JP2008255556A - Method for producing bulky paper and bulky paper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing bulky paper improving bulking effects while keeping strength of paper (in particular, inner strength), with a reduced addition amount of a bulking agent. <P>SOLUTION: The method for producing bulky paper in which paper making is carried out after adding a bulking agent (1) containing a fatty acid modified polyamide resin (A) containing a tertiary amido group and a tertiary amino group obtained by reacting a polyamine compound (a1) containing a secondary amino group, a mono carboxylic acid compound (a2) and a compound containing a glycidyl group (a3), and a paper strengthening agent (2) containing amphoteric polyacrylamide (B) to a paper stock (3) is characterized in that the paper strengthening agent (2) has at least 50 ml of the difference between Canadian standard freeness (ml) of paper stock (3) containing a paper strengthening agent (2) and the Canadian standard freeness (ml) of paper stock (3) without containing the paper strengthening agent (2). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a method for producing a bulky paper and a bulky paper obtained by the production method.

  Bulky paper refers to lightweight paper that has been reduced in density while maintaining the thickness of the paper (hereinafter sometimes referred to as “bulky effect”), and contributes to resource conservation because the amount of pulp per unit volume of paper is small. In recent years, the demand for paper has increased significantly.

There are various methods for producing bulky paper, but the method of adding an organic or inorganic additive (bulkiening agent) to the stock during papermaking gives the paper other required performance in addition to the bulky effect. There are many advantages such as being easy and not requiring the use of a special device (see Patent Documents 1 and 2, etc.). In particular, according to the bulking agent using fatty acid-modified amides, a size effect can be imparted to the printing paper in addition to the bulky effect.

However, in order to obtain a further bulking effect using these bulking agents, it is generally necessary to add a large amount, but at the same time, the strength of the paper tends to decrease, and it is not economical. This is probably because the bulking agent has a weak adsorption power to pulp and a low yield rate to paper.
Japanese Patent Laid-Open No. 3-124895 JP 2003-96692 A

An object of the present invention is to provide a method for producing a bulky paper, which can improve the bulkiness effect while maintaining the strength (particularly the internal strength) of the paper with a small amount of bulking agent. Moreover, this invention makes it a subject to provide the bulky paper which is excellent in the bulky effect, maintaining the intensity | strength (especially internal strength) of paper.

As a result of studying means for increasing the yield of the bulking agent bulking agent relative to the paper stock, the present inventor has found that the object can be achieved according to the following configuration. That is, the present invention is:

1. Fatty acid containing tertiary amide group and tertiary amino group obtained by reacting secondary amine group-containing polyamine compound (a1), monocarboxylic acid compound (a2), and glycidyl group-containing compound (a3) A bulky paper manufacturing method in which paper making is performed after adding a bulking agent (1) containing a modified amide resin (A) and a paper strength enhancing agent (2) containing an amphoteric polyacrylamide (B) to the stock (3). In the above, the paper strength enhancer (2) does not contain [the Canadian standard freeness (ml) of the paper stock (3) containing the paper strength enhancer (2)] and [the paper strength enhancer (2). A method for producing a bulky paper, characterized in that it gives a value exceeding 50 ml as a difference from Canadian Standard Freeness (ml) of the stock (3),

2. (A1) formed from the number of secondary amino groups present in component x, and the secondary amino group present in component (a1) and the carboxyl group in component (a2) present in component (A) When the number of tertiary amide groups formed is y and the number of tertiary amino groups formed from the secondary amino group of component (a1) and the glycidyl group of component (a3) is z Wherein the value of y / x of the component (A) is 0.05 to 0.9 and the value of z / x is 0.1 to 0.95,

3. The component (a1) is represented by the general formula (I): H ₂ N — [— (CH ₂ ) _m —NH—] _n —H ( _where m is an integer of 1 to 3, and n is 2 to 6 The production method according to 1 or 2 above, which is a secondary amino group-containing polyamine compound represented by:

4). The component (a2) is a monocarboxylic acid compound having a linear alkyl group having 2 to 36 carbon atoms or a linear alkenyl group having 2 to 36 carbon atoms. ~ 3. The production method according to any one of

5. 1. The component (a3) is an epihalohydrin. ~ 4. The production method according to any one of

6). The component (A) is an aqueous dispersion. ~ 5. The production method according to any one of

7. 1. The turbidity unit (NTU) in a solution state of the paper strength enhancer (2) having a solid concentration of 1.0% by weight is 1000 or more and 4000 or less. ~ 6. The production method according to any one of

8). The amphoteric polyacrylamide (B) comprises (meth) acrylamide (b1), cationic (meth) acrylic monomer (b2), anionic (meth) acrylic monomer (b3), N-substituted (meth) acrylamide (b4). ), (Meth) allyl group-containing vinyl monomer (b5), which is a polymer obtained by copolymerization. ~ 7. The production method according to any one of

9. The production method according to any one of 1 to 8 above, wherein the amphoteric polyacrylamide (B) has a weight average molecular weight of 500,000 to 20 million.

10. 1 above. ~ 9. This relates to a bulky paper obtained by any one of the production methods.

  According to the production method of the present invention, the yield of the bulking agent to paper is improved, and the bulkiness effect can be improved while maintaining the strength (particularly internal strength) of the paper. In addition, the amount of bulking agent used can be reduced during papermaking. Furthermore, since the size effect is good, it is useful as various printing paper (for example, book paper, printing / information paper, newsprint paper, packaging paper, coated paper, inkjet recording paper, etc.).

The bulking agent (1) used in the present invention is a secondary amino group-containing polyamine compound (a1) (hereinafter referred to as (a1) component), a monocarboxylic acid compound (a2) (hereinafter referred to as (a2) component), And a fatty acid-modified amide resin (A) (hereinafter referred to as (A)) containing a tertiary amide group and a tertiary amino group, wherein the reaction component is a glycidyl group-containing compound (a3) (hereinafter referred to as component (a3)). Component).

Here, the “tertiary amide group” refers to an N, N-substituted amide group formed by the reaction between the secondary amino group of the component (a1) and the carboxyl group of the component (a2). It can be expressed as ¹ R ¹ N—CO—R ² . In the structural formula, R ¹ is a hydrocarbon group (an alkylene group or the like) of the component (a1), and R ² is a group derived from the hydrocarbon residue of the component (a2). For example, (a1) When the component is a polyalkylene polyamine, R ¹ corresponds to the alkylene group, and when the component (a2) is a monocarboxylic acid compound having a linear alkyl group, R ² is the straight chain. Corresponds to an alkyl group.

The “tertiary amino group” refers to a group formed by a reaction between a secondary amino group of the component (a1) and a glycidyl group of the component (a3), and R ¹ R ¹ N— it can be expressed as R ^3. In the structural formula, R ¹ is the same as described above, and R ³ corresponds to a hydrocarbon group (an alkylene group or the like) derived from the glycidyl group of the component (a3).

Further, the content of the tertiary amide group and the tertiary amino group contained in the component (A) is not particularly limited, but usually, the number of secondary amino groups contained in the component (a1) is x, and The number of tertiary amide groups formed from the secondary amino group of component (a1) and the carboxyl group of component (a2) present in component (A) is y, and component (a1) When the number of tertiary amino groups formed from the secondary amino group having the glycidyl group of the component (a3) is z, the y / x value of the component (A) is 0.05-0. 9 (preferably 0.2 to 0.7) and the value of z / x is 0.1 to 0.95 (preferably 0.2 to 0.8).

The value of y / x is the ratio of the secondary amino group specific to component (a1) converted to a tertiary amide group, and the value of z / x is specific to component (a1) Of the secondary amino groups, the ratio of those converted to tertiary amino groups. Each value can be derived from each usage amount (mol) of the components (a1) to (a3) described later.

As the component (a1), various known compounds can be used without particular limitation as long as they are polyamine compounds containing one or more secondary amino groups in the molecule. The hydrocarbon group constituting the component (a1) may be linear, cyclic, or branched, and the hydrocarbon group has a carbon-carbon unsaturated double bond. Also good.

In the specific example, the component (a1) is represented by the general formula (I): H ₂ N — [— (CH ₂ ) _m NH—] _n —H ( _where m is an integer of 1 to 3, and n is 2 Represents an integer of ˜6.), For example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamine, pentapropylene Hexamine etc. are mentioned, These can be used individually by 1 type or in combination of 2 or more types. Among the components (a1), low viscosity at normal temperature, good handleability, easy availability, and stable dispersion when component (A) is dispersed in water in the presence of an emulsifier In particular, at least one selected from the group consisting of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine is preferable because of providing a body.

As the component (a2), various known compounds can be used without particular limitation as long as they are monocarboxylic acid compounds having one carboxyl group in the molecule. The hydrocarbon group constituting the component (a2) may be linear, cyclic, or branched, and the hydrocarbon group has a carbon-carbon unsaturated double bond. Also good. Specific examples of the component (a2) include, for example, acetic acid, saturated fatty acids [butyric acid, propionic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoserine. Acid, serotic acid, montanic acid, melicic acid, etc.), unsaturated fatty acids (palmitoleic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, etc.), vegetable oils and animal fats (castor oil fatty acids, coconut oil fatty acids, palm oil fatty acids) , Beef tallow fatty acid, soybean oil fatty acid, rapeseed oil fatty acid, tall oil fatty acid and the like], and the like can be used alone or in combination of two or more. In the case where two or more types of component (a2) are used in combination, structural control becomes possible, for example, a plurality of types of hydrocarbon groups can be incorporated into component (A). Among these, from the viewpoints of reactivity with the component (a1), the bulking effect of the resulting bulking agent (1) and viscosity stability, the number of carbon atoms is 2 to 36 (preferably about 12 to 22 and more preferably. 16-22) or a straight chain alkenyl group having 2 to 36 (preferably about 12 to 22, more preferably 16 to 22) carbon atoms is preferred.

As the component (a3), various known compounds can be used without particular limitation as long as they are compounds having one glycidyl group in the molecule. By using the component (a3), a cationic group or a branched structure / crosslinked structure is introduced into the component (A). Specific examples of the component (a3) include epihalohydrins [epichlorohydrin, epibromohydrin, epiiohydrin, etc.], glycidols [2,3-epoxy-1-propanol, 3,4-epoxy, for example. -1-butanol and the like], and the like can be used singly or in combination of two or more. Among these, the reactivity with the component (a2) is high, the cationic group / branched structure / crosslinked structure is easily introduced, the size effect of the resulting bulky paper is improved, and the cost is low. For these reasons, the epihalohydrins, particularly epichlorohydrin, are preferred.

When the component (A) is produced, the amount of each of the component (a1), the component (a2) and the component (a3) is not particularly limited, but is usually in the range where the y / x and z / x values are used. If it is. Specifically, when the number of primary amino groups of the component (a1) is M and the number of secondary amino groups is N, 1 mole of the component (a1) (that is, the primary amino group is M Component (a2) is usually about (M + 0.05N) mol to (M + 0.9N) mol (preferably (M + 0.2N) mol to (M + 0.7N) mol). The component (a3) is usually in the range of about 0.1 N mol to 1.5 N mol (preferably 0.3 N mol to 1.00 N mol).

In addition, when using 2 or more types of (a1) component combining, it is necessary to make the value of said M and N into an average value, respectively. For example, when 1 mol of component (a1) is a 1 mol / 4 mol mixture of diethylenetriamine (M = 2, N = 1) and pentaethylenehexamine (M = 2, N = 4), M = 2 0.0 and N≈3.4.

Moreover, when the usage-amount of (a2) component is less than (M + 0.05N) mol, the quantity of the branched structure and bridge | crosslinking structure introduce | transduced into (A) component decreases, and it is difficult to maintain a bulky effect. is there. On the other hand, when the amount used exceeds (M + 0.9N) mol, the viscosity stability and various performances of the resulting bulky paper are affected by the side reaction between the remaining component (a2) and component (a3). May get worse.

In addition, when the amount of the component (a3) used is less than 0.1 N mol, the amount of the cationic group introduced into the component (A) decreases, so that the component (A) becomes difficult to fix to the pulp, It tends to be difficult to maintain the bulky effect. On the other hand, when the amount used exceeds 1.5 Nmol, the unreacted component (a3) tends to remain excessively in the system.

  The manufacturing method of (A) component is not specifically limited, Various well-known amidation reaction and addition reaction are employable. Since the structure of the component (A) can be easily controlled, the (a1) component and the (a2) component are subjected to an amidation reaction (dehydration condensation reaction) to produce a tertiary amide group-containing compound (A ′) (hereinafter referred to as “a”). , (A ′) component) is once produced, and then the (A ′) component and the (a3) component are subjected to an addition reaction.

  The amidation reaction is not particularly limited, and various known methods can be employed. Specifically, in the presence or absence of a solvent or a catalyst, the reaction product water is removed for about 2 to 8 hours at a temperature of about 150 ° C. to 200 ° C. The component (a2) in the range may be subjected to a dehydration condensation reaction.

  In addition, as said solvent, various well-known things can be especially used without a restriction | limiting. Specific examples include aromatic hydrocarbons [benzene, toluene, xylene, chlorobenzene, etc.], pyridines [N-methyl-2-pyrrolidone, etc.], etc., and these may be used alone or in combination. Two or more kinds can be used in combination. Of these, those that readily azeotrope with the reaction product water (such as toluene) are preferred. Moreover, the usage-amount of this solvent should just be a range from which the solid content concentration of a reaction system will be about 50 to 100 weight% normally.

As the catalyst, various known catalysts can be used without particular limitation. Specific examples include acid catalysts [alkyl sulfonic acid, p-toluene sulfonic acid, benzene sulfonic acid, sulfuric acid, phosphorous acid, etc.], basic catalysts [pyridine, trimethylamine, triethylamine, etc.], etc. One kind can be used alone, or two or more kinds can be used in combination. In addition, the usage-amount of this catalyst should just be the range used as about 3 weight% or less normally with respect to the total weight of (a1) component and (a2) component.

  The addition reaction is not particularly limited, and various known methods can be employed. Specifically, the component (A ′) and the component (a3) may be reacted usually in the presence of water at about 50 to 100 ° C. for about 2 to 6 hours. In addition, this (A ') component can also be used for reaction with (a3) component in the state made into the water dispersion according to the method mentioned later. In that case, a co-solvent (ethanol, propanol, isopropyl alcohol, etc.) can also be used as needed.

The obtained component (A) can be used as a bulking agent (1) as it is, but it is preferable to use it as an aqueous dispersion in consideration of the fact that the stock (3) is aqueous.

The method for preparing the aqueous dispersion of component (A) is not particularly limited, and various known methods can be used without particular limitation. Specifically, for example, a method of dispersing the obtained component (A) in water in the presence or absence of an emulsifier, or the components (A ′) and (a3) as the water dispersion Examples thereof include a method using the reaction product as it is.

  As the emulsifier, various known non-reactive emulsifiers or reactive emulsifiers can be used without particular limitation. In addition, the usage-amount of this emulsifier is the range used as about 1 to 10 weight% normally with respect to the said (A) component (solid content).

Examples of the non-reactive emulsifier include, for example, cationic emulsifiers [tetraalkyl ammonium chloride, monoalkyl ammonium chloride, dialkyl ammonium chloride, trialkyl ammonium chloride, tetraammonium chloride trialkylbenzyl ammonium chloride oxyethylene alkyl amine. Acetate or hydrochloride, acetate or hydrochloride of polyoxyethylene alkylamine, etc.), nonionic emulsifier (polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene styryl phenyl ether, Sorbitan monolaurate, sorbitan trioleate, polyoxyethylene sorbitan monolaurate, polyoxy Ethylene monolaurate, polyoxyethylene monooleate, oleic acid monoglyceride, stearic acid monoglyceride, polyoxyethylene / polyoxypropylene / block copolymer, etc.), anionic emulsifier (sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecyl sulfate, dodecylbenzene) Sodium sulfonate, sodium dialkylsulfosuccinate, potassium alkyl phosphate, sodium polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium polyoxyethylene tridecyl ether sulfate, etc.). Can be used alone or in combination of two or more.

As the reactive emulsifier, an emulsifier having a carbon-carbon double bond, a hydrophilic group and a hydrophobic group in the molecule can be used. Examples of the carbon-carbon double bond include (meth) allyl group, 1-propenyl group, 2-methyl-1-propenyl group, vinyl group, isopropenyl group, (meth) acryloyl group and the like. . Specific examples of the reactive emulsifier include polyoxyalkylene alkyl ethers having at least one carbon-carbon double bond in the molecule, sulfosuccinic acid ester salts, sulfate ester salts; and the carbon-carbon double bonds. Polyoxyalkylene phenyl ethers having at least one molecule, sulfosuccinic acid ester salts, sulfate ester salts thereof; polyoxyalkylene alkyl phenyl ethers having at least one carbon-carbon double bond in the molecule and sulfosuccinic acid thereof Ester salts, sulfate esters; polyoxyalkylene aralkylphenyl ethers having at least one carbon-carbon double bond in the molecule, sulfosuccinate esters thereof, sulfate esters; and the carbon-carbon double bond in the molecule Polio with at least one Aliphatic cycloalkylene alkylphenyl ethers and aromatic carboxylates having at least one carbon-carbon double bond in the molecule; acid anhydride modified product of rosin glycidyl ester acrylate (see JP-A-4-256429) ); Acidic phosphoric acid (meth) acrylic acid ester emulsifier; other known reactive emulsifiers (JP 63-23725, JP 63-240931, JP 62-104802, JP 4-50204, JP-A-4-53802, etc.), and these can be used singly or in combination of two or more. The “oxyalkylene” includes oxyethylene, oxypropylene, oxyethylene / oxypropylene, and the like.

  Examples of the water dispersion method include a mechanical emulsification method for forcibly emulsifying the component (A) and water, and gradually adding water to the melt of the component (A) to reverse the oil phase and the water phase. An inversion emulsification method, a high-pressure emulsification method in which the component (A) and water are emulsified under high pressure can be employed. In addition, the emulsifier used for this mechanical emulsification method is not specifically limited, For example, a homomixer, a high-pressure homogenizer (made by Manton-Gaurin) etc. can be used.

The physical properties of the obtained aqueous dispersion are not particularly limited. For example, the solid content concentration is usually about 0.1 to 50% by weight in consideration of workability and the like, and the component (A) is added to the pulp. The zeta potential is usually about +10 to +60 mV in consideration of fixing and the like, and the particle size is usually about 0.2 to 10 μm in consideration of the dispersibility of the component (A) in the paper (3). Preferably there is. The pH is usually about 4 to 7, and the appearance is usually white to yellowish white.

The aqueous dispersion may contain additives such as a pH adjuster as necessary. Examples of the pH adjuster include alkali metal compounds [sodium hydroxide, potassium hydroxide, etc.], mineral acids [phosphoric acid, sulfuric acid, hydrochloric acid, etc.], and organic acids [formic acid, acetic acid, etc.] ammonia. One kind can be used alone, or two or more kinds can be used in combination.

In the present invention, the paper strength enhancer (2) contains [Canadian standard freeness (ml) of paper stock (3) containing paper strength enhancer (2)] and [paper strength enhancer (2). It is characterized in that a material that gives a value exceeding 50 ml (preferably, a value of 70 ml to 300 ml) as a difference from the Canadian standard freeness (ml) of the paper material (3) not to be used is used. The Canadian standard freeness (hereinafter referred to as “freeness value”) is an index representing the degree of drainage (ml) of pulp as defined in JIS P 8121. The difference (hereinafter referred to as freeness difference) is an index representing the degree of pulp aggregation by the paper strength enhancer (2).

The reason why the effect of the present invention can be obtained by the paper strength enhancer (2) is not clear, but probably the stock (3) of the bulking agent (1) due to the difference in freeness exceeding 50 ml. This is thought to be due to an improvement in the yield rate.

The “paper (3) containing the paper strength enhancer (2)” (hereinafter abbreviated as test paper) is the same as the paper (3) described later including the paper strength enhancer (2). It may be. The “paper material (3) not containing the paper strength enhancer (2)” (hereinafter abbreviated as blank paper material) may be the same as the paper material (3) described later. (In other words, it may be the same as the test strip except that it does not contain the paper strength enhancer (2).)

In the measurement of the freeness value, the pulp types of the test paper stock and the blank stock material are not limited, but it is necessary to make the paper stock the same. Further, the pulp beating degree in both paper stocks is required to have a freeness value in a range of about 200 to 500 ml in any case. Further, the test paper stock and the blank stock material may contain the bulk improver (1) in a range of usually about 0.01 to 5% by weight.

Further, the paper strength enhancer (2) has a turbidity unit (NTU) in a solution state of a solid content concentration of 1.0% by weight usually 1000 or more and 4000 or less, particularly about 1500 to 4000. Those are preferred. Here, the turbidity unit (NTU) indicates how much the so-called polyion complex is formed by the amphoteric polyacrylamide (B) (hereinafter referred to as component (B)) in the paper strength enhancer (2). It is an index, and when it is less than 1000, the force of aggregating the amphoteric polyacrylamide (B) pulp becomes too weak, and the intended bulky paper tends to be difficult to obtain. If it exceeds 4000, the pulp agglomeration effect by the paper strength enhancer (2) becomes too strong, and it tends to be difficult to obtain the desired bulky paper.

In addition, the turbidity unit (NTU) is specifically measured by using an ANALITE turbidity meter “NEP-160 Portable Turbidity Meter” (manufactured by MacVan) and measuring scattered light of 180 degrees in 900 nm infrared light. Is a relative value with respect to a standard substance (formazine standard solution (400 NTU), manufactured by Wako Pure Chemical Industries, Ltd.).

As the component (B), those that give the difference in freeness or preferably the turbidity unit (NTU) can be appropriately selected from various known ones.

The component (B) specifically includes (meth) acrylamide (b1) (hereinafter referred to as (b1) component), a cationic (meth) acrylic monomer (b2) (hereinafter referred to as (b2) component), Anionic (meth) acrylic monomer (b3) (hereinafter referred to as component (b3)), N-substituted (meth) acrylamide (b4) (hereinafter referred to as component (b4)), (meth) allyl group-containing vinyl monomer ( b5) (hereinafter referred to as component (b5)) and, if necessary, a composition comprising a polymer obtained by copolymerizing vinyl monomer (b6) other than (b1) to (b5) (hereinafter referred to as component (b6)) It is a thing. (Hereinafter, “(meth) acryl” means “acryl” or “methacryl”.)

Examples of the component (b1) include acrylamide and methacrylamide, and these can be used alone or in combination of two or more.

As the component (b2), various known compounds can be used without particular limitation as long as the compound has at least one (meth) acryloyl group and one cationic functional group in the molecule. Specifically, for example, tertiary amino group-containing (meth) acrylic monomers [N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (Meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, etc.], salt of the tertiary amino group-containing (meth) acrylic monomer [hydrochloride, sulfate, acetate, etc.], the tertiary amino Examples include quaternary ammonium salt-containing (meth) acrylic monomers formed by the reaction of group-containing (meth) acrylic monomers and quaternizing agents (methyl chloride, benzyl chloride, dimethyl sulfate, epichlorohydrin, etc.). Can be used singly or in combination of two or more.

As the component (b3), various known compounds can be used without particular limitation as long as they are compounds having at least one (meth) acryloyl group and an anionic functional group in the molecule. Specifically, for example, α, β-unsaturated monocarboxylic acids [acrylic acid, methacrylic acid, crotonic acid, etc.], α, β-unsaturated dicarboxylic acid [maleic acid, (anhydrous) maleic acid, fumaric acid, itacon Acid, muconic acid, citraconic acid, etc.], α, β-unsaturated sulfonic acid (styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc.), and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) These may be used alone or in combination of two or more.

  As the component (b4), various known compounds can be used without particular limitation as long as they are N-substituted (meth) acrylamides other than the component (b2). Specifically, for example, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) ) Acrylamide, N-isopropyl (meth) acrylamide, Nt-butyl (meth) acrylamide, and the like. These may be used alone or in combination of two or more.

As the component (b5), various known compounds can be used without particular limitation as long as they are compounds having one (meth) allyl group in the molecule. Specific examples include sodium (meth) allylsulfonate and neutralized salts thereof, allyl alcohol, allylamine, and the like. These can be used alone or in combination of two or more. Examples of the neutralized salt include alkali metal salts (sodium salt, potassium salt, etc.), ammonium salts, and the like. Among the components (b5), the component (B) has a high molecular weight, and the effect of improving the paper strength can be easily obtained. Therefore, sodium (meth) allylsulfonate and its neutralized salt particularly have its own stability. In consideration, sodium methallylsulfonate and neutralized salts thereof are preferred.

In the present invention, vinyl monomers other than the above (b1) to (b5) (hereinafter referred to as (b6) component) can be used as necessary. Specific examples of the component (b6) include alkyl esters of the α, β-unsaturated monocarboxylic acids [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth ) Octyl acrylate, decyl (meth) acrylate, myristyl (meth) acrylate, stearyl (meth) acrylate, isopropyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid isostearyl alcohol, etc.], polyfunctional vinyl monomers [methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, divinylbenzene, 1, 3, 5-triacroyl hexahydride Ro-S-triazine, triallyl isocyanurate, triallylamine, tetramethylolmethanetetraacrylate, etc.], and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use the polyfunctional vinyl monomer because the paper strength effect is improved by increasing the molecular weight of the component (B).

  The amount of the (b1) component to (b6) component used is not particularly limited, but in general, the component (b1) is in the range of about 57 to 99.78 mol% (preferably 63 to 97.8 mol%). The component (b2) is in the range of about 0.1 to 15 mol% (preferably 1 to 15 mol%), and the component (b3) is in the range of about 0.1 to 15 mol% (preferably 1 to 15 mol%). The component (b4) is in the range of about 0.01 to 2 mol% (preferably 0.1 to 1 mol%), and the component (b5) is in the range of about 0.01 to 10 mol% (preferably 0.1 to 5 mol%). %), And the component (b6) is preferably less than 1 mol%.

  In addition, when either or both of the component (b2) and the component (b3) are less than 0.1 mol%, the polyion complex forming ability of the component (B) is lowered and the degree of aggregation of the pulp is not sufficient. Disappear. As a result, the yield ratio of the bulking agent to the paper tends to decrease, and the bulkiness effect tends to be difficult to obtain. On the other hand, when either or both components exceed 15 mol%, the acrylamide content in the component (B) decreases, so that the paper strength effect tends to be difficult to obtain. Further, when the component (b4) is less than 0.01 mol%, the component (B) is difficult to increase in molecular weight, whereas when it exceeds 2.0 mol%, the component (B) is produced. Gelation tends to occur. Further, when the component (b5) is less than 0.01 mol%, the chain transfer effect is weakened, and the branched structure tends not to be sufficiently introduced into the component (B), whereas it exceeds 10 mol%. In some cases, the chain transfer effect is too strong, and it tends to be difficult to increase the molecular weight of component (B).

The manufacturing method of (B) component is not specifically limited, Various well-known methods are employable. Specifically, for example, a method in which the components (b1) to (b5) (and further (b6) as necessary) are added dropwise to the reaction vessel while the polymerization reaction is performed, or each component is collectively added to the reaction vessel. A method of charging and polymerization reaction is exemplified. In addition, what is necessary is just to perform each superposition | polymerization method normally at about 20-140 degreeC and about 2 to 12 hours in presence of various well-known radical polymerization initiators and water, and presence of a chain transfer agent as needed.

As the polymerization initiator, various known ones can be used without particular limitation. Specifically, for example, organic peroxides [benzoyl peroxide, dicumyl peroxide, lauryl peroxide, etc.], inorganic peroxides [hydrogen peroxide, ammonium persulfate, potassium persulfate, etc.], azo compounds [2 2′-azobisisobutyronitrile, dimethyl-2, 2′-azobisisobutyrate, etc.] and the like. These may be used alone or in combination of two or more. In addition, what is necessary is just to make the usage-amount of this polymerization initiator into the range of about 0.01-5 weight% normally with respect to the total weight of said (b1) component-(b6) component.

The chain transfer agent can be used as necessary for the purpose of adjusting the molecular weight and viscosity of the component (B). Specific examples include alcohol chain transfer agents such as ethyl alcohol, methyl alcohol, and isopropyl alcohol. The amount of the chain transfer agent used is usually in the range of about 0 to 5% by weight based on the total weight of the components (b1) to (b5) (and further (b6) if necessary). That's fine. The chain transfer agent also acts as a solvent.

  In the present invention, the component (B) obtained by the above method can be Hoffman-decomposed or Mannich-modified (hereinafter referred to as component (B ')) by various known methods. .

The method for preparing the component (B ′) by the Hofmann decomposition is not particularly limited, and various known methods may be employed. Specifically, for example, by adding a hypohalite and an alkali catalyst to the aqueous solution of the component (B), the acrylamide polymer and the hypohalous acid are reacted in the alkaline region, and then the acid is added. The reaction system is usually adjusted to about pH 3.5 to 5.5 by adding. The acrylamide polymer in the component (B ′) generally contains about 5 to 50 mol% of a cationic monomer unit and usually about 60 to 95 mol% of an acrylamide unit, and has a weight. The average molecular weight is preferably about 5 to 3 million.

In the present invention, in addition to the component (B ′), Hofmann degradation products exemplified below can be used. Specifically, a cation-modified product prepared by decomposing a polyacrylamide polymer in the presence of choline chloride (Japanese Patent Laid-Open No. 53-109594), a tertiary amine having a hydroxyl group in the Hofmann decomposition reaction, A cation modified product prepared by adding a quaternary or a reaction product with benzyl or a derivative thereof (Japanese Patent Publication No. 58-8682), a cation modified product prepared by adding an organic polyvalent amine as a stabilizer in the Hofmann decomposition reaction ( JP-B-60-17322) and cation-modified products prepared by adding a specific cationic compound as a stabilizer in the Hofmann decomposition reaction (JP-B-62-45884).

The method for preparing the component (B ′) by the Mannich reaction is not particularly limited, and various known methods may be employed. Specifically, for example, formalin and a secondary amine (dimethylamine or the like) are added to the aqueous solution of the component (B), and the reaction is usually performed at about 40 to 60 ° C. for about 1 to 5 hours. In addition, the acrylamide polymer in the component (B ′) generally contains about 10 to 60 mol% of the cationic monomer unit and usually about 40 to 90 mol% of the acrylamide unit.

  The physical properties of the component (B) (or the component (B ′)) are not particularly limited. For example, the weight average molecular weight is usually 500,000 or more, specifically 700,000 to 20 million. When the weight average molecular weight is 500,000 or more, a sufficient bulky effect tends to be easily obtained. This is probably because the yield of the bulking agent (1) to the stock (3) has been improved due to the molecular weight.

In addition, this weight average molecular weight says the polyethylene oxide conversion value by GPC-LALLS method or GPC-RALLS method. In either method, the measurement conditions were 0.5 mol / l acetate buffer (0.5 mol / l acetic acid + 0.5 mol / l sodium acetate aqueous solution, pH about 4.2) as a solvent (eluent), polymer The concentration is 0.025%, the solution temperature is 40 ° C., and the light scattering angle is 5 ° or 90 °.

Further, the component (B) preferably has a viscosity of usually 50,000 mPa · sec / 25 ° C. or less, specifically about 20,000 to 1,000,000 mPa · sec / 25 ° C. The viscosity is a value measured using a B-type viscometer at a solid content concentration of 5% and a temperature of 25 ° C.

Specifically, the stock (3) used in the paper making used in the present invention includes pulp, water, and various additives (fixing agent, filler, pH adjusting agent, etc.) as necessary. This refers to pulp slurry. However, the paper material (3) here does not contain either the bulking agent (1) or the paper strength enhancing agent (2).

As the pulp, various known ones can be used without particular limitation. Specifically, for example, mechanical pulp such as ground pulp (GP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), bleached kraft pulp (L, N-BKP), kraft pulp (L, N- KP), chemical pulp such as semi-chemical pulp (SCP), deinked pulp (DIP), non-wood pulp such as kenaf, straw, bagasse, etc., and one kind selected from waste paper produced using these pulps. Or two or more types can be used in combination. In addition, although the beating degree of the said pulp is not specifically limited, Usually, what has a Canadian standard freeness measured by JIS P 8121 (hereinafter sometimes referred to as freeness value) is usually in the range of about 200 to 500. Used.

In addition, the content of the pulp in the stock (3) is not particularly limited, but considering the dispersibility of the bulking agent (1) and the paper strength enhancer (2), usually about 0.1 to 4% by weight, Preferably it is 0.3 to 3.5 weight%.

  Various known aluminum compounds can be used as the fixing agent. Specifically, for example, polyaluminum chloride, alumina sol, polyaluminum sulfate, polyaluminum sulfate silicate, aluminum chloride, aluminum sulfate, alum can be used, and these can be used alone or in combination of two or more. Can do. In addition, although content of the said fixing agent in paper stock (3) is not specifically limited, What is necessary is just to set it as the range of 0 to 10 weight% normally with respect to a pulp.

  Examples of the filler include clay, talc, kaolin, calcium carbonate, titanium oxide, and white carbon, and these can be used alone or in combination of two or more. In addition, although content of the said filler in paper stock (3) is not specifically limited, What is necessary is just to set it as the range of about 0 to 100 weight% normally with respect to a pulp.

  In addition, in the present invention, in addition to the above additives, additives such as a sizing agent, starch, pitch control agent, slime control agent, yield improver, antifoaming agent, pigment, dye, etc. can be used alone. Alternatively, two or more types can be used in combination.

  In addition, the water temperature of this stock (3) is not specifically limited, Usually, about 10-60 degreeC. Moreover, the pH is not specifically limited, Usually, it is about 4-9.

  When adding the bulking agent (1) and the paper strength enhancer (2) to the stock (3), the order of addition is not particularly limited, but in order to improve the effect of the present invention, the bulking agent ( After adding 1) to the stock (3), it is preferable to add the paper strength enhancer (2) before paper making. In addition, both addition is normally performed under strong stirring.

In addition, the amount of each of the bulking agent (1) and the paper strength enhancing agent (2) used in the papermaking system is not particularly limited, but the bulking agent (1) is usually 0. About 01 to 5% by weight (preferably 0.01 to 2% by weight), and paper strength enhancer (2) is in the range of about 0.01 to 2% by weight (preferably 0.05 to 1% by weight). Is good.

In addition, the point at which the bulking agent (1) and the paper strength enhancer (2) are added to the paper stock (3) in the paper production line is not particularly limited. For example, the mixing chest, machine chest, raw material in the pulp preparation process It may be any point such as a transfer pump.

Moreover, about a paper machine, a form and form, such as an inlet, a wire part, a press part, a dryer part, a surface coating apparatus, a calendar part, are not specifically limited.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. “Parts” means parts by weight.

Production Example 1
A reaction vessel equipped with a stirrer, a dehydrating tube, a cooling tube, a thermometer, and a nitrogen gas introduction tube was charged with 1095.2 parts of stearic acid as the component (a2), heated and melted, and then triethylenetetramine 166 as the component (a1). .6 parts was added and the reaction system was heated to 180 ° C. in a nitrogen atmosphere. (Stearic acid is about 3.38 mol with respect to 1 mol of triethylenetetramine.) Next, the reaction system was maintained at 180 ° C. to 200 ° C. while removing the reaction product water, and generation of the reaction product water was not observed. After confirming this, heating was stopped, and the reaction system was cooled to room temperature to obtain a tertiary amide-containing compound. Next, 20 parts of isopropyl alcohol was added to 100 parts of the tertiary amide-containing compound, and the reaction system was maintained at 80 ° C to 90 ° C. Subsequently, 1247 parts of ion-exchanged water at 80 ° C. was added, and the reaction system was vigorously stirred to prepare a suspension solution. Subsequently, 52.7 parts of epichlorohydrin was added as the component (a3), and the reaction system was held at 80 ° C. to 85 ° C. for about 4 hours to obtain an aqueous dispersion of the component (A-1). In addition, the value of y / x of the component (A-1) was about 0.69, and the value of z / x was about 0.31. Next, 24.0 parts of a nonionic emulsifier (trade name: Epan 720, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to the same reaction system and stirred well, and the resulting solution was mixed with a high-pressure emulsifier (model 15MR, APV GAULIN). The mixture was further emulsified using a product (trade name) to obtain an aqueous dispersion (emulsion) of the component (A-1). The particle diameter of the emulsion was about 1.8 μm as a measured value using a laser diffraction particle size distribution measuring device (device name: SALD2000, manufactured by Shimadzu Corporation). (Hereinafter, the same applies to the particle diameter.) The emulsion is used as a bulking agent (1-1).

Production Example 2
In a reaction vessel similar to Production Example 1, 601.2 parts by weight of a mixture of stearic acid and palmitic acid (stearic acid / palmitic acid = 65/35 (weight ratio)) as component (a2) was charged and melted by heating. As the component a1), 207.2 parts by weight of tetraethylenepentamine was added. (The mixture is about 2.0 mol with respect to 1 mol of tetraethylenepentamine.) Then, the reaction system is heated to 180 ° C. under a nitrogen atmosphere, and then the reaction system is removed while removing water produced by the amidation reaction. Was kept at 180 ° C. to 200 ° C. for 3 hours, and when the reaction product water reached 39.4 parts by weight, the heating was stopped and the mixture was cooled. Next, 188.5 parts by weight of decanoic acid is further added as the component (a2) to the obtained product (about 1.0 mol with respect to 1 mol of tetraethylenepentamine), and water produced by the reaction is again added to the system. The reaction was carried out at 180 ° C. to 200 ° C. for 3 hours while removing the mixture to obtain a tertiary amide group-containing compound. Then, at 80 ° C., 30 parts by weight of isopropyl alcohol with respect to 100 parts by weight of the tertiary amide group-containing compound, and further 1002 parts by weight of ion-exchanged water at 80 ° C., nonionic emulsifier (trade name: Epan 720, 18.8 parts by weight of Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred well to obtain a suspended solution. Next, 202.5 parts by weight of epichlorohydrin is added to the solution as the component (a3), kept at 80 ° C. to 85 ° C. for about 4 hours, cooled to room temperature, and water of component (A-2) A dispersion (emulsion) was obtained. In addition, the value of y / x in the component (A-2) was 0.33, and the value of z / x was 0.67. The emulsion is used as a bulking agent (1-2).

Production Examples 3-5
The emulsions of the components (A-3) to (A-5) were prepared in the same manner as in Production Example 2, except that the species and amounts used of the components (a1) to (a3) were changed as shown in Table 1. Obtained. Each emulsion is used as a bulking agent (1-3) to (1-5) in order.

Production Example 6
In a reaction vessel similar to Production Example 1, 114.3 parts by weight of stearic acid was charged as component (a2), heated and melted, and then 166.6 parts by weight of triethylenetetramine was added as component (a1). The temperature was raised to 180 ° C. Next, the reaction is carried out at 180 ° C. to 200 ° C. while removing water produced by the reaction, and after confirming that no reaction product water is produced, the heating is stopped and cooled to obtain a tertiary amide group-containing compound. Got. Subsequently, 25 parts by weight of isopropyl alcohol was added to 100 parts by weight of the tertiary amide group-containing compound, and 1247 parts by weight of ion-exchanged water at 80 ° C. was added and stirred to obtain a suspension solution. Next, 52.7 parts by weight of epichlorohydrin as the component (a3) was added to the suspension, and the mixture was incubated at 80 ° C. to 85 ° C. for about 2 to 4 hours, and then a cationic emulsifier (trade name: Catiogen L, 14.0 parts by weight of Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred well, and an aqueous dispersion of component (A-6) was obtained using the high-pressure emulsifier. In addition, the value of y / x in the component (A-6) was 0.75, and the value of z / x was 0.25. The aqueous dispersion is used as a bulking agent (1-6).

Production Example 7
(A-7) An emulsion of component (A-7) was obtained in the same manner except that the types and amounts of components (a1) to (a3) were changed as shown in Table 1. The emulsion is used as a bulking agent (1-7).

In Table 1, each symbol is as follows.
(A1) component:
(A1-1) ... triethylenetetramine (a1-2) ... tetraethylenepentamine (a1-3) ... mixture of diethylenetriamine and triethylenetetramine (diethylenetriamine / triethylenetetramine = 1/3 (molar ratio))
(A1-4) ... Mixture of diethylenetriamine and tetraethylenepentamine (diethylenetriamine / tetraethylenepentamine = 1/5 (molar ratio))
(A2) component:
(A2-1) ... Stearic acid (a2-2) ... Mixture of stearic acid and palmitic acid (stearic acid / palmitic acid = 65/35 (weight ratio))
(A2-3) ... capric acid (a2-4) ... behenic acid (a2-5) ... palmitic acid (a2-6) ... oleic acid (a2-7) ... decanoic acid (a3) component:
(A3-1)… Epichlorohydrin

In Table 1, with respect to the component (a2), the “molar ratio” of “for primary amino group” reacts with the primary amino group in the component (a1) among all the components (a2) ( The molar ratio of component a2) and “molar ratio” of “for secondary amino group” react with the secondary amino group in component (a1) among all components (a2) (a2) Represents the molar ratio of the components.
In addition, the “molar ratio” of the component (a3) means that the secondary amino group of the component (a1) reacts with the remaining secondary amino group obtained by subtracting the component reacted with the component (a2) (a3 ) The molar ratio of components.

In Table 1, “Nonion” means a nonionic emulsifier (trade name: Epan 720, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and “Cation” means a cationic emulsifier (trade name: Katiogen L, Daiichi Kogyo Seiyaku). Means "Made by Co., Ltd." (In the case of using a cationic emulsifier, epichlorohydrin was added and added after incubation). Further, the “amount” of the emulsifier represents the part by weight used for 100 parts by weight of the compound to be emulsified in each production example. “High pressure” is the same method as the emulsification method described in Production Example 1 (using a high pressure emulsifier), and “inversion” is the same method as the emulsification method described in Production Example 2. Each means something.

  Table 2 shows the values of x, y, z, y / x and z / x of the components (A-1) to (A-7).

Production Example 8 (Preparation of paper strength enhancer)
A reactor equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube was charged with 82.6 parts of acrylamide, 7 parts of 62.5% sulfuric acid, 14.1 parts of dimethylaminoethyl methacrylate, and itaconic acid 2 0.5 part, 0.4 part of sodium methallylsulfonate, 0.6 part of dimethylacrylamide and 360 parts of ion-exchanged water were added, and oxygen in the reaction system was removed through nitrogen gas. The system was brought to 55 ° C., and 0.14 part of ammonium persulfate and 20 parts of ion-exchanged water were added as a polymerization initiator with stirring. After raising the temperature to 90 ° C., the temperature was kept for 30 minutes, and 0.2 part of ammonium persulfate and 10 parts of ion-exchanged water were added and kept for 1 hour. After completion of the polymerization, 200 parts of ion-exchanged water was added to obtain an aqueous solution of amphoteric polyacrylamide (hereinafter referred to as PAM-1) having a solid content of about 15.2% and a viscosity (25 ° C.) of 10,000 mPa · s. The aqueous solution is used as a paper strength enhancer (2-1). Table 3 shows the composition of PAM-1 and the ratio of its use, and Table 4 shows its physical properties. The weight average molecular weight of PAM-1 was determined under the following conditions (hereinafter determined in the same manner).

GPC body: Tosoh Co., Ltd. column: Tosoh Co., Ltd. guard column PWXL 1 and GMPWXL 2 (temperature 40 ° C.)
Eluent: 0.5 mol / l acetate buffer (0.5 mol / l acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.) + 0.5 mol / l sodium acetate (manufactured by Kishida Chemical Co., Ltd.), aqueous solution, pH about 4.2 )
Flow rate: 0.8 ml / min Detector: TDA MODEL301 (concentration detector and 90 ° light scattering detector and viscosity detector (temperature: 40 ° C.)) manufactured by Viscotech (GC-RALLS method)

Production Examples 9 to 11 (Preparation of paper strength enhancer)
In Production Example 8, aqueous solutions of PAM-2 to PAM-4 were obtained in the same manner except that the composition of amphoteric polyacrylamide and the use ratio thereof were changed as shown in Table 3. The aqueous solution is used as a paper strength enhancer (2-2) to a paper strength enhancer (2-4). Tables 3 and 4 show the compositions and physical properties of PAM-2 to PAM-4.

Production Example 12 (Preparation of paper strength enhancer)
350 parts of ion-exchanged water was charged into a reaction apparatus similar to Production Example 8 and a reaction apparatus equipped with two dropping funnels.
Then, in one dropping funnel, a monomer solution adjusted to pH 3 (179 parts of acrylamide, 11 parts of 62.5% sulfuric acid, 12.8 parts of 80% aqueous acrylic acid solution, 2.3 parts of sodium methallylsulfonate) Dimethylaminoethyl methacrylate, 22.4 parts, dimethylacrylamide 2.8 parts and ion-exchanged water 340 parts), and another dropping funnel containing a polymerization initiator solution (ammonium persulfate 0.3 parts, 100 parts of ion exchange water) was charged.
Next, after removing oxygen in the reaction system through a nitrogen gas introduction tube, the reaction system is heated to 90 ° C., and the monomer solution and the polymerization initiator solution are dropped into the reaction system from the dropping funnels over about 3 hours. did.
After completion of the dropping, a polymerization initiator solution (0.45 parts of ammonium persulfate, 10 parts of ion-exchanged water) was further charged from the other dropping funnel, and the polymerization reaction was completed by keeping the reaction system for 1 hour.
Next, by adding 80 parts of ion-exchanged water, an amphoteric polyacrylamide (hereinafter referred to as PAM-5) having a solid content concentration of about 20.2% by weight and a viscosity of 6000 mPa · s and a weight average molecular weight of 2,500,000 is obtained. An aqueous solution was obtained. The aqueous solution is used as a paper strength enhancer (2-5). Tables 3 and 4 show the composition and physical properties of PAM-5.

(Measurement of turbidity unit (NTU))
Water was added to the aqueous solution obtained in Production Example 8 to obtain a solution having a solid concentration of 1.0% by weight, and the turbidity unit thereof was an ANALITE turbidity meter “NEP-160 Portable Turbidity Meter” (manufactured by MacVan). Measured. The measured value is a relative value with respect to a standard substance (formazine standard solution (400 NTU), manufactured by Wako Pure Chemical Industries, Ltd.). Moreover, the turbidity unit was similarly measured about the aqueous solution obtained by manufacture examples 9-12. The results are shown in Table 4.

In Table 3,
AM: acrylamide DM: dimethylaminoethyl methacrylate DML: benzyl chloride quaternized product of dimethylaminoethyl methacrylate IA: itaconic acid AA: acrylic acid DMAA: N, N-dimethylacrylamide SMAS: sodium methallylsulfonate TAIC: triallyl isocyanurate MBAA: Methylenebisacrylamide

(Measurement of freeness value)
The test conditions for measuring the freeness value are as follows.
・ Testing equipment: “Canadian Freeness Tester No.2580-A” sold by Kumagai Rikyu Kogyo Co., Ltd.
・ Number of tests: 2 times ・ Paper water temperature: 20.0 ± 0.5 ° C.
・ Pulp concentration in paper: About 0.3%
Pulp type in paper stock: Pulp containing recycled pulp of high-quality waste paper and L-BKP beaten with Niagara Beater in a ratio of 7: 3 by weight.
・ Pulpability of pulp type in paper stock: Freeness value is 420ml
-Correction of actual measurement value: The actual measurement value is corrected according to the correction table of JIS P 8121, and the value obtained by dividing the correction value by the number of tests is taken as the measurement value.

Example 1
The pulp and water were mixed to prepare a pulp slurry containing 2% pulp concentration. Next, from the pulp slurry, a bulking agent (1-1) (0.8% by weight of pulp), a paper strength enhancer (2-1) (0.3% by weight of pulp), aluminum sulfate ( Pulp 0.7% by weight) and light calcium carbonate (20% by weight of pulp) were added and dispersed well under stirring to prepare a test sample. Subsequently, the freeness value was measured about the said test paper stock. The results are shown in Table 5.

Examples 2-9, Comparative Examples 1-8
The freeness values were measured in the same manner except that the bulking agent and paper strength enhancer were changed to those shown in Table 5. The results are shown in Table 5.

Comparative Example 9
The pulp and water were mixed to prepare a pulp slurry containing 2% pulp concentration. Next, an amount capable of producing a hand-made paper (sheet) of 80 g / m ² was collected from the pulp slurry, and a paper strength enhancer (2-1) (0.3% by weight of pulp), sulfuric acid was added thereto. Aluminum (0.7% by weight of pulp) and light calcium carbonate (20% by weight of pulp) were added and dispersed well under stirring to prepare a test sample. Subsequently, the freeness value was measured about the said test paper stock. The results are shown in Table 5.

Comparative Examples 10-13
In Comparative Example 9, the freeness value was measured in the same manner except that the paper strength enhancer was changed to that shown in Table 5.

Comparative Example 14
In Comparative Example 9, the bulking agent (1-1) (0.8% by weight of pulp) was used instead of the paper strength enhancer (2-1) (0.3% by weight of pulp). A test strip was prepared and the freeness value was measured in the same manner. The results are shown in Table 5.

Comparative Examples 15-20
In Comparative Example 14, the freeness value was measured in the same manner except that the bulking agent was changed to that shown in Table 5.

Reference Example The pulp and water were mixed to prepare a pulp slurry containing a pulp concentration of 2%. Next, an amount capable of producing a hand-made paper (sheet) of 80 g / m ² was collected from the pulp slurry, and aluminum sulfate (0.7% by weight with respect to pulp) and light calcium carbonate (with respect to 20% by weight of pulp) were collected. %) Was added and dispersed well with stirring to prepare a paper stock. Next, the freeness value was measured for the stock.

(Calculation of freeness difference)
In addition, the freeness difference (180 ml) of Example 1 is [freeness value (556 ml) of sample (including bulking agent and paper strength enhancer) in Example 1]] and [stock of Comparative Example 14 (the same bulking agent). And the freeness value (376 ml) of a paper strength enhancer that does not contain a paper strength enhancing agent)]. The difference in freeness between the other Examples and Comparative Examples 1 to 8 was determined in the same manner.

  Further, the freeness difference (191 ml) of Comparative Example 9 was determined as a difference between [freeness value of test paper test in Comparative Example 9 (578 ml)] and [freeness value of paper stock in Reference Example (387 ml)]. Value. The freeness difference of Comparative Examples 10 to 13 was determined in the same manner.

(Creation of bulky paper)
An amount capable of producing a hand-made paper (sheet) of 80 g / m ² was collected from the test paper in Example 1 and diluted with water to 1% by weight. Next, the diluted solution was subjected to paper making with a round paper machine (Tappi Standard Sheet Machine) to obtain a wet sheet. Then, the wet sheet was dehydrated with an automatic press machine (343 kPa) for 2 minutes and then dried with a rotary dryer (105 ° C., 1 minute) to obtain paper (A).

Next, the paper (A) was conditioned for 24 hours in a constant humidity chamber at a temperature of 23 ° C. and a humidity of 50% to obtain a test sheet. Thereafter, the test sheet was evaluated based on the following items.

(1) Density
The density of each test sheet was measured in accordance with JIS P 8118 (paper and paperboard-thickness and density test method). The results are shown in Table 5.
(2) Internal strength
The internal strength of each test sheet was measured according to the test method of JAPAN TAPPI paper pulp test method No.54-93. The results are shown in Table 5.

  Papers (a) to (e) were prepared in the same manner as described above for Examples 2 to 9, Comparative Examples 1 to 20, and the reference materials. Each paper was used as a test sheet in the same manner as described above, and evaluated in the same manner as described above. The results are shown in Table 5.

Claims (10)

Contains a tertiary amide group and a tertiary amino group obtained by reacting the secondary amino group-containing polyamine compound (a1), monocarboxylic acid compound (a2), and glycidyl group-containing compound (a3). Production of bulky paper for papermaking after adding bulking agent (1) containing fatty acid-modified amide resin (A) and paper strength enhancing agent (2) containing amphoteric polyacrylamide (B) to stock (3) In the method, the paper strength enhancer (2) contains [Canadian standard freeness of paper (3) containing paper strength enhancer (2) (ml)] and [paper strength enhancer (2). A method for producing a bulky paper, characterized in that it gives a value exceeding 50 ml as a difference from the Canadian standard freeness (ml) of the stock (3) not to be treated. (A1) formed from the number of secondary amino groups present in component x, and the secondary amino group present in component (a1) and the carboxyl group in component (a2) present in component (A) When the number of tertiary amide groups formed is y and the number of tertiary amino groups formed from the secondary amino group of component (a1) and the glycidyl group of component (a3) is z 2. The method according to claim 1, wherein the component (A) has a y / x value of 0.05 to 0.9 and a z / x value of 0.1 to 0.95. The component (a1) is represented by the general formula (I): H ₂ N — [— (CH ₂ ) _m —NH—] _n —H ( _where m is an integer of 1 to 3, and n is 2 to 6 The production method according to claim 1, which is a secondary amino group-containing polyamine compound represented by: The component (a2) is a monocarboxylic acid compound having a linear alkyl group having 2 to 36 carbon atoms or a linear alkenyl group having 2 to 36 carbon atoms. The manufacturing method as described. The manufacturing method in any one of Claims 1-4 whose said (a3) component is epihalohydrins. The manufacturing method in any one of Claims 1-5 whose said (A) component is a water dispersion. The manufacturing method in any one of Claims 1-6 whose turbidity unit (NTU) in the solution state of the solid content density | concentration of 1.0 weight% of the said paper strength enhancer (2) is 1000 or more and 4000 or less. The amphoteric polyacrylamide (B) comprises (meth) acrylamide (b1), cationic (meth) acrylic monomer (b2), anionic (meth) acrylic monomer (b3), N-substituted (meth) acrylamide (b4). ) And a (meth) allyl group-containing vinyl monomer (b5). The production method according to claim 1. The manufacturing method in any one of Claims 1-8 whose weight average molecular weights of the said amphoteric polyacrylamide (B) are 500,000 or more and 20 million or less. Bulky paper obtained by the production method according to claim 1.