the above-mentioned item, wherein the weight ratio of the component (B1) to the component (B2) is [(B2)/{(B1)). +(B2)}] is 0.05 to 0.5.

The rosin-based emulsion sizing agent according to any one of the above-mentioned items, wherein the component (A) is used in an amount of 5 to 12 parts by weight based on 100 parts by weight of the component (B). Share.

The rosin-based emulsion sizing agent according to any one of the items 1 to 15, further comprising at least one emulsified product (C) selected from the group consisting of: ‧ fortified rosin (C1), which is an addition reaction of rosin-containing rosin (c1) and (b2) components; ‧ rosin ester (C2), which is a reaction product of (c1) component and (b3) component .

17. The rosin-based emulsion sizing agent according to the above item 16, wherein the weight ratio [(C)/{(B)+(C)}]] of the component (B) to the component (C) is 0.05. ~0.5.

The rosin-based emulsion sizing agent according to any one of the items 1 to 17, further comprising a water-soluble aluminum compound (D).

The rosin-based emulsion sizing agent according to any one of the items 1 to 18, wherein the average primary particle diameter is 0.3 to 1.2 μm.

A rosin-based emulsion sizing agent according to any one of the items 1 to 19 above. [Effect of the invention]

In the present invention, rosin containing a specific amount of a resin acid is used, and thus it is emulsifiable. Moreover, the obtained rosin-based emulsion sizing agent is also excellent in storage stability, mechanical stability, and sizing effect.

The rosin-based emulsion sizing agent (hereinafter also referred to as "sizing agent") of the present invention is an emulsion to be emulsified in the presence of a polymer dispersant (A) (hereinafter referred to as component (A)) B) (hereinafter referred to as component (B)) is emulsified, and the emulsified product (B) is at least one selected from the group consisting of: reinforced rosin (B1) (hereinafter referred to as (B1)) a component) is an addition product of a rosin (b1) (hereinafter referred to as (b1) component) and an α,β-unsaturated carboxylic acid (b2) (hereinafter referred to as a component (b2)), and the rosin (b1) ) containing 0.1 to 8 wt% of communicic acid, 15 to 34.9% by weight of pimaric acid, and 65 to 84.9% by weight of abietic acid; and, rosin esters (B2) (hereinafter referred to as component (B2)), which is a reaction product of the component (b1) and the polyol (b3) (hereinafter referred to as component (b3)).

[Regarding component (A)] As the component (A), various known dispersing agents can be used without particular limitation. Specific examples include an anionic copolymer and/or a salt thereof (A1) (hereinafter referred to as a component (A1)) and a cationic polyamine polyamine (A2) (hereinafter referred to as a component (A2)). The details are explained below.

(A1) component (A1), a known anionic copolymer and/or a salt thereof can be used without particular limitation, and an anionic unsaturated monomer (a1) (hereinafter referred to as (a1) is exemplified. a component), a hydrophobic unsaturated monomer (a2) (hereinafter referred to as (a2) component), and a chain transfer unsaturated monomer (a3) (hereinafter referred to as (a3) component) as a copolymer of a reaction component or salt.

The component (a1) is an unsaturated monomer having one polymerizable carbon-carbon double bond and an anionic functional group, and various known unsaturated monomers can be used without particular limitation. In addition, the "polymerizable carbon-carbon double bond" includes, for example, a (meth) acrylonitrile group, a 1-propenyl group, a 2-methyl-1-propenyl group, an isopropenyl group, a vinyl group, etc. (the same applies hereinafter) ).

The component (a1) may, for example, be at least one selected from the group consisting of a carboxyl group-containing unsaturated monomer, a sulfonic acid group-containing unsaturated monomer, a phosphate group-containing unsaturated monomer, and the like. Salt.

Examples of the carboxyl group-containing unsaturated monomer and a salt thereof include α,β-unsaturated monocarboxylic acids such as (meth)acrylic acid and crotonic acid; maleic acid, maleic anhydride, fumaric acid, and itaconic acid. An α,β-unsaturated dicarboxylic acid such as citraconic acid or citraconic anhydride; and such salts. Examples of the sulfonic acid group-containing unsaturated monomer and a salt thereof include styrenesulfonic acid, vinylsulfonic acid, and 2-sulfoethyl (meth)acrylate; and these salts. Further, examples of the unsaturated group containing a phosphoric acid group and salts thereof include mono [(2-hydroxyethyl acrylate) acid phosphate and mono [(hydroxy) acrylate] Acid phosphate, mono[(methyl) chloro-2-hydroxypropyl] acid phosphate, (meth)allyl acid phosphate and mono [(meth)acrylic acid 2-hydroxyethyl) Ester] acid phosphite; and such salts and the like. These unsaturated monomers may be used alone or in combination of two or more.

The component (a1) is preferably selected from the group consisting of carboxyl group-containing unsaturated monomers, and the like, from the viewpoints of copolymerizability with other unsaturated monomer components, dispersion stability of the sizing agent of the present invention, sizing effect, and the like. At least one selected from the group consisting of a sulfonic acid unsaturated monomer and the salts, more preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and the like. Particularly preferred is itaconic acid and/or its salt.

The component (a2) is an unsaturated monomer having one polymerizable carbon-carbon double bond and a hydrophobic functional group in the molecule, and various known unsaturated monomers can be used without particular limitation. Further, the component (a2) is "hydrophobic", and means that the solubility of the component in water (g/water 100 g) is about 0 to 2.5. Further, examples of the "hydrophobic functional group" include an alkyl group and an aryl group.

The component (a2) may, for example, be at least one selected from the group consisting of styrenes, alkyl (meth)acrylates, vinyl carboxylates, and unsaturated dicarboxylic acid alkyl esters. Wait.

Examples of the styrenes include styrene, α-methylstyrene, tert-butylstyrene, dimethylstyrene, ethoxylated styrene, hydroxystyrene, vinyltoluene, and vinyl chloride. Base toluene and the like.

The alkyl (meth)acrylate may, for example, be an alkyl (meth)acrylate having an alkyl group having a carbon number of about 1 to 18. Further, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tertiary butyl group, an n-octyl group, a 2-ethylhexyl group, and a decyl group. , dodecyl, hexadecyl, octadecyl, octadecyl, behenyl, cyclopentyl and cyclohexyl.

Examples of the vinyl carboxylate include vinyl acetate, vinyl propionate, and vinyl laurate. Further, examples of the unsaturated dicarboxylic acid alkyl esters include monoalkyl esters or dialkyl esters of α,β-unsaturated dicarboxylic acids. Among them, styrene and/or (meth)acrylic acid is preferred from the viewpoints of copolymerizability with other unsaturated monomers, emulsifying properties, storage stability, and sizing effect of the sizing agent of the present invention. The esters, as the styrenes, are especially preferably styrene and/or α-methylstyrene. Further, as the (meth)acrylic acid alkyl ester, an alkyl (meth)acrylate having an alkyl group having a carbon number of about 4 to 8 is preferable, and the alkyl group is particularly low in terms of low foaming property. Branched or lipid rings are preferred.

The component (a3) is an unsaturated monomer having one polymerizable carbon-carbon double bond and a chain transfer functional group in the molecule, and various known unsaturated monomers can be used without particular limitation. When the component (a3) is used, the molecular weight of the component (A) can be appropriately controlled by the chain transfer effect.

Specific examples of the component (a3) include (meth)allylsulfonic acid and/or a salt thereof, and N-substituted acrylamide. Examples of the (meth)allylsulfonic acid and/or a salt thereof include allylsulfonic acid and methallylsulfonic acid, or the like; and, as an N-substituted acrylamide Examples thereof include dimethyl (meth) acrylamide, isopropyl (meth) acrylamide, hydroxymethyl (meth) acrylamide, diacetone acrylamide, and acryl morpholine. . Among them, (meth)allylsulfonic acid and/or a salt thereof is preferred from the viewpoint of chain transfer property, and as the salt, a sodium salt is preferred.

The reaction component of the component (A-1) may further contain, if necessary, a acrylamide-containing compound (a4) (hereinafter also referred to as (a4) component) or a hydroxyl group-containing unsaturated monomer (a5) (hereinafter also referred to as It is at least one of the group consisting of (a5) component) and a crosslinkable unsaturated monomer (a6) (hereinafter also referred to as (a6) component).

Specific examples of the component (a4) include acrylamide and/or methacrylamide. By using the component (a4), the mechanical stability of the sizing agent of the present invention can be improved. Therefore, it is possible to reduce the stain after papermaking, and to obtain a paper having excellent sizing effect.

The component (a5) is an unsaturated monomer having one polymerizable carbon-carbon double bond and a hydroxyl group, and various known unsaturated monomers can be used without particular limitation for the same purpose as the component (a4). Further, specific examples of the component (a5) include hydroxyl group-containing (meth) acrylates and/or hydroxyl group-containing vinyl monomers. Examples of the hydroxyl group-containing (meth) acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth) propylate, hydroxybutyl methacrylate, and (meth)acrylic acid 4- Hydroxybutyl ester, 2-hydroxy-2-methylpropyl (meth)acrylate, and the like. Further, examples of the hydroxyl group-containing vinyl monomer include hydroxymethyl vinyl ether, hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, and ethylene glycol monoallyl. Alkyl ether, 4-hydroxycyclohexyl vinyl ether, 3-allyloxy-1,2-propanediol, and glycerol α-monoallyl ether. Further, these unsaturated monomers may be used in combination of two or more kinds.

The component (a6) is an unsaturated monomer having at least two polymerizable carbon-carbon double bonds in the molecule, and is not particularly limited for the purpose of improving the mechanical stability or the sizing effect of the sizing agent of the present invention. Various well-known unsaturated monomers are used. Specific examples thereof include divinylbenzene, trivinylbenzene, divinylanthracene, polyethylene glycol diacrylate, propylene glycol diacrylate, trimethylolpropane triacrylate, and tetramethylolethane methane. Acrylate, ethylene glycol dimethacrylate, dipropylene glycol dimethacrylate, hexaethylene glycol diacrylate, N, N'-propyl propylene propylene amide, dipropylene decyl dimethyl ether and N, N'-methylenebis acrylamide or the like; and two or more types may be combined.

The reaction component of the component (A1) may further contain an unsaturated monomer other than the components (a1) to (a6) (hereinafter also referred to as component (a7)), and various known unsaturated groups may be used without particular limitation. monomer. Specific examples of the component (a7) include a cationic unsaturated monomer, an α-olefin, a polyalkylene glycol-based unsaturated monomer, a nitrile-based monomer, and a reactive emulsifier.

The cationic unsaturated monomer is an unsaturated monomer having one polymerizable carbon-carbon double bond and a cationic functional group in the molecule, and various known unsaturated monomers can be used without particular limitation. Specific examples thereof include N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, and N,N-(meth)acrylate. Diethylaminomethyl ester, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N (meth)acrylate -diethylaminopropyl ester, N,N-dimethylaminomethyl(meth)acrylamide, N,N-dimethylaminoethyl(meth)acrylamide, N,N -diethylaminomethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl (methyl) Acrylamide, N,N-diethylaminopropyl(meth)acrylamide, 3-diethylamino-2-hydroxypropyl (meth)acrylate, 3-(meth)acrylate N',N'-dimethylamino-N-methylamino)-2-hydroxypropyl ester, 3-dimethylamino-2-hydroxypropyl (meth) acrylamide, 3-di Ethylamino-2-hydroxypropyl(meth)acrylamide, 3-allyloxy-2-hydroxypropyldimethylamine, vinylbenzyldimethylamine and 4-(vinyl Benzyl)morpholine; and, with epihalohydrin, methyl halide, benzal The reaction of a halogen compound four methyl sulfate and the like thereof; and can be a combination of two or more.

Examples of the α-olefins include 2,4,4-trimethyl-1-pentene, 3-methyl-1-butene, 3-methyl-1-pentene, and 4-methyl- 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecane, 1-octadecene, 1- Eicosylene, 1-tetracosene, 1-triaconne, cyclohexene, methylcyclohexene, vinylcyclohexane, 4-vinylcyclohexene, cyclopentene, methyl Cyclopentene or the like; and two or more kinds may be combined.

Examples of the polyalkylene glycol-based unsaturated monomer include β-propiolactone, γ-butyrolactone, δ-valerolactone, and β-methyl-δ-valerolactone among the component (a5). And a lactone such as ε-caprolactone as a reaction component; and two or more types may be combined.

Examples of the nitrile include acrylonitrile and/or methacrylonitrile.

The reactive emulsifier may, for example, be a reactive emulsifier having a polymerizable carbon-carbon double bond in the molecule and an oxygen-extended alkyl group having a repeating number of from 1 to 100. Further, examples of the oxygen-extended alkyl group include an oxygen-extended ethyl group, an oxygen-extended propyl group, an oxygen-extended isopropyl group, an oxygen-terminated butyl group, and the like. Specific examples of the reactive emulsifier include the following reactive emulsifiers having a polymerizable carbon-carbon double bond: a sulfosuccinate salt of a polyoxyalkylene ether or a polyoxyalkylene ether. Sulfate salt of polyoxyethylene ether, polyoxyethylidene ether, sulfosuccinate salt of polyoxyethylidene ether, sulfate salt of polyoxyethylidene ether, poly Sulfosuccinate salt of polyoxyethylidene ether, polyoxyalkylene ethyl phenyl ether, sulfate salt of polyoxyethylidene ether, polyoxyethylene ethyl aralkyl Sulfonic succinate salt of phenyl ether, polyoxyethylene ethyl aralkyl phenyl ether, sulphate salt of polyoxyethylene aralkyl phenyl ether, phosphoric acid of polyoxyethylidene phenyl ether Ester salt; aliphatic or aromatic carboxylate of polyoxyethylene ethyl phenyl ether, emulsifier of acid (meth) acrylate, bis (polyoxyethylidene phenyl ether) Acrylated sulfate ammonium salt; methacryloxyethyl sulfonate, polyethylene glycol methacrylate, and the like. For example, JP-A-63-23725, JP-A-63-240931, JP-A-62-104802, JP-A-4-50204, JP-A-4-53802, and The reactive emulsifier described in JP-A-H05-256429, JP-A-H09-324394, JP-A-2003-293288, and JP-A-2010-242280. Further, these may be combined in two or more types.

The amount of each of the components (a1) to (a7) is not particularly limited, and in general, when all the unsaturated monomers are 100, the emulsification and sizing effect of the sizing agent of the present invention are considered. When the molar % is used, it can be specified in the following manner depending on whether or not the component (a4) is used. Further, the total mole % of the components used does not exceed 100.

<When the component (a4) is not used> (a1) component: about 15 to 80 mol%, preferably about 20 to 70 mol%. Component (a2): about 19 to 80 mol%, preferably about 28 to 70 mol%. Component (a3): about 0.01 to 10 mol%, preferably about 0.05 to 8 mol%. (a4) Ingredients: 0% by mole.

In this case, when any one or combination of the component (a5), the component (a6), and the component (a7) is used in combination, the amount of each component used is not particularly limited, and is generally as follows. (a5) Component: 0.05 to 20 mol%, preferably 0.05 to 15 mol%. Component (a6): about 0.05 to 5 mol%, preferably about 0.5 to 3 mol%. Component (a7): about 0.05 to 10 mol%, preferably about 1 to 5 mol%.

<When the component (a4) is used> The component (a1): about 3 to 30 mol%, preferably about 5 to 20 mol%. Component (a2): about 3 to 30 mol%, preferably about 5 to 20 mol%. (a3) Component: about 0.01 to 10 mol%, preferably about 0.05 to 5 mol%. Component (a4): about 60 to 90 mol%, preferably about 65 to 85 mol%.

In this case, when any one or combination of the component (a5), the component (a6), and the component (a7) is used in combination, the amount of each component used is not particularly limited, and is generally as follows. Component (a5): about 0.05 to 10 mol%, preferably about 3.5 to 5 mol%. Component (a6): about 0.05 to 5 mol%, preferably about 0.1 to 3 mol%. Component (a7): about 0.05 to 10 mol%, preferably about 1 to 5 mol%.

The component (A1) can be obtained, for example, by subjecting the component (a1), the component (a2), and the component (a3) to a component selected from the component (a4) and (a5), as required, by various known methods. At least one of the components, the group consisting of the component (a6) and the component (a7) is subjected to radical polymerization. Further, the polymerization method is not particularly limited, and various known methods such as solution polymerization, emulsion polymerization, suspension polymerization, and the like can be employed. Further, the polymerization conditions are not particularly limited, and the reaction temperature is usually about 80 to 180 ° C, and the reaction time is usually about 1 to 10 hours. Further, at the time of the polymerization reaction, various reaction solvents, radical polymerization initiators, chain transfer agents, and surfactants may be used as needed. Further, the carboxyl group derived from the component (a1) in the obtained copolymer may be neutralized with a neutralizing agent as needed.

The reaction solvent is not particularly limited, and examples thereof include alcohols such as ethanol and isopropanol; lower ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as toluene and benzene; and ethyl acetate, chloroform and dimethyl An organic solvent such as carbamide; water; and a mixed solvent of the organic solvent and water.

The radical polymerization initiator is not particularly limited, and examples thereof include inorganic peroxides such as hydrogen peroxide, ammonium persulfate and potassium persulfate; tertiary butyl peroxybenzoate and dicumyl peroxide; And an organic peroxide such as a lauryl peroxide; and an azo compound such as 2,2'-azobisisobutyronitrile or dimethyl 2,2'-azobisisobutyrate; and the like These may be used alone or in combination of two or more. In addition, the amount of the radical polymerization initiator to be used is not particularly limited. Generally, when the amount of the unsaturated monomer constituting the component (A) is 100 parts by weight, it is about 1 to 8 parts by weight.

The chain transfer agent is not particularly limited, and examples thereof include tertiary dodecanethiol, n-dodecyl mercaptan, n-octyl mercaptan, cumene, bromotrichloromethane, and 2-mercaptobenzothiazole, and α. - an oil-soluble chain transfer agent such as methyl styrene dimer; and, ethanethiol, propanethiol, thioglycolic acid, mercapto succinic acid, dimethyldithiocarbamic acid, isopropanol and sodium hypophosphite A water-soluble chain transfer agent or the like; and these may be used alone or in combination of two or more. In addition, the amount of the chain transfer agent to be used is not particularly limited. Generally, when the amount of the unsaturated monomer constituting the component (A) is 100 parts by weight, it is about 0.05 to 4 parts by weight.

The surfactant is not particularly limited, and examples thereof include the reactive emulsifier and an anionic surfactant and/or a nonionic surfactant having no polymerizable carbon-carbon double bond in the molecule. Examples of the anionic surfactant include dialkyl sulfosuccinate, alkyl sulfonate, α-olefin sulfonate, polyoxyethylidene ether sulfosuccinate, and polyoxyethylene A styrylphenyl ether sulfosuccinate salt, a naphthalene sulfonic acid formaldehyde condensate, a polyoxyethylene ethyl ether ether sulfate salt, and a polyoxyalkylene methyl phenyl ether sulfate salt. Further, examples of the nonionic surfactant include polyoxyethylene ethyl ether, polyoxyethylidene phenyl ether, and polyoxyethyl sorbitan fatty acid ester. Further, these may be combined in two or more types.

The physical properties of the component (A1) obtained in this manner are not particularly limited, and the emulsification, workability, sizing effect, and the like of the sizing agent of the present invention are considered, for example, weight average molecular weight (refers to gel permeation chromatography). The value in terms of polystyrene in the method is generally about 4,000 to 100,000, preferably 5,000 to 50,000. Further, when the component (A) is obtained as an aqueous solution, the solid content concentration is generally about 20 to 40% by weight, and when the nonvolatile component is 25% by weight, the viscosity is about 5 to 2,000 mPa ‧ s / 25 ° C, and the pH is It is around 4 to 12.

[Component (A2)] As the component (A2), a known component can be used without particular limitation, and for example, an anionic agent (β) (hereinafter referred to as a component (β)) can be used for the aliphatic component. A component obtained by modifying a polycondensate (α) of a polybasic acid and a polyalkylene polyamine (hereinafter referred to as an (α) component).

[Regarding the (α) component] The constituent component of the (α) component is an aliphatic dibasic acid, and various known aliphatic dibasic acids can be used without particular limitation. Examples of the aliphatic dibasic acid include an aliphatic dibasic acid and/or a derivative thereof. Examples of the aliphatic dibasic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, and sebacic acid. Examples of the derivative of the aliphatic dibasic acid include an acid anhydride of the aliphatic dibasic acid and an ester compound of a lower alcohol such as methanol. Among them, adipic acid is preferred from the viewpoint of emulsifying properties. Further, as the polyalkylenepolyamine, various known polyalkylene polyamines can be used without particular limitation. Examples of the polyalkylene polyamine include di-ethyltriamine, tri-ethylidene tetraamine, tetraethylidene pentaamine, penta-ethylhexamine, and bis(2-aminoethyl)amine. Iminodipropylamine and the like. Among them, from the viewpoint of emulsifying properties, di-ethyltriamine is preferred. The ratio of use of the polyalkylene polyamine to the aliphatic dibasic acid and/or its derivative is preferably from the viewpoint of emulsifying property with the component (B) or storage stability of the sizing agent. The molar ratio of the dibasic acid and/or its derivative to the polyalkylene polyamine is set to be 90 to 110%, more preferably 98 to 102%. Further, a diamine can be used as a part of the polyalkylene polyamine. As the diamine, various known diamines can be used without particular limitation, and examples thereof include ethyl diamine, butyl diamine, hexamethylene diamine, and cyclohexyl diamine.

The (α) component in the present invention is not particularly limited. For example, in the presence or absence of a catalyst such as sulfuric acid, benzenesulfonic acid or p-toluenesulfonic acid, the reaction temperature is about 110 to 250 ° C and 2 to 2 It is manufactured under conditions of about 24 hours. Further, in order to adjust the viscosity of the aqueous solution of the obtained (α) component to the range described later, it is preferred that the molar ratio of the aliphatic dibasic acid and/or its derivative to the polyalkylamine polyamine is in the former: The latter is used in the range of about 1:0.9 to 1.2.

The physical properties of the (α) component obtained in this manner are not particularly limited. For example, the viscosity of the aqueous solution at a solid concentration of 50% by weight and a temperature of 25° C. is generally 200 to 1000 mPa·s. In the viscosity range, the emulsifiability with the component (B) and the storage stability of the obtained sizing agent are easily improved.

[Regarding the (β) component] The (β) component is added in order to cation-modify the (α) component, and various known cationizing agents can be used without particular limitation. Specific examples thereof include epihalohydrins such as epichlorohydrin, epibromohydrin and methylepichlorohydrin; and inorganic acids and/or organic acids which are soluble in water at normal temperature (25 ° C). Examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and examples of the organic acid include acetic acid, propionic acid, succinic acid, malic acid, maleic acid, and citric acid; They may be used alone or in combination of two or more. Further, among them, from the viewpoint of emulsifying property and sizing effect of the sizing agent of the present invention, an epihalohydrin and/or an inorganic acid is preferred, and epichlorohydrin and/or sulfuric acid is more preferred, particularly preferably sulfuric acid.

The amount of the (β) component to be used is not particularly limited. From the viewpoint of the emulsifiability and sizing effect of the sizing agent of the present invention, the equivalent ratio of the proton to the amine group in the (α) component is generally 30 to 75% or so, preferably 40 to 60%. In addition, the "equivalent ratio" means a proton derived from the (β) component in the case where all protons derived from (β) are consumed for neutralization of all the amine groups contained in the (α) component. The ratio (%) of the number (moles) to the number of all amine groups (moles) in the (α) component. The method of the cationization reaction is not particularly limited. For example, the (β) component may be directly added to the (α) component obtained by the above method, and mixed and stirred. Further, at this time, dilution water can be added.

The physical properties of the component (A2) obtained in this manner are not particularly limited. For example, the viscosity of the 23.5% by weight aqueous solution at 25 ° C is usually about 5 to 100 mPa·s, preferably about 10 to 50 mPa·s.

[Regarding component (B)] In the sizing agent of the present invention, the component (B) is used, and the component (B) is at least one selected from the group consisting of the component (B1) and the component (B2).

In the component (B), it is necessary to use the component (b1), and the component (b1) contains each specific amount of sesquimarin acid and rosin acid. The component (b1) will be described in detail below.

The terpene acid contained in the component (b1) is, in the present specification, meant to include isomers such as cisplatin, trans-cemblanic acid, or mirceo-communic acid. An example of the structure is shown below.

The total content of all the resin acids contained in the component (b1) is 100% by weight, and the content of cedaric acid is 0.1 to 8% by weight, preferably 1 to 6% by weight. When the content of cedaric acid is less than 0.1% by weight, the storage stability and mechanical stability of the sizing agent are insufficient. On the other hand, when the content exceeds 8% by weight, a sufficient sizing effect of the sizing agent cannot be obtained.

The sea pine acid contained in the component (b1) means sea rosin acid, isopimaric acid, sandaracopimaric acid, and the like, and the like. An example of the structure is shown below.

(In the formula (2), X represents a CH ₂ CH ₃ group or a CH=CH ₂ group. Further, the bonding of the broken line portion means that there may be a carbon-carbon bond at that point.)

The total content of all the resin acids contained in the component (b1) is 100% by weight, and the content of the sea rosin acid is 15 to 34.9% by weight, preferably 18 to 25% by weight. When the content of the abietic acid is less than 15% by weight, the storage stability and mechanical stability of the sizing agent are insufficient. On the other hand, when the content exceeds 34.9% by weight, a sufficient sizing effect of the sizing agent cannot be obtained.

The rosin acid in the component (b1) means palustric acid, rosin acid, neostearic acid, and dehydroabietic acid, and the like, and the like. An example of the structure is shown below.

(In the formula (3), in two of all the broken lines, the carbon-carbon bond exists in such a manner as to form a conjugated double bond.)

The total content of all the resin acids contained in the component (b1) is 100% by weight, and the content of the rosin acid is 65 to 84.9% by weight, preferably 68 to 81% by weight. When the content of rosin acids is less than 65% by weight, a sufficient sizing effect of the sizing agent cannot be obtained. On the other hand, when the content exceeds 84.9 wt%, the storage stability and mechanical stability of the sizing agent are insufficient.

The method of obtaining the component (b1) is not particularly limited, and examples thereof include the following. [1] For the turpentine (natural turpentine or its derivatives) which does not contain cedaric acid, a combination of separately obtained cedaric acid; [2] The combination originally contains turpentine of eucalyptus and rosin which does not contain cedar [3] For a rosin which originally contains cedaric acid, a combination of one or more resin acids selected from the group consisting of cedaric acid, abietic acid and rosin acid; [4] Direct use originally contained Arbutin rosin.

Further, various known methods such as ruthenium column chromatography (J. Am. Chem. Soc., 77, 2823 (1955), etc.) may be used, from natural rosin or its derivative containing tartaric acid. Leaving cedar acid.

Further, the content of cedaric acid in the rosin which originally contains cedaric acid is generally about 1 to 8% by weight, preferably about 1 to 6% by weight. Further, the content of cedaric acid in the rosin which originally contains cedaric acid can also be measured by various known methods. For example, when the rosin is natural turpentine, gas chromatography (GC) is used to determine the ratio (%) of the peak area of cedaric acid to the peak area (100%) of all resin acids. This gives the content of cedaric acid. Further, when the rosin is a natural rosin derivative, the content of cedaric acid is obtained by an absolute calibration curve method by gas chromatography (GC) in consideration of the fact that it is a high molecular weight substance.

Further, examples of the rosin which does not contain cedaric acid include natural turpentine such as rosin gum, tall oil rosin, and turpentine; or polymerized rosin obtained by polymerizing the natural turpentine, and hydrogenating the natural turpentine And obtained hydrogenated rosin and the like.

In the present invention, the content of the above-mentioned resin acid contributes to the emulsifiability of the component (B) and the storage stability and sizing effect of the obtained sizing agent. Although the details are not determined, it is presumed that crystallization of the component (b1) can be suppressed by the content.

[Regarding (B1) component] The component (B1) is a fortified rosin obtained by adding the component (b2) to the component (b1).

As the component (b2), various known α,β-unsaturated carboxylic acids can be used without particular limitation, and examples thereof include α,β-unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, and fumaric acid; And an α,β-unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid. Further, the amount of the component (b2) to be used is not particularly limited, and is usually about 1 to 30 parts by weight based on 100 parts by weight of the component (b1).

The method for producing the component (B1) is not particularly limited, and examples thereof include a method in which a component (b1) and a component (b2) are mixed together in a suitable reaction vessel, followed by heating and melting, and at 190 to 230. The Diels-Alder reaction is carried out at about °C for about 1 to 3 hours.

The physical properties of the component (B1) obtained in this manner are not particularly limited, and from the viewpoint of the emulsifiability and sizing effect of the sizing agent of the present invention, the softening point is generally about 85 to 140 ° C, and The acid value is about 195 to 320 mgKOH/g, preferably: the softening point is about 95 to 130 ° C, and the acid value is about 240 to 295 mg KOH/g.

[Regarding (B2) component] The component (B2) is a rosin ester which is produced by the reaction of the component (b1) and the component (b3).

As the component (b3), various known polyols can be used without particular limitation. Specifically, a triol and/or a tetrahydric alcohol are preferable, and the former may, for example, be glycerin, trimethylolethane, trimethylolpropane, and 3-methylpentane-1,3,5- Triol or the like; and the latter may, for example, be pentaerythritol, diglycerin or the like.

The component (B2) can be produced by any known method without any particular limitation. Specifically, it can be obtained by subjecting the component (b1) and the component (b3) to an esterification reaction for about 6 to 20 hours, generally at about 200 to 350 °C. Further, the reaction may be carried out under any conditions of normal pressure, reduced pressure, and pressure. Further, the ratio of the amount of the component (b1) to the component (b2) is not particularly limited, and generally, the equivalent ratio [OH _(eq) / COOH _(eq )] of the carboxyl group of the former to the hydroxyl group of the latter is 0.2. It may be in the range of about ~1.5, and it is preferable to be in the range of about 0.4 to 1.2. Further, at the time of the reaction, an esterification catalyst such as p-toluenesulfonic acid or various antioxidants can be used. Again, the reaction can be carried out under a stream of nitrogen.

The physical properties of the component (B2) are not particularly limited. In view of the emulsifiability and sizing effect of the sizing agent of the present invention, the softening point is generally about 80 to 100 ° C, and the acid value is 0 to 25 mg KOH / The pH is about 0 to 30 mgKOH/g, preferably the softening point is about 85 to 95 ° C, the acid value is about 10 to 20 mgKOH/g, and the hydroxyl value is about 0 to 10 mgKOH/g.

The weight ratio [(B1)/{(B1)+(B2)}]) of the component (B1) and the component (B2) is not particularly limited, and the emulsification and sizing effect of the sizing agent of the present invention are considered. And so on, it is generally about 0.05 to 0.5, preferably about 0.15 to 0.4. In particular, when the sizing effect at the time of papermaking in a weakly acidic to neutral region, for example, a pH of 6.0 to 7.5 is considered, the weight ratio is preferably about 0.15 to 0.3.

The amount of the component (A) to be used in the component (B) is not particularly limited, and in consideration of the emulsifiability of the component (A) and the component (B) of the present invention and the sizing effect of the obtained sizing agent, In general, the amount of the component (A) (in terms of solid content) is preferably in the range of about 5 to 12 parts by weight, based on 100 parts by weight of the component (B) (in terms of solid content). It is in the range of about 6 to 10 parts by weight.

The sizing agent of the present invention may contain an emulsified product (C) (hereinafter referred to as a component (C)) as needed, and the component (C) is at least one selected from the group consisting of the following. Reinforcing rosin (C1) (hereinafter referred to as (C1) component), which is an addition reaction of rosin-containing rosin (c1) (hereinafter referred to as (c1) component) and (b2) component; rosin The ester (C2) (hereinafter referred to as (C2) component) is a reaction product of the component (c1) and the component (b3).

In the component (C), the component (c1) must be used. The component (c1) is not particularly limited, and examples thereof include rosins described in paragraph [0087]. These may be used alone or in combination of two or more.

Further, the method for producing the (C1) component and the (C2) component is the same as the method described in the paragraphs [0091] and [0095].

The weight ratio [(C)/{(B)+(C)}]) of the component (B) and the component (C) is not particularly limited, and the emulsification and sizing effect of the sizing agent of the present invention are considered. And so on, generally about 0.05 to 0.5, preferably about 0.05 to 0.3.

Further, in order to enhance the sizing effect, the sizing agent of the present invention may contain a water-soluble aluminum compound (D) (hereinafter referred to as a component (D)) as needed. The component (D) is not particularly limited, and for example, at least one selected from the group consisting of aluminum sulfate, aluminum chloride, basic aluminum sulfate, basic aluminum chloride, aluminum sulfate, and the like is preferably used. . Among them, in terms of cost, it is particularly preferred to be aluminum sulfate.

In the sizing agent of the present invention, the component (B) is emulsified with the component (C) and the component (D) as needed in the presence of the component (A). The emulsification method is not particularly limited, and various known means can be employed. For example, a high-pressure emulsification method (refer to Japanese Patent Publication No. Sho 53-22090) and a reverse emulsification method (refer to Japanese Laid-Open Patent Publication No. SHO58-4938). In the case of the high-pressure emulsification method, the component (B) is previously dissolved in the organic solvent as needed, and the component (C) is further added, and then the component (A), water, and neutralizing agent are further added, and added as needed (D). The component is then emulsified using a homogenizer or a piston type high pressure emulsifier, an ultrasonic emulsifier or the like, and then the organic solvent is distilled off, whereby a target sizing agent is obtained. Moreover, in the case of the inversion emulsification method, the component (A) and the component (B) are melted under heating as needed, and then the hot component is added to the opposite phase, and then added as needed (D). The ingredient, whereby the target sizing agent is obtained. Further, at the time of emulsification, the above surfactant may be used in combination as needed.

The physical properties of the sizing agent obtained in this manner are not particularly limited, and from the viewpoints of storage stability and sizing effect of the sizing agent, generally, the average primary particle diameter (refers to by laser diffraction) The measured value of the average primary particle diameter measured by the scattering method is the same as that of 0.3 to 1.2 μm.

Further, various additives such as celluloses such as carboxymethyl cellulose, polyvinyl alcohols, polypropylene decyl amines, and water-soluble polymers such as sodium alginate may be added to the sizing agent. And anti-slip agent, preservative, rust inhibitor, pH adjuster, defoamer (tantal defoamer, etc.), thickener, filler, antioxidant, water resistance agent, filming aid, pigment , dyes, etc.

The paper of the present invention is obtained by using the sizing agent of the present invention. As a method of sizing, internal sizing and surface sizing, and combinations of these are mentioned.

In the internal sizing, the sizing agent of the present invention is added to the pulp slurry, and papermaking is carried out in an acidic region or a neutral region. Moreover, the amount of the sizing agent used in the present invention is not particularly limited, and is generally in the range of about 0.05 to 3% by weight based on the dry weight of the pulp. Further, the type of the pulp is not particularly limited, and examples thereof include chemical pulp such as hardwood wood pulp (LBKP) and softwood pulp (NBKP); and machinery such as groundwood pulp (GP) and thermomechanical pulp (TMP). Pulp; other waste pulp and so on. Further, in the case of internal sizing, the component (D) can be used as the fixing agent, and in particular, aluminum sulfate and/or aluminum hydroxide are preferable. Further, the pH of the pulp slurry can be adjusted by using sulfuric acid or sodium hydroxide. Further, as another neutral sizing agent, for example, epichlorohydrin modified product, alkenyl succinic anhydride, alkyl ketene dimer of styrene-dimethylaminoethyl methacrylate copolymer may be used in combination. An epichlorohydrin modification of a fatty acid-polyalkyl polyamine condensate. Further, as the paper strength agent, for example, a cationized starch, an epichlorohydrin modified product of a polyamidamine polyamine resin, an epichlorohydrin modified product of dicyandiamide, and styrene-A may be used in combination. Epichlorohydrin modification of dimethylaminoethyl acrylate copolymer, Mannich modification of polyacrylamide, acrylamide-dimethylaminoethyl methacrylate copolymer, poly A Hofmann decomposition product of acrylamide, a copolymer of dialkyl diallyl ammonium chloride and sulfur dioxide, and the like. Further, a filler such as talc, clay, kaolin, titanium dioxide or calcium carbonate may be added to the pulp slurry.

In the surface sizing, the sizing agent of the present invention is diluted to a nonvolatile content of about 0.01 to 2.0% by weight to prepare a sizing liquid, which is applied to a base paper by various known means. The coating means is not particularly limited, and examples thereof include a size press method, a gate roll method, a bar coater method, and a calender method. Spraying method, etc. Further, examples of the sizing pressurization method include a two-roll sizing press coating method and a rod-metering size press coating method. Further, the coating amount (solid content) of the sizing liquid is not particularly limited, but is generally about 0.001 to 2.0 g/m ² , preferably about 0.005 to 0.5 g/m ² . Further, the base paper is not particularly limited, and for example, uncoated paper using wood cellulose fibers as a raw material can be used. Moreover, as the pulp which comprises a base paper, the said pulp is mentioned. Further, the base paper may be a base paper obtained by papermaking using one selected from the group consisting of the aforementioned fixing agent, a neutral sizing agent, a paper strength agent, and a filler, and may be coated on the surface. The base paper obtained from the neutral sizing agent and/or paper strength agent.

The paper of the present invention is provided for various products in accordance with the basis weight. For example, a low-to-medium basis weight paper of about 20 to 150 g/m ² can be used as, for example, a recording paper, a plain paper copying machine (PPC) paper, a thermal recording base paper, and a pressure sensitive recording base paper; and Art paper; coated paper such as cast coated paper and high-quality coated paper; packaging paper such as kraft paper and white single-light paper; foreign paper (mechanical paper) such as note paper, book paper, printing paper and newsprint. Further, a high basis weight paper of 150 g/m2 or more can be used as, for example, a Manila board, a white lined chipboard, a chipboard, or a liner board. Wait for cardboard and so on. [Examples]

The present invention will be specifically described below by way of examples and comparative examples. Of course, the scope of the present invention is not limited to the examples and comparative examples. Further, in each of the examples, the parts and % are based on the weight unless otherwise specified.

[Weight Average Molecular Weight] Regarding the component (A-1), the weight average molecular weight was measured by the method specified below. ‧ When the component (a4) is not used: by gel permeation chromatography (using device: product name "HLC 8120GPC", manufactured by Tosoh Corporation. Column: product name "TSK-GEL ALPHA-M", The value measured in polystyrene measured by Tosoh Corporation. ‧ When using component (a4): by gel permeation chromatography (using device: HLC 8120GPC (product name) manufactured by Tosoh Corporation; pipe column: TSK-GEL ALPHA manufactured by Tosoh Corporation) The value in terms of polyethylene glycol standard material measured by M (product name); development solvent: 0.2 M aqueous sodium nitrate solution).

[Viscosity] The viscosity of the sizing agent kept at 25 ° C was measured using a Brookfield rotational viscometer (product name "VISCOMETER TVK-10", manufactured by Toki Sangyo Co., Ltd.).

[pH value] The pH of the sizing agent kept at 25 ° C was measured using a commercially available measuring machine (product name "pH METER F-14", manufactured by Horiba, Ltd.).

[Softening Point] The softening point was measured in accordance with Japanese Industrial Standards (JIS) K5902 using a commercially available measuring instrument (product name "EX-719PD4", manufactured by FLEX SCIENTIFIC Co., Ltd.).

[Average primary particle size] The average primary level of the sizing agent was measured using a laser diffraction/scattering method based on a particle size measuring device (product name "LASER DIFFRACTION PARTICLE SIZE ANALYZER SALD-2000J", manufactured by Shimadzu Corporation) Particle size.

[Content of dibasic diterpene carboxylic acid in the raw material rosin] The diterpene dicarboxylate in the raw material rosin was measured using a gas chromatograph measuring machine (product name "HP6890/5973", manufactured by Agilent). The acid content.

[Storage Stability] 220 g of the sizing agent after filtration through a metal mesh of 350 mesh was allowed to stand in a thermostat set at 40 ° C for one week, and then the resulting agglomerates were filtered through a metal mesh of 350 mesh. The amount of filtration residue was calculated according to Formula 1. Furthermore, the smaller the value of the storage stability, the better. (Formula 1) Filtration residue amount (ppm) = [(absolute dry weight of aggregates - absolute dry weight of metal mesh) / (absolute dry weight of sample emulsion sizing agent)] × 1000000

[Mechanical stability] Weigh 50g of sizing agent to the container of MARON type stability tester (manufactured by Xinxing Industry Co., Ltd.), and the temperature is 25 ° C, the load is 10 kg, and the rotation speed is 1000 rpm. After vigorous stirring for 5 minutes, the resulting agglomerates were filtered through a metal mesh of 350 mesh, and the values were calculated according to Equation 2. Furthermore, the smaller the value of mechanical stability, the better. (Formula 2) Mechanical stability (%) = (absolute dry weight of agglomerates / absolute dry weight of sample emulsion sizing agent) × 100

<Production of non-acrylamide-based anionic copolymer salt (A1-1)> (Production Example 1) In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 56.25 as a component (a1) was charged. g (53.98 mol%) 80% methacrylic acid, 5.00 g (3.97 mol%) of itaconic acid, 5.00 g (4.03 mol%) of butyl acrylate as component (a2), 5.00 g (2.80 mol%) 2-ethylhexyl acrylate, 25.00 g (24.79 mol%) of styrene, 5.00 g (3.27 mol%) of sodium methallylsulfonate as component (a3), and 10.00 as component (a5) g (7.16 mol%) hydroxybutyl acrylate, 1.0 g of surfactant (HITENOL LA-10 (product name), manufactured by Dai-Il Pharmaceutical Co., Ltd.), 300 g of ion-exchanged water, and 4.00 g as a chain transfer agent The α-methylstyrene dimer was then allowed to warm to 60 ° C while stirring the mixture while stirring with nitrogen. Then, 5.00 g of ammonium persulfate (APS) as a polymerization initiator was added, and the temperature was raised to 90 ° C for 100 minutes, and then 2.0 g of ammonium persulfate (APS) as a catalyst for subsequent polymerization was further added. And keep at 90 ° C for 60 minutes. Then, 49.9 g of a 48% aqueous sodium hydroxide solution was added to neutralize methacrylic acid, itaconic acid, and then ion-exchanged water was added, thereby obtaining an anionic copolymer salt (A1-1) having a weight average molecular weight of 12,000. Aqueous solution. Further, the aqueous solution had a nonvolatile content of 25.0%, a viscosity at 25 ° C of 45 mPa ‧ and a pH of 9.3.

<Production of non-acrylamide-based anionic copolymer salt (A1-2)> (Production Example 2) 1.0 g of a surfactant (HITENOL) was placed in a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. LA-10 (product name), manufactured by Daiichi Pharmaceutical Co., Ltd.), 63.79 g (59.40 mol%) 80% methacrylic acid, 4.00 g (1.95 mol%) sodium styrene sulfonate, 16.00 g (16.03 Mol%) methyl methacrylate, 14.00 g (7.62 mol%) 2-ethylhexyl acrylate, 15.00 g (14.44 mol%) styrene, 300 g of ion-exchanged water, and 5.00 g as a chain transfer agent The α-methylstyrene dimer was then allowed to warm to 60 ° C while stirring the mixture while stirring with nitrogen. Then, 4.00 g of APS was added, and then the temperature was raised to 90 ° C for 100 minutes, after which 2.0 g of APS was further added and kept at 90 ° C for 60 minutes. Then, 43.7 g of a 48% aqueous sodium hydroxide solution was added, and ion-exchanged water was added, whereby an aqueous solution of a copolymer (A1-2) having a weight average molecular weight of 19,000 was obtained. Further, the aqueous solution had a nonvolatile content of 25.0%, a viscosity at 25 ° C of 200 mPa ‧ and a pH of 10.1.

<Production of reinforced turpentine (B1-1)> (Production Example 3) 600.0 g of rosin derived from Chinese slash pine was added as a component (b1) in a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a cooler. Glue [17.2% by weight of sea rosin acid, 79.8% by weight of rosin acid, and 3.0% by weight of cedaric acid (hereinafter referred to as SL rosin)] melt at about 160 ° C, rich as 42.0 g of (b2) component The horse acid was then reacted at 200 ° C for 2 hours while stirring under a nitrogen gas stream, whereby a fortified rosin (B1-1) having a softening point of 104.5 ° C and an acid value of 219.5 mg KOH / g was obtained.

<Production of the reinforced turpentine (B1-2)> (Production Example 4) In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen gas introduction tube, and a cooler, 600.0 g of rosin derived from the Brazilian slash pine was introduced as the component (b1). Glue [25.8 wt% of sea rosin acid, 69.1 wt% of rosin acid, and 5.1 wt% of eucalyptus acid (hereinafter referred to as BSL rosin)] melt at about 160 ° C, rich as 42.0 g of (b2) component The horse acid was then reacted at 200 ° C for 2 hours while stirring under a nitrogen gas stream, whereby a fortified rosin (B1-2) having a softening point of 103.2 ° C and an acid value of 218.9 mg KOH / g was obtained.

<Production of the reinforced rosin (i)> (Comparative Production Example 1) In the same reaction vessel as in Production Example 1, 600.0 g of rosin gum derived from Chinese Pinus massoniana was added as the component (c1) [sea rosin acid was 10.3 by weight). %, rosin acid is 89.7% by weight, and yttrium acid is 0% by weight (hereinafter referred to as CN rosin)] melt at about 160 ° C, 42.0 g of fumaric acid as component (b2), and then under a nitrogen stream The mixture was reacted at 200 ° C for 2 hours while stirring, whereby a reinforced rosin (i) having a softening point of 105.7 ° C and an acid value of 221.1 mg KOH / g was obtained.

<Preparation of rosin-based emulsion sizing agent (1)> (Example 1) 100 g of the reinforced rosin (B1-1) of Production Example 3 was placed in the same reaction container as in Production Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-1) of Production Example 1 was gradually added dropwise under stirring to prepare an emulsion in the form of water-in-oil (W/O). Then, hot water is further added to form a stable oil-in-water (O/W) type emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained. The physical properties of the obtained sizing liquid are shown in Table 1. (the same below)

(Example 2) 100 g of the reinforcing rosin (B1-2) of Production Example 4 was placed in the same reaction container as in Production Example 1, and heat-melted at about 160 °C. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-1) of Production Example 1 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 3) 100 g of the reinforcing rosin (B1-1) of Production Example 3 was placed in the same reaction container as in Production Example 1, and heat-melted at about 160 °C. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-2) of Production Example 2 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 4) 100 g of the reinforcing rosin (B1-2) of Production Example 4 was placed in the same reaction container as in Production Example 1, and heat-melted at about 160 °C. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-2) of Production Example 2 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Comparative Example 1) 100 g of the reinforcing rosin (i) of Comparative Production Example 1 was placed in the same reaction container as in Production Example 1, and heat-melted at about 160 °C. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-1) of Production Example 1 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Comparative Example 2) 100 g of the reinforcing rosin (i) of Comparative Production Example 1 was placed in the same reaction container as in Production Example 1, and heat-melted at about 160 °C. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-2) of Production Example 2 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

[Table 1]

<Experiment 1: Using L-BKP; Evaluation of Acidic Papermaking and Stockigt Sizing Degree> For broadleaf bleached kraft pulp (hereinafter referred to as L-BKP), an amount of pulp concentration of 2.0% was added. Tap water and beater to a 300 ml Canadian standard freeness using a beater. Then, the obtained pulp slurry was further diluted with tap water to prepare a slurry having a pulp concentration of 1.0%. In this diluted pulp slurry, a filler (mixture of calcium carbonate and talc) based on 16.0% (based on absolute dry weight, the same below) relative to the pulp, 1.5% aluminum sulfate relative to the pulp, and relative to the pulp were added. A 0.3% commercial cation modified starch was formulated to prepare a pulp slurry of pH 5.0. Furthermore, the pH of the papermaking system is adjusted using an aqueous solution of sulfuric acid. Then, the sizing agent of Example 1 was added to the pulp slurry in an amount of 0.3% (calculated as solid content) with respect to the pulp, and a paper machine (Tappi Standard Sheet Machine (circular), the same applies hereinafter) was used. Papermaking is carried out to obtain wet paper. The wet paper was dehydrated by a roll press (condition: line pressure: 5.5 kg/cm, feed rate: 2 m/min), and dried at 90 ° C for 360 seconds using a rotary dryer. The obtained dried paper was subjected to humidity conditioning under constant temperature and humidity (23 ° C, 50% relative humidity) for 24 hours, whereby a paper (test paper) having a basis weight of 80 g/m ² was obtained. In Examples 2 to 4 and Comparative Examples 1 and 2, the same method was also carried out to obtain paper. Then, for each test paper, the Stoke sizing degree was measured in accordance with JIS-P8122. The results are shown in Table 2. Furthermore, the greater the value of the Stoke sizing degree, the better.

<Test 2: Use of waste paper pulp; evaluation of acid papermaking and Cobb water absorption> For corrugated paper waste paper (containing ash 12%), tap water was added in an amount such that the pulp concentration became 2.0%, and beater was used for beating. Up to 400ml Canadian Standard Freeness. Then, the obtained pulp slurry was further diluted with tap water to adjust the pulp concentration to 1.0%. To this diluted pulp slurry, 1.0% aluminum sulfate was added to the pulp to prepare a pulp slurry having a pH of 5.0. Furthermore, the pH of the papermaking system is adjusted using an aqueous solution of sulfuric acid. Then, the sizing agent of Example 1 was added to the pulp slurry in an amount of 0.3% (calculated as solid content) with respect to the pulp, and papermaking was carried out using a paper machine to obtain a wet paper. The wet paper was dehydrated by a roll press (condition: line pressure: 5.5 kg/cm, feed rate: 2 m/min), and dried at 90 ° C for 360 seconds using a rotary dryer. The obtained dried paper was subjected to humidity conditioning under constant temperature and humidity (23 ° C, 50% relative humidity) for 24 hours, whereby a paper (test paper) having a basis weight of 150 g/m ² was obtained. In Examples 2 to 4 and Comparative Examples 1 and 2, the same method was also carried out to obtain paper. Then, for each test paper, the absorbability (contact time: 1 minute) was measured in accordance with JIS-P8140. The results are shown in Table 2. Furthermore, the smaller the value of the water absorption, the better.

[Table 2]

<Manufacture of rosin ester (B2-1)> (Production Example 5) In the same reaction container as in Production Example 1, 663.2 parts of SL rosin as the component (b1) and 55.6 parts of glycerin as the component (b3) were charged (equivalent ratio) [-OH _(eq) /COOH _(eq) ] = 0.91), and added 10 parts of Nocrac 300 (product name, manufactured by Ouchi Shinko Chemical Co., Ltd.) as an antioxidant, and 0.1 part of p-toluene as a catalyst. The sulfonic acid was then reacted at 270 ° C for 15 hours while stirring under a nitrogen gas stream, thereby obtaining a rosin ester having an acid value of 16.1 mg KOH/g, a hydroxyl value of 8.1 mg KOH/g and a softening point of 90.8 ° C (B2- 1).

<Manufacture of rosin ester (B2-2)> (Production Example 6) In the same reaction container as in Production Example 1, 663.2 parts of BSL rosin as the component (b1) and 55.6 parts of glycerin as the component (b3) were charged (equivalent ratio) [-OH _(eq) /COOH _(eq) ] = 0.91), and added 10 parts of Nocrac 300 (manufactured by Ouchi Shinko Chemical Co., Ltd.) as an antioxidant, and 0.1 part of p-toluenesulfonic acid as a catalyst. Then, the mixture was reacted at 270 ° C for 15 hours while stirring under a nitrogen gas stream, whereby a rosin ester (B2-2) having an acid value of 15.9 mgKOH/g, a hydroxyl value of 8.1 mgKOH/g and a softening point of 90.5 °C was obtained.

<Manufacture of rosin ester (C2-1)> (Production Example 7) In the same reaction container as in Production Example 1, 663.2 parts of CN rosin as the component (c1) and 55.6 parts of glycerin as the component (b3) were charged (equivalent ratio) [-OH _(eq) /COOH _(eq) ] = 0.91), and added 10 parts of Nocrac 300 (manufactured by Ouchi Shinko Chemical Co., Ltd.) as an antioxidant, and 0.1 part of p-toluenesulfonic acid as a catalyst. Then, the mixture was reacted at 270 ° C for 15 hours while stirring under a nitrogen gas stream, whereby a rosin ester (C2-1) having an acid value of 16.3 mgKOH/g, a hydroxyl value of 8.0 mgKOH/g and a softening point of 91.0 °C was obtained.

<Preparation of rosin-based emulsion sizing agent (2)> (Example 5) In the same reaction container as in Example 1, 80 g of the reinforcing rosin (B1-1) of Production Example 3 and 20 g of the rosin ester of Production Example 5 were charged. (B2-1), and heat-melted at about 160 °C. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-1) of Production Example 1 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained. The physical properties of the obtained sizing agent are shown in Table 3. (the same below)

(Example 6) 80 g of the reinforcing rosin (B1-2) of Production Example 4 and 20 g of the rosin ester (B2-2) of Production Example 6 were placed in the same reaction container as in Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-1) of Production Example 1 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 7) 80 g of the reinforced rosin (B1-1) of Production Example 3 and 20 g of the rosin ester (B2-1) of Production Example 5 were placed in the same reaction container as in Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-2) of Production Example 2 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained. The physical properties of the obtained sizing agent are shown in Table 3.

(Example 8) 80 g of the reinforcing rosin (B1-2) of Production Example 4 and 20 g of the rosin ester (B2-2) of Production Example 6 were placed in the same reaction container as in Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-2) of Production Example 2 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Comparative Example 3) 80 g of the reinforced rosin (i) of Comparative Production Example 1 and 20 g of the rosin ester (C2-1) of Production Example 7 were placed in the same reaction container as in Example 1, and heat-melted at about 160 ° C. . Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-1) of Production Example 1 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Comparative Example 4) 80 g of the reinforced rosin (i) of Comparative Production Example 1 and 20 g of the rosin ester (C2-1) of Production Example 7 were placed in the same reaction container as in Example 1, and heat-melted at about 160 ° C. . Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-2) of Production Example 2 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

[table 3]

<Experiment 3: Using L-BKP; Evaluation of Neutral Papermaking and Stokes Sizing Degree> To L-BKP, tap water was added in an amount to make the pulp concentration 2.0%, and beaten to 300 ml Canadian Standard Free using a beater. So far. Then, the obtained pulp slurry was further diluted with tap water to adjust the pulp concentration to 1.0%. Then, in the diluted pulp slurry, a filler (a mixture of calcium carbonate and talc) having a ratio of 16.0% (based on absolute dry weight, the same below) to the pulp, 1.5% aluminum sulfate relative to the pulp, and relative to The pulp was 0.3% of commercially available cationic modified starch to prepare a pulp slurry of pH 6.7. Further, the pH of the papermaking system is adjusted by using an aqueous sodium hydroxide solution. Then, the sizing agent of Example 5 was added to the pulp in an amount of 0.3% (calculated as a solid content), and papermaking was carried out using a paper machine to obtain a wet paper. Then, each wet paper was dehydrated by a roll press having a line pressure of 5.5 kg/cm and a feed rate of 2 m/min, and dried at 90 ° C for 360 seconds using a rotary dryer. Then, the obtained dried paper was subjected to humidity conditioning under constant temperature and humidity (23 ° C, 50% relative humidity) for 24 hours, whereby a paper (test paper) having a basis weight of 80 g/m ² was obtained. In Examples 6 to 8 and Comparative Examples 3 to 4, the same method was also carried out to obtain paper formation. Then, for each test paper, the Stoke sizing degree was measured in accordance with JIS-P8122. The results are shown in Table 4.

<Test 4: Use of waste paper pulp; evaluation of neutral papermaking and Bob water absorption> For corrugated waste paper (containing 12% ash), tap water was added in an amount to make the pulp concentration 2.0%, and beaten to 400 ml using a beater. Canadian standard freeness up to now. Then, the obtained pulp slurry was further diluted with tap water to adjust the pulp concentration to 1.0%. Then, in this diluted pulp slurry, 1.0% of aluminum sulfate was added to the pulp to prepare a pulp slurry of pH 6.7. Further, the pH of the papermaking system is adjusted by using an aqueous sodium hydroxide solution. Then, the sizing agent of Example 5 was added to the pulp slurry in an amount of 0.3% (calculated as solid content) with respect to the pulp, and papermaking was carried out using a paper machine to obtain a wet paper. Then, each wet paper was dehydrated by a roll press having a line pressure of 5.5 kg/cm and a feed rate of 2 m/min, and dried at 90 ° C for 360 seconds using a rotary dryer. Then, the obtained dried paper was subjected to humidity conditioning under constant temperature and humidity (23 ° C, 50% relative humidity) for 24 hours, whereby a paper (test paper) having a basis weight of 150 g/m ² was obtained. In Examples 6 to 8 and Comparative Examples 3 to 4, the same method was also carried out to obtain paper formation. Then, for each test paper, the absorbability (contact time: 1 minute) was measured in accordance with JIS-P8140. The results are shown in Table 4.

[Table 4]

<Production of acrylamide-based anionic copolymer salt (A1-3)> (Production Example 8) In the same reaction container as in Production Example 1, 7.00 g (4.91 mol%) of the component (a1) was charged. Kang acid and 4.00 g (1.77 mol%) sodium styrene sulfonate, 5.00 g (2.47 mol%) 2-ethylhexyl acrylate and 16.00 g (8.69 mol%) methacrylic acid as component (a2) Cyclohexyl ester, 5.00 g (2.88 mol%) of sodium methallylsulfonate as component (a3), 61.50 g (78.93 mol%) of acrylamide as component (a4), as component (a6) 1.50 g (0.35 mol%) of hexaethylene glycol diacrylate, and 220 g of ion-exchanged water and 250 g of isopropyl alcohol were then allowed to warm up to 50 ° C with a nitrogen gas bubble while stirring. Then, 2.20 g of APS was added, and then the temperature was raised to 80 ° C and maintained for 180 minutes. Then, isopropanol was distilled off by blowing water vapor, and then ion-exchanged water was added, whereby an aqueous solution of an anionic copolymer salt (A1-3) having a weight average molecular weight of 16,000 was obtained. Further, the aqueous solution had a nonvolatile content of 25.0%, a viscosity at 25 ° C of 480 mPa ‧ and a pH of 4.7.

<Production of acrylamide-based anionic copolymer salt (A1-4)> (Production Example 9) In the same reaction vessel as in Production Example 1, 25.00 g (18.30 mol%) of itaconic acid and 8.00 g (in terms of 4.13 mol%) 2-ethylhexyl acrylate, 10.00 (5.67 mol%) cyclohexyl methacrylate, 2.50 g (1.51 mol%) sodium methallyl sulfonate, 52.50 g (70.34 mol) %) acrylamide, 220 g of ion-exchanged water, 250 g of isopropanol, and 0.50 g of 2-mercaptoethanol as a chain transfer agent, and then the mixture was stirred while raising the temperature to 50 ° C with a nitrogen bubble. until. Then, 2.20 g of APS was added, and then the temperature was raised to 80 ° C and maintained for 180 minutes. Then, an isopropanol was distilled off by blowing water vapor, and then a specific amount of ion-exchanged water was added to obtain an aqueous solution of an anionic copolymer salt (A1-4) having a weight average molecular weight of 12,000. Further, the aqueous solution had a nonvolatile content of 25.0%, a viscosity at 25 ° C of 650 mPa ‧ s, and a pH of 5.1.

<Production of the reinforced turpentine (B1-3)> In the same reaction vessel as in Production Example 1, 400.0 g of SL rosin as a component (b1) was melted at about 160 ° C, and 48.0 g of horse as a component (b2) was charged. The acid was introduced, and the mixture was reacted at 200 ° C for 2 hours while stirring under a nitrogen gas stream, whereby a fortified rosin (B1-3) having a softening point of 97.9 ° C and an acid value of 241.5 mg KOH / g was obtained.

<Production of the reinforced turpentine (B1-4)> (Production Example 11) In the same reaction vessel as in Production Example 1, 300.0 g of a melt of SL rosin at a temperature of about 160 ° C was introduced as (b1) as (c1) The melt of 300.0 g of CN rosin of the composition at about 160 ° C [13.8% by weight of abietic acid, 81.7% by weight of rosinic acid and 1.5% by weight of cedaric acid), and 48.0 g of Malay as component (b2) The acid was then reacted at 200 ° C for 2 hours while stirring under a nitrogen gas stream, whereby a reinforced rosin (B1-4) having a softening point of 98.3 ° C and an acid value of 241.8 mg KOH / g was obtained.

<Production of the reinforced turpentine (B1-5)> (Production Example 12) In the same reaction container as in Production Example 1, 50.0 g of a SL rosin as a component (b1) was melted at about 160 ° C as (c1). The melt of 550.0 g of CN rosin of the composition at about 160 ° C [10.9% by weight of abietic acid, 88.9 % by weight of rosin acid and 0.2% by weight of cedaric acid), and 48.0 g of Malay as component (b2) The acid was then reacted at 200 ° C for 2 hours while stirring under a nitrogen gas stream, whereby a fortified rosin (B1-5) having a softening point of 98.5 ° C and an acid value of 242.0 mg KOH / g was obtained.

<Production of the reinforced turpentine (B1-6)> (Production Example 13) In the same reaction container as in Production Example 1, 600.0 g of a BSL rosin as a component (b1) was melted at about 160 ° C as (b2). 48.0 g of maleic acid as a component was reacted at 200 ° C for 2 hours while stirring under a nitrogen gas stream, whereby a reinforced rosin (B1-6) having a softening point of 97.3 ° C and an acid value of 241.1 mg KOH / g was obtained.

<Production of reinforced turpentine (ii)> (Comparative Production Example 2) In the same reaction vessel as in Production Example 1, 600.0 g of CN rosin was melted at about 160 ° C with 48.0 g of maleic acid, and then under a nitrogen stream. The mixture was reacted at 200 ° C for 2 hours while stirring, whereby a reinforced rosin (ii) having a softening point of 98.8 ° C and an acid value of 242.2 mg KOH / g was obtained.

<Preparation of rosin-based emulsion sizing agent (3)> (Example 9) 70 g of the reinforcing rosin (B1-3) of Production Example 10 and 30 g of the rosin ester of Production Example 5 were placed in the same reaction container as in Example 1. (B2-1), and heat-melted at about 160 °C. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-3) of Production Example 8 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained. The physical properties of the obtained sizing agent are shown in Table 5. (the same below)

(Example 10) 70 g of the reinforcing rosin (B1-4) of Production Example 11 and 30 g of the rosin ester (B2-1) of Production Example 5 were placed in the same reaction container as in Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-3) of Production Example 8 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 11) 70 g of the reinforced rosin (B1-5) of Production Example 12 and 30 g of the rosin ester (B2-1) of Production Example 5 were placed in the same reaction vessel as in Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-3) of Production Example 8 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 12) 70 g of the reinforcing rosin (B1-3) of Production Example 10 and 30 g of the rosin ester (C2-1) of Production Example 7 were placed in the same reaction container as in Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-3) of Production Example 8 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 13) 70 g of the reinforcing rosin (B1-6) of Production Example 13 and 30 g of the rosin ester (B2-2) of Production Example 6 were placed in the same reaction container as in Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-3) of Production Example 8 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 14) 70 g of the reinforced rosin (B1-3) of Production Example 10 and 30 g of the rosin ester (C2-1) of Production Example 7 were placed in the same reaction vessel as in Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-4) of Production Example 9 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 15) 70 g of the reinforcing rosin (B1-6) of Production Example 13 and 30 g of the rosin ester (B2-2) of Production Example 6 were placed in the same reaction container as in Example 1, and heated at about 160 °C. Melt. Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-4) of Production Example 9 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Comparative Example 5) 70 g of the reinforcing rosin (ii) of Comparative Production Example 2 and 30 g of the rosin ester (C2-1) of Production Example 7 were placed in the same reaction container as in Example 1, and heat-melted at about 160 ° C. . Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-3) of Production Example 8 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Comparative Example 6) 70 g of the reinforcing rosin (ii) of Comparative Production Example 2 and 30 g of the rosin ester (C2-1) of Production Example 7 were placed in the same reaction container as in Example 1, and heat-melted at about 160 ° C. . Then, an aqueous solution (6 g in terms of solid content) of the anionic copolymer salt (A1-4) of Production Example 9 was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further heat was added. Water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

[table 5]

<Experiment 5: Use of L-BKP; Evaluation of Neutral Papermaking and Stokes Sizing Degree> Using the sizing agents of Examples 9 to 15 and Comparative Examples 5 to 6, and using L- according to Test 3 described above, Neutral papermaking of BKP to obtain a paper having a basis weight of 80 g/m ² . The results of the measurement of the Stoke sizing degree of each paper sheet are shown in Table 6.

<Test 6: Use of waste paper pulp; evaluation of neutral papermaking and Bob water absorption> Using the sizing agents of Examples 9 to 15 and Comparative Examples 5 to 6, and performing neutral using waste paper pulp in accordance with the above test 4 Papermaking was carried out to obtain a paper having a basis weight of 150 g/m ² . The measurement results of the absorbability (contact time: 1 minute) of each paper formation are shown in Table 6.

[Table 6]

<Production of cationic polyamine polyamine (A2-1)> (Production Example 14) In the same reaction vessel as in Production Example 1, 730 g (about 5 mol) of adipic acid and 516 g (about 5 m) were charged. Further, ethyltriamine was added, and the resulting water was removed to the outside of the system, and the reaction system was heated, and allowed to react at 120 to 200 ° C for 4 hours, thereby obtaining a polyamine polyamine (polycondensate). Further, the viscosity of the 50% by weight aqueous solution of the polyamine polyamine was 450 mPa ‧ / 25 ° C. Then, 3720 g of water and 137.7 g of 98% sulfuric acid were gradually added to the polyamine polyamine under stirring, thereby obtaining a solid concentration of 23.5% by weight, a viscosity of 25 mPa s at 25 ° C, and a pH of 2.4. An aqueous solution of a cationic polyamine polyamine (A2-1).

<Production of cationic polyamine polyamine (A2-2)> (Production Example 15) 530 g of the polyamine polyamine used in each of the above production examples and 255 g of ion-exchanged water were added to the same reaction container as in Production Example 1. And set to 20 ° C. 168 g of epichlorohydrin was added dropwise over 3 hours and incubated at 35 ° C for 1 hour. 540 g of ion-exchanged water was added and further incubated for 1 hour, followed by heating to 65 °C. 15 g of 62.5% sulfuric acid and 119 g of ion-exchanged water were added and cooled to 30 °C. An aqueous solution of a cationic polyamidamine polyamine (A2-2) having a solid concentration of 23.5%, a viscosity of 25 mPa s at 25 ° C and a pH of 2.3 was obtained.

<Preparation of rosin-based emulsion sizing agent (4)> (Example 16) 100 g of the reinforced rosin (B1-1) of Production Example 3 was placed in the same reaction vessel as in Example 1, and heated at about 160 °C. Melt. Then, the aqueous solution of the cationic polyamine polyamine (A2-1) of Production Example 14 (6 g in terms of solid content) was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further Add hot water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained. The physical properties of the obtained sizing agent are shown in Table 7. (the same below)

(Example 17) A water-soluble aluminum compound (D1) obtained by mixing 31.4 g of a 50% aqueous aluminum sulfate solution and 13.5 g of a 19.2% sodium carbonate aqueous solution was added to 100 g of the sizing agent of Example 16 which had been heated to 65 ° C. Medium and evenly stirred to obtain a sizing agent.

(Example 18) 100 g of the reinforcing rosin (B1-1) of Production Example 3 was placed in the same reaction container as in Example 1, and heat-melted at about 160 °C. Then, the aqueous solution of the cationic polyamine polyamine (A2-2) of Production Example 15 (6 g in terms of solid content) was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further Add hot water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 19) 100 g of the reinforcing rosin (B1-2) of Production Example 4 was placed in the same reaction container as in Example 1, and heat-melted at about 160 °C. Then, the aqueous solution of the cationic polyamine polyamine (A2-1) of Production Example 14 (6 g in terms of solid content) was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further Add hot water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Example 20) A water-soluble aluminum compound (D1) obtained by mixing 31.4 g of a 50% aqueous aluminum sulfate solution and 13.5 g of a 19.2% sodium carbonate aqueous solution was added to 100 g of the sizing agent of Example 19 which had been heated to 65 °C. Medium and evenly stirred to obtain a sizing agent.

(Example 21) 100 g of the reinforcing rosin (B1-2) of Production Example 4 was placed in the same reaction container as in Example 1, and heat-melted at about 160 °C. Then, the aqueous solution of the cationic polyamine polyamine (A2-2) of Production Example 15 (6 g in terms of solid content) was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further Add hot water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Comparative Example 7) 100 g of the reinforcing rosin (i) of Comparative Production Example 1 was placed in the same reaction container as in Example 1, and heat-melted at about 160 °C. Then, the aqueous solution of the cationic polyamine polyamine (A2-1) of Production Example 14 (6 g in terms of solid content) was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further Add hot water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

(Comparative Example 8) A water-soluble aluminum compound (D1) obtained by mixing 31.4 g of a 50% aqueous aluminum sulfate solution and 13.5 g of a 19.2% sodium carbonate aqueous solution was added to 100 g of the sizing agent of Comparative Example 7 which had been heated to 65 ° C. Medium and evenly stirred to obtain a sizing agent.

(Comparative Example 9) 100 g of the reinforcing rosin (i) of Comparative Production Example 1 was placed in the same reaction container as in Example 1, and heat-melted at about 160 °C. Then, the aqueous solution of the cationic polyamine polyamine (A2-2) of Production Example 15 (6 g in terms of solid content) was gradually added dropwise under stirring to prepare an emulsion in a W/O form, and then further Add hot water to make a stable O/W emulsion. Thereafter, the emulsion was cooled to room temperature, whereby a sizing agent was obtained.

[Table 7]

<Experiment 7: Use of L-BKP; Evaluation of Neutral Papermaking and Stokes Sizing Degree> Using the sizing agents of Examples 16 to 21 and Comparative Examples 7 to 9, and using L- according to Test 3 described above, Neutral papermaking of BKP to obtain a paper having a basis weight of 80 g/m ² . The results of the measurement of the Stoke sizing degree of each paper sheet are shown in Table 8.

<Test 8: Use of waste paper pulp; evaluation of neutral papermaking and Bob water absorption> Using the sizing agents of Examples 16 to 21 and Comparative Examples 7 to 9, and performing neutral using waste paper pulp in accordance with the above test 4 Papermaking was carried out to obtain a paper having a basis weight of 150 g/m ² . The measurement results of the absorbability (contact time: 1 minute) of each paper formation are shown in Table 8.

[Table 8]

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no

Claims (20)

A rosin-based emulsion sizing agent obtained by emulsifying an emulsion (B) in the presence of a polymer dispersant (A), the emulsified product (B) being selected from the group consisting of At least one of: a reinforced rosin (B1) which is an addition product of rosin (b1) and an α,β-unsaturated carboxylic acid (b2), and the rosin (b1) contains 0.1 to 8% by weight of hydrazine. Beric acid, 15 to 34.9% by weight of cedaric acid and 65 to 84.9% by weight of rosin acid; and rosin ester (B2) which is a reaction product of the component (b1) and the polyol (b3). The rosin-based emulsion sizing agent according to claim 1, wherein the component (A) is an anionic copolymer and/or a salt thereof (A1). The rosin-based emulsion sizing agent according to claim 2, wherein the component (A1) is an anionic unsaturated monomer (a1), a hydrophobic unsaturated monomer (a2), and a chain-transfer unsaturated monomer. (a3) A copolymer or a salt thereof as a reaction component. The rosin-based emulsion sizing agent according to claim 3, wherein the component (a1) comprises a group selected from the group consisting of a carboxyl group-containing unsaturated monomer, a sulfonic acid group-containing unsaturated monomer, and the like. At least one of them. The rosin-based emulsion sizing agent according to claim 3, wherein the component (a2) comprises styrenes and/or alkyl (meth)acrylates. The rosin-based emulsion sizing agent according to any one of claims 3 to 5, wherein the component (a3) comprises (meth)allylsulfonic acid and/or a salt thereof. The rosin-based emulsion sizing agent according to any one of claims 2 to 6, wherein the component (A1) is further selected from the group consisting of acrylamide (a4), a hydroxyl group-containing unsaturated monomer (a5), and At least one of the group consisting of the ethylenically unsaturated monomers (a6) is used as a reaction component. The rosin-based emulsion sizing agent according to any one of claims 2 to 7, wherein the (A1) component has a weight average molecular weight of 4,000 to 100,000. The rosin-based emulsion sizing agent according to claim 1, wherein the component (A) is a cationic polyamine polyamine (A2). The rosin-based emulsion sizing agent according to claim 9, wherein the component (A2) is a polycondensate of an aliphatic dibasic acid and a polyalkylene polyamine by a cationizing agent (β). α) is obtained by upgrading. The rosin-based emulsion sizing agent according to claim 10, wherein the (α) component has a viscosity of 200 to 1,000 mPa·s at a solid concentration of 50% by weight and a temperature of 25°C. The rosin-based emulsion sizing agent according to claim 10, wherein the (β) component comprises an epihalohydrin and/or an inorganic acid. The rosin-based emulsion sizing agent according to any one of claims 1 to 12, wherein the component (b3) comprises a triol and/or a tetrahydric alcohol. The rosin-based emulsion sizing agent according to any one of claims 1 to 13, wherein the weight ratio of the (B1) component to the (B2) component is [(B2)/{(B1)+(B2)} ] is 0.05 to 0.5. The rosin-based emulsion sizing agent according to any one of claims 1 to 14, wherein the component (A) is used in an amount of 5 to 12 parts by weight based on 100 parts by weight of the component (B). The rosin-based emulsion sizing agent according to any one of claims 1 to 15, further comprising at least one emulsified product (C) selected from the group consisting of: ‧ fortified rosin (C1), It is an addition reaction product of the rosin-free rosin (c1) and (b2) components; ‧ rosin ester (C2), which is a reaction product of the component (c1) and the component (b3). The rosin-based emulsion sizing agent according to claim 16, wherein the weight ratio [(C)/{(B)+(C)}]] of the component (B) to the component (C) is 0.05 to 0.5. The rosin-based emulsion sizing agent according to any one of claims 1 to 17, further comprising a water-soluble aluminum compound (D). The rosin-based emulsion sizing agent according to any one of claims 1 to 18, wherein the average primary particle diameter is 0.3 to 1.2 μm. A paper obtained by using the rosin-based emulsion sizing agent according to any one of claims 1 to 19.