JP2016153541A - Liquid oily chemical-impregnated paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid oily chemical-impregnated paper that has high permeation speed of a liquid oily chemical and has strength.SOLUTION: The liquid oily chemical-impregnated paper is a paper produced by paper-making a raw material fiber composed mainly of pulp consisting of at least either one of wood pulp and non-wood pulp and contains an additive including a cationic surfactant having a heterocyclic structure and a 11-35C aliphatic hydrocarbon group. Preferably, the impregnated paper has a thickness of 0.3 mm to 1.5 mm and a density of 0.3 g/cmto 0.55 g/cmeach as stipulated in JIS P 8118.SELECTED DRAWING: None

Description

  The present invention relates to a liquid oil-based chemical impregnated paper for use in impregnation with liquid oil-based chemicals such as insect repellents.

  Various insect repellent products are used to repel clothing, human bodies, foods and the like from pests. In recent years, the variety of insect repellent products has been diversified, and various products corresponding to the needs of consumers are widely available on the market. For example, in outdoor activities such as hiking and camping, products for the purpose of preventing insect bites are used. In addition, products for protecting stored clothes from pests are used in closets, chests and the like. Thus, insect repellent products have become a necessity in modern life.

There are various types of insect repellent products, but among the insect repellent products used in closets, chests and the like, matte paper type products are the main products.
As a mat paper type insect repellent product, there is one in which an impregnated paper mainly composed of pulp is provided as a base material (mat), and the base material is impregnated with an insect repellent (see, for example, Patent Document 1). Such an insect repellent product usually has an insect repellent effect since the insect repellent chemical impregnated in the base material naturally volatilizes from the point of opening the bag body etc. in which the insect repellent product is packaged. Lasts from half a year to one year. In addition, there is a product having an indicator function in which characters such as “end” appear on the surface of the impregnated paper when the insect repellent effect is lost and the user is notified of the end of the period of use.

  Empentrin, which is a pyrethroid liquid oily chemical, is mainly used as an insect repellent chemical to be impregnated. Empentrin has low odor and is extremely safe for the human body, but it volatilizes at room temperature and spreads evenly to every corner of the space. continue.

JP 2003-250414 A

Such mat paper type insect repellent products are usually manufactured through an impregnation step in which a liquid oily chemical such as empentrin is dropped and impregnated on the impregnated paper. In the impregnation step, liquid oily chemicals are required to rapidly penetrate into the impregnated paper in a short time from the viewpoint of the productivity of the insect repellent product.
In view of this, studies have been made to increase the penetration speed of liquid oily chemicals into impregnated paper by reducing the beating degree of pulp used for the production of impregnated paper and reducing the density of the impregnated paper to be produced. In addition, when calendering is not performed or when calendering is performed, the pressure is lowered to reduce the density of the impregnated paper to be manufactured, thereby increasing the penetration speed of the liquid oily chemical into the impregnated paper. Consideration has also been made.

  However, impregnated paper obtained from pulp having a low beating degree has low wet paper strength due to weak entanglement between pulp fibers and is likely to break during paper making. In addition, when calendering is not performed or when the calendering pressure is lowered, the penetration speed of the liquid oily chemical is improved but insufficient.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a liquid oil chemical-impregnated paper having high liquid oil chemical penetration speed and high strength.

The present invention has the following configuration.
[1] Cations having a heterocyclic structure and an aliphatic hydrocarbon group having 11 to 35 carbon atoms, a paper on which a raw material fiber mainly composed of at least one of wood pulp and non-wood pulp is made. Liquid oil-based chemical-impregnated paper containing an additive containing a reactive surfactant.
[2] a defined thickness in JIS P 8118 is 0.3 mm to 1.5 mm, and density as specified in JIS P 8118 is ^{0.3g / cm 3 ~0.55g / cm 3} , [1] Liquid oil-based chemical-impregnated paper.
[3] The liquid oil-based chemical-impregnated paper according to [1] or [2], wherein the content of the additive is 0.2 parts by mass or more with respect to 100 parts by mass of the raw fiber.
[4] The liquid oil chemical impregnated paper of [1] to [3], wherein the additive contains acetate ions.
[5] The liquid oily chemical-impregnated paper of [1] to [4], wherein the heterocyclic structure has at least one nitrogen atom.

  According to the present invention, it is possible to provide a liquid oil chemical-impregnated paper having a high penetration speed of liquid oil chemical and high strength, and a method for producing the same.

Hereinafter, the present invention will be described in detail.
The liquid oily chemical impregnated paper of the present invention is a paper for impregnating a liquid oily chemical.

[Liquid oily chemicals]
Examples of the liquid oily chemicals include insect repellents used for repelling clothes, human bodies, foods and the like from pests, aromatic chemicals that impart a scent to living spaces, and deodorizing chemicals.
As the insect repellent, for example, a liquid containing one or more pyrethroid compounds such as empentrin, transfluthrin, profluthrin, teraleslin, and metfurthrin can be used, and this can be impregnated.
Examples of aromatic chemicals include liquids containing various fruit and plant extracts and essential oils, and one or more of these can be impregnated.
Examples of the deodorizing chemical include cyclodextrin derivatives that include and deodorize odor components, and liquids that contain betaine compounds that react with odor components to deodorize, and one or more of these can be impregnated.

[Liquid oil-impregnated paper]
(pulp)
The liquid oil-based chemical-impregnated paper of the present invention (hereinafter also referred to as “impregnated paper”) is a paper on which raw fibers mainly composed of pulp composed of at least one of wood pulp and non-wood pulp are made.
In addition, a main component means the component contained exceeding 50 mass% in 100 mass% of impregnated paper.

Wood pulp includes wood pulp that is generally used for papermaking. Specifically, chemical pulp such as kraft pulp (KP), sulfite pulp (SP) and soda pulp (AP); semi-chemical pulp such as semichemical pulp (SCP) and chemi-grandwood pulp (CGP); groundwood pulp (GP), thermomechanical pulp (TMP, BCTMP), refiner grandwood pulp (RGP) and other mechanical pulp; waste paper pulp; and the like.
Kraft pulp includes softwood pulp (NBKP) and hardwood pulp (LBKP).
Wood pulp may be used alone or in combination of two or more.

Non-wood pulp is a fiber collected from the skin, stem, leaf, and leaf sheath of a plant. Specific examples include cotton linters, straw / esparto, rags (cotton, linen, hemp, ramie, etc.), Manila hemp such as abaca, bamboo / gabas, ganpi / mitsu, and pulp from mulberry / mulberry. .
Among non-wood pulps, cotton linters are the most water absorbent and are suitable for use in impregnated paper. However, when cotton linter is used, the texture of the impregnated paper may be lowered. Therefore, when used, it is preferably used in the range of 80% by mass or less in the raw fiber (100% by mass). It is preferable to use in the range of 80% by mass.
A non-wood pulp may be used individually by 1 type, or may use 2 or more types together.

  Wood pulp and non-wood pulp may be used alone or in combination, but from the viewpoint of economy, wood pulp is 20 to 100% by mass in raw fiber (100% by mass). And it is preferable that non-wood pulp is 0-80 mass%.

(Synthetic fiber)
The raw material fibers may contain fibers other than pulp such as synthetic fibers as long as the main component is pulp composed of at least one of wood pulp and non-wood pulp.
The synthetic fiber is not particularly limited, and examples thereof include vinylon fiber, polyester fiber, polypropylene fiber, acrylic fiber, nylon fiber, aramid fiber, and polyethylene fiber. When synthetic fibers are used, the density of the impregnated paper is lowered and tends to be advantageous in improving the penetration speed of the liquid oily chemical, but the texture of the impregnated paper tends to be deteriorated. Moreover, it is more expensive than wood pulp and non-wood pulp. Further, when the impregnated paper is colored by the method of adding the colorant during the paper making of the impregnated paper (internal coloration), if the impregnated paper contains synthetic fibers, the synthetic fibers are not colored by the colorant. May not be colored. Considering these balances, when using synthetic fiber, it is preferably used in the range of 30% by mass or less in the raw fiber (100% by mass), and in the range of 10-30% by mass. preferable.
A synthetic fiber may be used individually by 1 type, or may use 2 or more types together.

  As the synthetic fiber, for example, a fiber having a fiber diameter of 5 to 25 μm and a fiber length of 1 to 15 mm can be used.

(Additive)
The impregnated paper of the present invention contains an additive including a cationic surfactant having a heterocyclic structure and an aliphatic hydrocarbon group having 11 to 35 carbon atoms. When such a cationic surfactant is contained in the impregnated paper, it is considered that the density of the impregnated paper is reduced, the surface of the raw fiber is modified, and the liquid oil chemical penetration speed into the impregnated paper is excellent. .
As will be described in detail later, the additive may be included in the impregnated paper by blending it into the papermaking slurry at the time of making the impregnated paper, or it may be diluted with water as necessary and attached to the paper after papermaking. It may be included in the impregnated paper.

The heterocyclic structure possessed by the cationic surfactant is preferably a heterocyclic structure having at least one nitrogen atom and exhibiting cationic properties.
Examples of the structure having one nitrogen atom include a pyridine ring structure and a salt-type pyridinium ring structure in which the pyridine ring structure is neutralized with an acid.
Examples of the structure having two nitrogen atoms include an imidazoline ring structure and a salt (neutralized product) obtained by neutralizing the imidazoline ring structure with an acid.
Examples of the structure having three or more nitrogen atoms include a triazole ring and a salt (neutralized product) obtained by neutralizing the triazole ring structure with an acid.
Among these, when an additive containing a heterocyclic structure having two nitrogen atoms, that is, a cationic surfactant having at least one of an imidazoline ring structure and a salt in which the imidazoline ring structure is neutralized with an acid, is used. Impregnated paper that is superior in the penetration speed of liquid oily chemicals is likely to be obtained.

A cationic surfactant having an imidazoline ring structure as a heterocyclic structure and having an aliphatic hydrocarbon group having 11 to 35 carbon atoms (hereinafter also referred to as “cationic surfactant (α)”), For example, it can be produced by a method having the following step (a) or a method having the following step (b), but a method having the following step (b) is preferred from the viewpoint of production efficiency.
(A) A step of reacting a fatty acid having 12 to 36 carbon atoms with ethylene urea.
(B) A step of reacting a fatty acid having 12 to 36 carbon atoms with polyethylene polyamine to obtain an amide compound and dehydrating the amide compound.

  In the step (a), a fatty acid having 12 to 36 carbon atoms and ethylene urea are mixed and heated to 200 ° C. or higher. Thereby, dehydration and decarboxylation occur, and a cationic surfactant (α) having an aliphatic hydrocarbon group having 11 to 35 carbon atoms and an imidazoline ring structure is generated. The molar ratio of the fatty acid to be reacted and ethylene urea is preferably 1: 1.

The step (b) is represented by, for example, the following formulas (1) to (2). In the formula, R is an aliphatic hydrocarbon group having 11 to 35 carbon atoms. Further, the following formula shows a case where diethylenetriamine is used as the polyethylene polyamine.
First, as shown in the following formula (1), diethylenetriamine and a fatty acid having 12 to 36 carbon atoms react at a molar ratio of 1: 2 to obtain a fatty acid amide of diethylenetriamine, which is an amide compound.

  Next, by heating the obtained amide compound, that is, fatty acid amide of diethylenetriamine, a dehydration reaction represented by the following formula (2) occurs, and an imidazoline ring structure and an aliphatic hydrocarbon group having 11 to 35 carbon atoms are formed. The cationic surfactant (α) is produced.

  The cationic surfactant (α) thus produced is neutralized with an acid to form a salt, which will be described later.

Examples of the fatty acid having 12 to 36 carbon atoms used in each of the above steps include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid, lactelic acid, Oleic acid, ricinoleic acid, linoleic acid, linolenic acid, erucic acid, 10-hydroxystearic acid, isotridecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, dimer acid obtained by dimerizing unsaturated fatty acid, tall oil fatty acid, beef tallow Examples include fatty acids, coconut fatty acids, castor fatty acids, and hardened fatty acids thereof.
A fatty acid may be used individually by 1 type, or may use 2 or more types together.

Of the fatty acids having 12 to 36 carbon atoms, unsaturated fatty acids having 12 to 22 carbon atoms are preferably used. When an additive containing a cationic surfactant obtained using an unsaturated fatty acid having 12 or more carbon atoms is added, the density of the resulting impregnated paper is more likely to be reduced, and in terms of the surface state of the raw fiber In addition, the penetration speed of the liquid oily chemical into the impregnated paper tends to be more excellent. Cationic surfactants obtained using unsaturated fatty acids having 22 or less carbon atoms have good water dispersibility or emulsification properties. Therefore, when the additive containing the cationic surfactant is contained in the impregnated paper, the additive is easily mixed with the papermaking slurry, or the additive is diluted with water and easily attached to the paper after papermaking. Thereby, the effect of increasing the penetration speed of the liquid oily chemical can be sufficiently imparted to the impregnated paper.
As the unsaturated fatty acid having 12 to 22 carbon atoms, an unsaturated fatty acid having 16 to 20 carbon atoms is preferable, and at least one of oleic acid and linoleic acid is particularly preferable.

Examples of the polyethylene polyamine used in the step (b) include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
Polyethylene polyamines may be used alone or in combination of two or more.

  Among polyethylene polyamines, it is preferable to use at least one of ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, and it is more preferable to use at least one of diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. More preferably, diethylenetriamine is used. Thereby, the dispersibility or emulsification property of the obtained cationic surfactant in water is more excellent. Therefore, when the additive containing the cationic surfactant is contained in the impregnated paper, the additive is easily mixed with the papermaking slurry, or the additive is diluted with water and easily attached to the paper after papermaking. Thereby, the effect of increasing the penetration speed of the liquid oily chemical can be sufficiently imparted to the impregnated paper.

There is no restriction | limiting in particular in the reaction conditions of the process of said (b).
In the reaction (see the above formula (1)) in which a fatty acid having 12 to 36 carbon atoms is reacted with polyethylene polyamine to obtain an amide compound (see the above formula (1)), for example, fatty acid and polyethylene polyamine are charged in a reaction vessel at a molar ratio of 2: 1. It heats to 160-170 degreeC and performs dehydration reaction. Thereby, an amide compound (a bis-fatty acid amide of polyethylene polyamine) can be obtained.
In the reaction for dehydrating the obtained amide compound (polyethylenepolyamine bis-fatty acid amide) (see the above formula (2)), the amide compound is heated to, for example, 200 to 250 ° C. As a result, dehydration and cyclization reactions occur, and a cationic surfactant compound (α) having an imidazoline ring structure can be produced.

As the cationic surfactant contained in the additive contained in the impregnated paper of the present invention, in addition to the cationic surfactant (α), a salt obtained by neutralizing the cationic surfactant (α) with an acid may be used. A cationic surfactant (β); a cationic surfactant (γ) composed of a urea derivative obtained by reacting a cationic surfactant (α) with urea to remove ammonia; a cationic surfactant (γ A cationic surfactant (δ), which is a salt neutralized with an acid.
The cationic surfactant (γ) can be obtained by adding urea to the cationic surfactant (α) and heating to 160 to 200 ° C. When an additive containing a cationic surfactant (γ) is used, the whiteness of the resulting impregnated paper tends to be improved.
The additive may include two or more of these cationic surfactants.

Of these cationic surfactants, the cationic surfactant (α) and the cationic surfactant (γ) may be difficult to dissolve, disperse or emulsify in water as they are. . In that case, it is preferable to use the additive containing these dissolved or dispersed or emulsified in an aqueous acid solution.
On the other hand, the cationic surfactants (β) and (δ) that are salts are easily dissolved, dispersed, or emulsified in water.

  There is no particular limitation on the acid used for the above-described neutralization and preparation of the aqueous acid solution, and examples thereof include organic acids such as formic acid, acetic acid, butyric acid and lactic acid, and inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid. Of these, acetic acid is preferred from the viewpoint of ease of handling and safety. The additive containing the salt-type cationic surfactant (β) neutralized with acetic acid will contain acetate ions.

The additive added to the impregnated paper may contain components such as water other than the unreacted raw material and the cationic surfactant generated by the reaction, in addition to the cationic surfactant.
For example, the reaction product obtained after the reaction of the above formula (2) includes an unreacted amide compound (a bis-fatty acid amide of polyethylene polyamine) in addition to the generated cationic surfactant (α), depending on the reaction conditions. ) May remain. As the additive, a cationic surfactant (α) isolated from the reaction product may be used, or a reaction product containing an unreacted raw material amide compound or the like may be used as it is.
When the reaction product is used as an additive as it is, the reaction product is obtained by converting 30% by mole or more of the amide compound obtained by the reaction between a fatty acid and polyethylene polyamine into a cationic surfactant (α). It is preferable that 50 mol% or more is converted to a cationic surfactant (α), more preferably 80 mol% or more is converted to a cationic surfactant (α). More preferably. Such reaction products tend to become semi-solid or liquefied. Further, it can be dissolved, dispersed or emulsified in water as it is.

  In addition, as described above, the cationic surfactant (α) is neutralized with an acid, or deammonia reaction with urea or subsequent neutralization is performed, so that the cationic surfactant (β ) To (δ) are prepared together with the cationic surfactant (α) without isolating the cationic surfactant (α) from the reaction product obtained after the reaction of the above formula (2). You may perform these reaction with respect to the above-mentioned reaction product containing the amide compound etc. of reaction. And the mixture obtained by this reaction may be used as an additive as it is. Also in this case, the above-mentioned reaction product containing an unreacted amide compound and the like together with the cationic surfactant (α) has 30% by mole or more of the amide compound obtained by the reaction of fatty acid and polyethylene polyamine. It is preferably one that has been converted to a surfactant (α), more preferably 50 mol% or more is converted to a cationic surfactant (α), and 80 mol% or more is a cationic interface. More preferably, it is converted into the activator (α).

  As explained above, cationic surfactants (α) to (δ) can be used as the cationic surfactant contained in the additive. Further, the reaction product obtained after the reaction described with the above formula (2) can be used as an additive as it is, and the reaction product is neutralized with acid, deammonia reaction with urea, Can also be used as an additive as it is, a mixture obtained by subsequent neutralization and the like.

  As a specific embodiment of the most preferable additive, a cationic surfactant (α) obtained by dehydrating an amide compound obtained by the reaction of an unsaturated fatty acid having 12 to 22 carbon atoms and polyethylene polyamine is used. Reaction product containing (cationic interface having 30% by mole or more, preferably 50% by mole or more, more preferably 80% by mole or more of the amide compound having an imidazoline ring structure and an aliphatic hydrocarbon group having 11 to 21 carbon atoms) Examples of the salt obtained by neutralizing with an acid to the activator (α). The salt contains a cationic surfactant (β).

The additive is preferably a liquid or a viscous liquid. For example, the viscosity at 20 ° C. (viscosity measured with a Brookfield viscometer) is preferably 400 to 700 mPa · s.
Although there is no restriction | limiting in particular in pH of an additive, When it is set as 1 mass% aqueous solution, it is preferable that it is 4.0-5.0.

  The content of the additive contained in the impregnated paper is preferably 0.2 parts by mass or more, preferably 0.5 parts by mass or more, and 1.0 parts by mass or more with respect to 100 parts by mass of the raw fiber. It is more preferable that When the content of the additive is not less than the above lower limit, the penetration speed of the liquid oily chemical into the impregnated paper is more excellent. The upper limit of the content of the additive contained in the impregnated paper is not particularly limited, but the permeation speed is not further improved even if added excessively. In addition, the strength of the paper may be reduced. From these points, 10 parts by mass or less is preferable, 5 parts by mass or less is preferable, and 1.5 parts by mass or less is more preferable with respect to 100 parts by mass of the raw fiber.

The content of the additive referred to here is the content of the nonvolatile content of the additive actually contained in the impregnated paper. For example, water contained in the additive produced by the method described above is not contained in the impregnated paper because it evaporates (volatilizes) in the impregnated paper production process.
The nonvolatile content is a solid component that remains when held at 105 ° C. and 1013 hPa for 1 hour.

(Other ingredients)
The impregnated paper of the present invention may contain known paper-making chemicals such as a retention agent (for example, a sulfuric acid band).

(Thickness, density and basis weight of impregnated paper)
The impregnated paper of the present invention preferably has a thickness specified by JIS P 8118 of 0.3 mm to 1.5 mm, more preferably 0.3 mm to 1.2 mm, and 0.4 mm to 0.00 mm. More preferably, it is 7 mm. Further, impregnated paper of the present invention is preferably a density as specified in JIS P 8118 is ^{0.30g / cm 3 ~0.55g / cm 3} , 0.30g / cm 3 ~0.45g / cm 3 more ^preferably, it is more preferably ^{0.30g / cm 3 ~0.40g / cm 3} .
If the thickness of the impregnated paper is not less than the lower limit of the above range, a necessary and sufficient amount of liquid oily chemical can be impregnated, and if it is not more than the upper limit of the above range, an excessive amount of liquid oily chemical will not be impregnated. .
If the density of the impregnated paper is not less than the lower limit of the above range, sufficient paper tensile strength for production and practical use can be obtained, and if it is not more than the upper limit of the above range, the penetration speed of the liquid oily chemical can be further increased. Excellent.
Moreover, although the basic weight prescribed | regulated to JISP8124 of an impregnation paper is decided by thickness and a density, 90-825 g / m < ² > is preferable, 90-540 g / m < ² > is more preferable, 120-280 g / m < ² > Further preferred.
If the basis weight of the impregnated paper is equal to or higher than the lower limit of the above range, it is difficult to receive production restrictions such as paper making speed, and if it is equal to or lower than the upper limit of the above range, an excessive amount of liquid oily chemical can be impregnated. Absent.

(Manufacturing method of impregnated paper)
The impregnated paper of the present invention can be produced, for example, by the following methods (c) to (e).
(C) A method of making a papermaking slurry containing raw material fibers and an additive (internal addition method).
(D) A method in which a raw material fiber and a papermaking slurry containing no additive are made, an additive-containing liquid containing the additive is applied to the obtained paper, and the additive is adhered (external addition method).
(E) A method of making a papermaking slurry containing raw material fibers and an additive, applying an additive-containing liquid containing the additive to the obtained paper, and attaching the additive (internal addition method and external addition method) Method that uses the same method).

The slurry for papermaking is a pulp slurry beaten by a known method (slurry made of pulp and water consisting of at least one of wood pulp and non-wood pulp), and synthetic fibers used as necessary, and if necessary Can be prepared by adding and mixing known papermaking chemicals used (eg, retention agents such as sulfuric acid bands).
When employing the above methods (c) and (e), an additive is also added to the pulp slurry. In this case, the additive may be added as it is, or may be added after being dissolved or dispersed or emulsified in advance in water or an aqueous acid solution.

  The beating degree of the pulp slurry is not particularly limited, but if the beating degree is low, the wet paper strength of the resulting impregnated paper is low, and the paper tends to break during paper making. From this point, it is preferable that the pulp slurry be beaten so that the Canadian standard freeness (freeness) is 600 mL or less. The Canadian standard freeness is preferably 450 mL or more from the viewpoint of easily obtaining an impregnated paper having a density capable of obtaining a desired amount of impregnation.

The content of the raw fiber (solid content) in 100% by mass of the papermaking slurry is preferably 0.5 to 1.0% by mass.
In the above methods (c) and (e), the amount of the additive added to the papermaking slurry is adjusted so that the additive content in the resulting impregnated paper is within a suitable range.
The amount of the papermaking chemical can be adjusted as appropriate. For example, in the case of aluminum sulfate (sulfuric acid band) used as a retention agent, a range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the raw fiber is preferable.

For papermaking, known papermaking machines such as a circular netting machine, a long netting machine, and an inclined type papermaking machine can be used.
The paper machine is, for example, a wire part that obtains wet paper from a paper slurry, a press part that presses and dehydrates the obtained wet paper, a dryer part that dries the wet paper that has passed through the press part, and paper after drying And a calendar part that performs calendar processing as needed. By performing the calendar treatment, the surface smoothness of the resulting impregnated paper is excellent. For example, when characters such as “end” are printed as an indicator function on the surface of the impregnated paper, the ink inking property is excellent.

  In the above methods (d) and (e), as a method for applying the additive-containing liquid to the paper after paper making, a method of applying the additive-containing liquid to the paper, a method of spraying the additive-containing liquid on the paper, addition And a method of immersing paper in the agent-containing liquid.

When the additive-containing liquid is applied to paper, for example, a coater part including a rod coater is provided between the dryer part and the calender part of the paper machine, and the additive-containing liquid is provided on at least one surface of the paper. The method of apply | coating is mentioned.
In the case of spraying the additive-containing liquid onto the paper, there is a method in which a spray part is provided between the dryer part and the calendar part and the additive-containing liquid is sprayed on at least one surface of the paper.
When the paper is immersed in the additive-containing liquid, it is preferable that a liquid tank containing the additive-containing liquid is provided between the dryer part and the calendar part, and the liquid tank is passed through the paper.
After making it adhere in this way, it dries suitably.

  As the additive-containing liquid, a liquid obtained by appropriately diluting the additive with water or an aqueous acid solution can be used. The concentration of the additive in the additive-containing liquid is preferably 10 to 90% by mass as the concentration of the nonvolatile content.

As described above, the impregnated paper of the present invention contains an additive including a cationic surfactant having a heterocyclic structure and an aliphatic hydrocarbon group having 11 to 35 carbon atoms. Therefore, the penetration speed of liquid oily chemicals such as insect repellents and aromatic chemicals is excellent. Therefore, in manufacturing the insect repellent product, the time required for the impregnation step of dripping and impregnating the liquid oily chemical onto the impregnated paper can be shortened, and the insect repellent product can be manufactured with excellent productivity.
Moreover, if the said additive is used, since the impregnation speed of the liquid oily chemical | medical agent to an impregnation paper will increase, it will not be necessary to use the pulp with a low beating degree in order to manufacture an impregnation paper with a high impregnation speed. Therefore, it is possible to obtain an impregnated paper having a sufficient strength by suppressing paper breakage during paper making, which is likely to occur when pulp having a low beating degree is used.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited by these.
In the following examples, when “parts” and “%” are simply used, they mean “parts by mass” and “% by mass”, respectively.

Example 1
A pulp slurry containing 30 parts of NBKP and 70 parts of LBKP as a solid content was mixed and beaten by the JIS P 8221 beater method so that the Canadian standard freeness was 550 mL. That is, NBKP and LBKP were used as raw fiber.
Then, 1 part of a sulfuric acid band was added as a solid content to 100 parts of the solid content of the raw fiber, and 0.2 part of an additive was added as a nonvolatile content, and mixed well.
The content of raw material fibers (solid content) in 100% by mass of the papermaking slurry thus obtained was 3.5% by mass.
Then, a papermaking slurry was made using a square sheet machine.
The obtained wet paper was dried and calendered with a calender linear pressure of 1 kg / cm (= 9.8 N / cm) to obtain a handmade sheet.
Using the handsheet as impregnated paper, the following measurements and tests were performed.
The results are shown in Table 1.

The additive used in Example 1 is an amide compound obtained by the reaction of tall oil fatty acid (mainly oleic acid and linoleic acid) and polyethylene polyamine according to the above formulas (1) and (2). A reaction product containing a cationic surfactant (α) obtained by dehydration reaction of amide compound with an imidazoline ring structure and an aliphatic hydrocarbon group having 11 to 21 carbon atoms. It is a salt (neutralized product) obtained by further neutralizing with acetic acid with respect to the cationic surfactant (α) that has been converted.
The nonvolatile content is about 90% by mass.

<Measurement and test>
(1) Basis weight Calculated according to JIS P 8124.
(2) Thickness and density Thickness and density were determined according to JIS P8118. The pressure between the pressure surfaces of the micrometer at the time of thickness measurement was 100 kPa ± 10 kPa.
(3) Drug impregnation speed test The impregnated paper is cut into a size of 30 mm × 40 mm and used as a sample. Using a burette at the center of the surface of the sample, 100 mg of liquid pendant empentrin (CAS No. 54406-48-3 manufactured by Fluka) is dropped. The state where the water film was not stretched on the surface of the impregnated paper (by visual confirmation) was set as the end point, and the time from the dropping point to the end point (chemical solution penetration time) was measured.
(4) Ink fillability test Impregnated paper is cut into a size of 200 mm × 20 mm and used as a sample. The sample was printed with red ink using an RI tester (printability tester), and the ink inking property was visually evaluated. “Yes” when it is confirmed that the ink has adhered to the entire surface of the sample, “△” when the color tone is slightly shaded or where the ink is slightly faded, and the ink is not faded. When the printed part was visually recognized, it was evaluated as “×”.

(Examples 2 to 4)
A handsheet was produced in the same manner as in Example 1 except that the additive amount was changed to the amount shown in Table 1 in terms of non-volatile content, and this was used as impregnated paper. went.
The results are shown in Table 1.

(Example 5)
As a raw material fiber, a handsheet was produced in the same manner as in Example 2 except that NBKP and cotton linter were used at the blending ratio shown in Table 1 and calendering was not performed. Measurements and tests similar to those in Example 1 were performed.
The results are shown in Table 1.

(Example 6)
As the raw material fibers, NBKP, cotton linters and polyester fibers (fiber diameter: 12 μm, fiber length: 10 mm) were used in the blending ratio shown in Table 1, and the same as in Example 2 except that the calendar treatment was not performed. A handsheet was produced, and this was used as impregnated paper, and the same measurements and tests as in Example 1 were performed.
The results are shown in Table 1.

(Example 7)
A handmade sheet was produced in the same manner as in Example 1 except that the calendar treatment was not performed, and this was used as impregnated paper, and the same measurements and tests as in Example 1 were performed.
The results are shown in Table 1.

(Example 8)
A handsheet was obtained in the same manner as in Example 1 except that no additive was added to the papermaking slurry and no calendering was performed.
On the other hand, the same additive as that used in Example 1 was added to water to prepare an additive-containing liquid, and this liquid was hand-coated and coated on one side of the sheet with a rod coater.
The coating amount of the additive was made to be 1.5 parts with respect to 100 parts of the raw fiber as a non-volatile content.
After drying, a calendar treatment was performed at a calendar linear pressure of 1 kg / cm (= 9.8 N / cm).
The obtained handsheet was used as impregnated paper, and the same measurements and tests as in Example 1 were performed.
The results are shown in Table 1.

(Comparative Example 1)
A handsheet was produced in the same manner as in Example 1 except that no additive was used, and this was used as impregnated paper. The same measurements and tests as in Example 1 were performed.
The results are shown in Table 1.

(Comparative Example 2)
A handsheet was produced in the same manner as in Example 1 except that no additive was used and no calendar treatment was performed, and this was used as impregnated paper. The same measurements and tests as in Example 1 were performed.
The results are shown in Table 1.

(Comparative Example 3)
A handsheet was produced in the same manner as in Example 5 except that no additive was used, and this was used as impregnated paper. The same measurements and tests as in Example 1 were performed.
The results are shown in Table 1.

(Comparative Example 4)
A handsheet was produced in the same manner as in Example 6 except that no additive was used, and this was used as impregnated paper. The same measurements and tests as in Example 1 were performed.
The results are shown in Table 1.

From the comparison between Examples 1 to 4 and Comparative Example 1, it was found that the chemical solution penetration time was shortened with the addition of the additive, and the penetration speed of the liquid oily chemical was improved. Moreover, it was found from the comparison between Example 2 and Example 8 that the effect of improving the penetration speed can be obtained without depending on the additive addition method (internal addition method, external addition method).
From the comparison between Example 5 and Comparative Example 3 and the comparison between Example 6 and Comparative Example 4, even when the raw material fiber contains cotton linter or polyester fiber, the addition of the additive shortens the chemical solution penetration time, and the liquid state It was found that the penetration speed of oily chemicals was improved.
From the comparison between Example 2 and Example 7, it was found that when the calendar process was not performed, the ink inking property was reduced, but the chemical solution penetration time was slightly shortened and the penetration speed was slightly improved. .
However, from the results of Comparative Example 1 and Comparative Example 2, it is clear that the chemical solution penetration time is slightly shortened by not performing the calender treatment, but sufficient penetration speed cannot be obtained without the addition of additives. It was.

From a comparison between Example 5 and Example 6 and Example 7, it was found that when cotton linter or polyester fiber was used instead of LBKP, the chemical solution penetration time was shortened and the penetration rate of the liquid oily chemical was improved. .
However, from the results of Comparative Example 2, Comparative Example 3 and Comparative Example 4, when cotton linter or polyester fiber is used instead of LBKP, the chemical solution penetration time is shortened, but sufficient without the addition of additives. It became clear that the penetration speed could not be obtained.

Claims (5)

A paper on which raw fibers mainly composed of at least one of wood pulp and non-wood pulp are made,
A liquid oil-based chemical-impregnated paper containing an additive containing a cationic surfactant having a heterocyclic structure and an aliphatic hydrocarbon group having 11 to 35 carbon atoms. A defined thickness in JIS P 8118 is 0.3 mm to 1.5 mm, and density as specified in JIS P 8118 is ^{0.3g / cm 3 ~0.55g / cm 3} , claim 1 Liquid oily chemical impregnated paper as described in 1.   The liquid oil-based chemical-impregnated paper according to claim 1 or 2, wherein a content of the additive is 0.2 parts by mass or more with respect to 100 parts by mass of the raw fiber.   The liquid oil-based chemical-impregnated paper according to any one of claims 1 to 3, wherein the additive contains acetate ions.   The liquid oily chemical impregnated paper according to any one of claims 1 to 4, wherein the heterocyclic structure has at least one nitrogen atom.