JP2000178895A - Water-soluble functional compound, internal additive for papermaking comprising the compound, and internal paper - Google Patents

Abstract

(57) [abstract] (with correction) [Problem] Water resistance, water repellency, oil resistance, oil repellency, low friction,
Adding functions such as slipperiness and antistatic properties, and drying strength,
Provided are a functional compound capable of improving paper strength such as wet strength, an internal additive obtained by dissolving the compound in water, and an internal paper. The branched polyethyleneimine represented by the following general formula (1) has a structure in which a secondary amino group, or both a primary or secondary amino group and an epoxy-modified silicone at one end are grafted. Water soluble compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to water resistance, water repellency,
Involvement of compounds that provide functions such as oil resistance, oil repellency, low friction, slipperiness, and antistatic properties, and improve paper strength such as dry strength and wet strength. It relates to chemicals and their internal paper, and is suitably used for various packaging papers, construction papers, specifically for frozen foods, take-out food paper trays, paper cups, water-resistant cardboard, instant food paper containers, decorative paper, etc. Is done.

[0002]

2. Description of the Related Art In recent years, a technology shift from environmental load-type technologies to environmental protection has been taking place all over the world. As one of them, petroleum-derived plastic material, which is a finite resource, has attracted attention as a natural renewable resource and inexhaustible wood cellulose.For example, in the past, instead of containers using synthetic resins such as expanded polystyrene, paper containers Demand is increasing. In addition, the paper industry is actively recycling waste paper, and it can be converted to energy by thermal recycling without damaging the furnace from low combustion heat, together with other combustible waste. Therefore, the demand tends to increase more and more.

[0003] However, paper has inferior physical properties to plastic materials. In particular, paper has a problem of water resistance because water easily enters between fibers due to hydrogen bonding of cellulose fibers. Oil resistance is also low.

Conventionally, methods of imparting functions such as water resistance and oil resistance to paper include a method of adding (internally adding) a chemical imparting a function to a pulp raw material at the time of papermaking, and a method of papermaking. Paper is impregnated (externally added).

[0005] As a method for imparting high water resistance and oil resistance to paper, a plastic film such as PE (polyethylene) or PET (polyethylene terephthalate) is laminated, and an acrylic resin is used in the impregnation (external addition) method. However, in these cases, water or oil is immersed from the end face of the paper.

On the other hand, in the internal addition method, an anionic group (oxygen atom) of a cellulose molecule which is a constituent of pulp is used.
Since it is bonded by ionic adsorption, it effectively blocks the hydrophilic groups of cellulose molecules and can be easily modified over the whole layer. Does not decrease. However, as an essential condition of the internal additive, it must be soluble or dispersible in water,
It is also considered necessary to have an ionic polar group that can be ionically adsorbed on the anionic group to the cellulose molecule. When the polar group is the same anionic as the cellulose molecule, the polar group is adsorbed to the cellulose molecule by a metal salt such as aluminum sulfate, various cationic dispersants, or a high molecular weight flocculant. However, if metal salts such as aluminum sulfate are contained in the paper, the cellulose fibers are eroded over time, and other chemicals require time to study conditions and workability. It can be said that the internal additive contained is preferable because the control of the fixing amount is easy.

[0007] Several chemicals have been proposed as chemicals that satisfy such papermaking and papermaking conditions and provide water resistance, oil resistance, wet paper strength, and the like. However, it can be said that there are few internal additives having both water resistance (water repellency, wet paper strength enhancement) and oil resistance (oil repellency).

The internal additives that have been used for a long time include
Examples include sizing agents such as rosin and alkyl ketene dimer (AKD), dry paper strength agents such as cationic starch and polyacrylamide (PAM), and wet paper strength agents such as epoxidized polyamide polyamine and dialdehyde starch. The properties are not sufficient for various applications that are expected to expand in the future.

Recently, fluorine-based drugs and silicone-based drugs have been used. However, in order to make the drugs expensive or to solubilize water-insoluble drugs into water, Even if a hydrophilic group is introduced, there is no cationic group and a combination of various retention aids and fixing agents is required, or a surfactant is used without a hydrophilic group to disperse or emulsify in water. However, due to low adsorption to pulp and a low limit on the increase in fixing amount, high water resistance and oil resistance cannot be expected, chemicals flowed out into white water, and recovery operations from pollution control to wastewater treatment And equipment are often required.

For example, as a conventional technique using silicone or organopolysiloxane as a fiber treatment agent, an organopolysiloxane disclosed in JP-A-57-111354 and an organic heavy metal (Ti, Ge, Zr) ester are used as a nonionic resin. Fiber treatment agents which are dispersed in water with a water-based or cationic surfactant to impart water repellency, flexibility, wrinkle resistance and elongation recovery, and organopolysiloxanes having epoxy groups disclosed in JP-A-9-16333. A mixture of a siloxane and an organopolysiloxane having an amino group is self-emulsified or emulsified with an emulsifier to provide antistatic properties, hygroscopicity,
There is a fiber treatment agent that gives sweat and softness, but the applicability of a paper impregnating agent or surface coating agent is strong, and the internal additive is a dispersion method using a surfactant (or emulsifier). Since it is not solubilized or self-emulsified in water at the molecular level, no effective fixability to pulp fibers is considered. As a method of introducing a hydrophilic group into silicone,
There is a foam inhibitor (antifoaming agent) such as a polyoxyalkylene-modified silicone oil disclosed in JP-A-6-302, but it is not fixed to pulp fibers as an internal additive due to its nonionicity.

Polyethyleneimine (hereinafter referred to as PEI)
As a conventional technique using as a fiber treatment agent, there is a reaction in which a linear or branched PEI and an alkylene oxide are subjected to an addition reaction in JP-A-58-120879 and JP-A-59-173378, Using an amphoteric polymer compound obtained by saponifying an ethylenically unsaturated monomer with a Michael addition reaction, it can be used as a fiber treating agent to impart antistatic properties, Water-dispersible adhesive comprising a reaction product obtained by reacting a compound, JP-A-60-9995
No. 63-42997 by mixing the anionic latex of No. 1 with an aqueous solution of PEI or an aqueous solution of a polyvalent metal salt and imparting strength enhancement, water resistance, heat resistance, and flexibility formed as aggregated particles. An internal additive for imparting high dry strength by using a mixture of PEI and starch, and a paper-making sizing agent obtained by the addition reaction of PEI and an alkylene oxide disclosed in JP-A-63-282395. There is no description regarding a hybridized internal additive that improves water resistance, oil resistance, and the like.

JP-A-9-169817 discloses a silicon-containing water-soluble polymer in which a water-soluble polymer compound having a primary, secondary or tertiary amino group or ammonium group and a silicon-containing compound having an epoxy group are bonded. Although patents for polymer compounds have been published, the internal additives of the present invention are those in which the amino group-containing water-soluble polymer is specified as a branched polyethyleneimine, and the silicon-containing compound is specified as a single-terminal modified silicone polymer. The silicon-containing compound disclosed in Japanese Patent Application Laid-Open No. 9-16918 has a specific formula of the silicon-containing compound in the specification, which does not have a repeating SiO ₂ structure which is a structural feature of a silicone polymer, that is, a dialkyl polyorgano compound. It corresponds not to a siloxane structure but to various silane coupling agents, and no silicone polymer is described in the examples.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has water resistance, water repellency, oil resistance,
A functional compound capable of imparting functions such as oil repellency, low friction, slipperiness, and antistatic properties, and improving paper strength such as dry strength and wet strength, and a compound obtained by dissolving the compound in water. An object of the present invention is to provide an internally added drug and its internal paper. It has a strong cationic group, so it has high ionic adsorption to pulp fiber, easy control of fixing amount, can be dissolved in water at the molecular level, and has excellent water resistance and oil resistance Can provide internal chemicals and internal papers for paper packaging paper, construction paper, specifically for frozen food, take-out food paper trays, paper cups, waterproof cardboard, instant food paper containers, decorative paper, etc. It is preferably used.

[0014]

Means for Solving the Problems The present inventors have studied to solve the above-mentioned problems, and as a result, they have been used as a wet paper strength enhancer overseas and mainly as a coagulation treatment agent for wastewater in Japan. Branched polyethylene imine and water repellent,
Silicone having an epoxy group at one end, which has high oil repellency, slipperiness, flexibility and antistatic property, is used as primary and secondary amino groups in polyethyleneimine and epoxy in one-terminal epoxy-modified silicone. The group is subjected to a ring-opening addition reaction,
It could be solubilized in water at the molecular level. In addition, because of the high cationicity of the branched polyethyleneimine structure, the amount of fixation to pulp fibers during papermaking or papermaking was easy to control, and high water resistance could be imparted.

[0015] The invention according to claim 1 is characterized in that a secondary amino group of a branched polyethyleneimine represented by the following general formula (1):
Alternatively, it is a water-soluble functional compound having water repellency in which both primary and secondary amino groups and one-terminal modified silicone are grafted.

Embedded image Formula 1 (where x, y, and p are integers of 1 or more, n is an integer of 1 or more, m is an integer of 0 or more and 2 or less, R ₁ represents hydrogen or alkyl, and R ₂ has 1 carbon atom. The above alkyl group is represented by R
R ₁ may combine with the carbon atom in ₂ to form a saturated carbocyclic ring. R ₃ and R ₄ are the same or different and each represent an alkyl group having 1 or more carbon atoms, and Z represents a direct bond or an oxygen atom. )

According to a second aspect of the present invention, there is provided the water-soluble functional compound according to the first aspect, wherein the secondary amino group of the branched polyethyleneimine represented by the following general formula 2, or the primary and secondary amino groups are provided. An amino group and an epoxy group of a one-terminal epoxy-modified silicone represented by the following general formula 3 undergo a ring-opening addition reaction, and are obtained by grafting a silicone represented by the following general formula 4. I do.

Embedded image General formula 2 (where x, y, and p are integers of 1 or more)

Embedded image Formula 3 (wherein, n is an integer of 1 or more, R ₁ represents hydrogen or an alkyl group, R ₂ represents an alkyl group having 1 or more carbon atoms,
The carbon atom in R ₂ and R ₁ may combine to form a saturated carbocyclic ring. R ₃ and R ₄ are the same or different and each have 1 carbon atom.
The above alkyl groups are shown, and Z represents a direct bond or an oxygen atom. )

Embedded image General formula 4 (wherein, x, y, and p are integers of 1 or more, n is an integer of 1 or more, m is an integer of 0 or more, 2 or less, R ₁ represents hydrogen or alkyl, and R ₂ represents 1 carbon atom. The above alkyl group is represented by R
R ₁ may combine with the carbon atom in ₂ to form a saturated carbocyclic ring. R ₃ and R ₄ are the same or different and represent an alkyl group having 1 or more carbon atoms, and Z represents a direct bond or an oxygen atom. )

According to a third aspect of the present invention, there is provided the water-soluble functional compound according to the second aspect, wherein the mixing ratio of the branched polyethyleneimine of the general formula (2) and the epoxy-modified silicone at one end of the general formula (3) is branched. The mole number of the active hydrogen and the mole number of the epoxy group of the primary amino group and the secondary amino group in the linear polyethyleneimine are in the range of 1: 0.5 to 1.0.

According to a fourth aspect of the present invention, there is provided an internal additive for papermaking, wherein the water-soluble functional compound according to the first to third aspects is dissolved in water.

According to a fifth aspect of the present invention, there is provided an internally added paper comprising the water-soluble functional compound by internally adding the internal additive for papermaking according to the fourth aspect.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The addition reactant of the branched polyethyleneimine (hereinafter referred to as BPEI) and the one-terminal epoxy-modified silicone of the present invention can be easily dissolved in water. Just by adding (internally adding) to pulp slurry, water resistance (low water absorption, high wet / dry
), Oil resistance, etc., can be produced.

The structure of the internal additive according to the present invention will be described. The BPEI structure is an adsorption site to pulp fiber at the time of internal addition, and exhibits the effect of improving paper strength such as dry / wet strength. The silicone structure grafted to the silicone provides water repellency, oil repellency, low abrasion, slipperiness, antistatic property, flexibility, and the like, which are characteristics of silicone. In particular, regarding the water repellency, the BPEI blocks the anionic hydrophilic oxygen atoms on the pulp fiber by the electric adsorption force, and the grafted silicone molecular chains exhibit water repellency at the site. Works very effectively.

PEI, which is a raw material of the internally added drug of the present invention,
Branched PEI is specified. The reason is that linear PEI (LPET) has high crystallinity, so it is hardly soluble in organic solvents and water, and its synthesis method is more complicated and costly than BPEI. It is mentioned. Other polyamines capable of undergoing an addition reaction with an epoxy group include poly (allylamine) (PAAm) and derivatives thereof, and poly (vinylamine) (P
VAm) and its derivatives, but with a structure having only a primary amino group, poor cationicity, low reactivity with an epoxy group, and a basic catalyst required for addition reaction. It is. That is, BPEI, which is a raw material of the internal medicine of the present invention, has a secondary amino group and a tertiary amino group in addition to the primary amino group. It reacts easily under the catalyst, and it is considered that the addition reaction of the primary amino group with the epoxy group also easily occurs due to the catalytic effect of the tertiary amino group.

Further, BP, which is a raw material of the internal additive of the present invention,
Since EI reacts with an epoxy group, BPEI which does not contain water is preferable in consideration of reaction conditions. BPEI
At present, ring-opening polymerization of ethyleneimine obtained by dehydration ring closure in the presence of monoethanolamine as a catalyst is industrially performed. Therefore, when the molecular weight of the synthesized BPEI increases, dehydration becomes difficult due to the hydration effect of the high cationicity of BPEI. With commercially available BPEI,
Those containing almost no water have a molecular weight of about 300 to 10,0.
The synthesis of the internal additive of the present invention was mainly performed within this molecular weight range. However, from a foreign-affiliated company, a product having a molecular weight of about 5,000,000 is also commercially available and contains water. Since the reaction of the BPEI with the epoxy group is also possible in the reaction system, the molecular weight of the BPEI is not particularly limited with respect to the internal additive of the present invention. Those that do not are suitable.

One-terminal epoxy-modified silicone, which is another raw material of the internal additive of the present invention, has one epoxy group at the terminal of its molecular structure, and therefore has a primary or secondary amino group of BPEI. To cause grafting.
The average molecular weight of the one-terminal epoxy-modified silicone used as a raw material of the internal additive of the present invention is usually about 500 to 10,000, and the standard is preferably 1,000 to 5,000. If the average molecular weight of the one-terminal epoxy-modified silicone is too small, the silicone properties will not be fully exhibited,
On the other hand, if the average molecular weight is too large, the solubility in water becomes low, and further, the fixability of the internal additive of the present invention hybridized with BPEI to the pulp fiber by the BPEI site decreases.

Further, as a method for synthesizing the internal additive of the present invention, it is preferable to dissolve the internal additive in an organic solvent in order to reduce the high viscosity of the raw material BPEI and to make it easy to mix with the reaction reagent. The organic solvent to be used is not particularly limited as long as it dissolves BPEI and one-terminal epoxy-modified silicone. However, when it is used as an internal additive, it is preferable to consider a wastewater treatment. However, because BPEI is highly cationic,
It can be said that water, alcohols, and acetones are generally soluble solvents. In the synthesis of the internal additive of the present invention, BPEI was dissolved in isopropanol, which is a tertiary alcohol, which hardly reacts with an epoxy group, and mixed with one-terminal epoxy-modified silicone, thereby causing a reaction without a catalyst.

Regarding the reaction conditions, the primary and secondary amino groups of PEI and the epoxy group of the modified silicone are more likely to react when heated than when the reaction is performed at room temperature. Also, PEI
The reaction molar ratio between the epoxy-modified silicone and one-terminal epoxy is PE
From the amine value of I and the composition ratio of primary, secondary, and tertiary amino groups, the molar concentration of active hydrogen of primary and secondary amino groups contained in 1 g of PEI was determined. It is preferable to react one end epoxy-modified silicone.
This is because unreacted modified silicone is insoluble in water and causes phase separation in water. Even if it is internally added, it does not settle on pulp fibers and flows out into white water, thus requiring drainage treatment.

The pulp used in the present invention may be coniferous or hardwood, or even vegetable pulp such as straw.
Bleached or unbleached sulphite pulp or kraft pulp, groundwood pulp, waste paper, thermomechanical pulp (TMP) or chemical thermomechanical pulp (CTMP) may be used alone or in combination of two or more.

The functional paper of the present invention is prepared by internally adding the internal additive of the present invention to a pulp slurry, followed by papermaking / papermaking, pressing, and drying with a Yankee dryer. The basis weight of the paper is not particularly limited, but is 30 to 200.
from g / m ² of the paper, it believed possible with 600 g / m ² of cardboard.

[0029]

Next, the present invention will be described more specifically based on examples.

<Production Example 1> BPEI (Nippon Shokubai Co., Ltd.)
Manufactured by Epomin SP-200, molecular weight: about 10.000).
V. = 20wt% isopropanol solution was prepared, and Epomin SP-200
The molar concentration of primary and secondary amino groups per 1 g of the above was determined, and a 20 wt% solution of epomin SP-200 in isopropanol was used in 39.4.
0 g (net: 7.88 g) [Active hydrogen molar concentration of primary and secondary amines; 1.0 mmol] and one-terminal epoxy-modified silicone (manufactured by Chisso Corporation, trade name: FM-0511, average molecular weight: 1.000) ) Was mixed with about 1 mmol (about 1.0 mmol) having substantially the same molar concentration, and the mixture was stirred and reacted in an oil bath at about 80 ° C. for 10 minutes. The reaction product was diluted with tap water (about 847.6 g) to obtain a pale white transparent aqueous solution of the internal additive of the present invention (NV = 1.0 wt%).

<Production Example 2> Approximately 80 ° C. under the reaction conditions of Production Example 1.
The procedure of Production Example 1 was repeated except that the place of stirring for 10 minutes in the oil bath was changed to stirring at room temperature for 10 minutes. NV = 1.0wt%
The aqueous solution was clear.

<Comparative Production Example 1> To confirm the BPEI hybridization effect of the present invention, alkyleneamines (H ₂ N- (CH ₂ CH ₂ NH) _n similar to the molecular structure of BPEI were used.
As -H), triethylenetetramine (n = 3) was used instead of PEI. 0.029 g of triethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd.) (1 mmol in the active hydrogen molar concentration of primary and secondary amines), epoxy-modified silicone at one end (manufactured by Chisso Corporation, trade name: FM-0511, average) (Molecular weight; 1.000) was mixed with 1 g (1 mmol) of the same molar concentration, and the mixture was stirred and reacted in an oil bath at about 80 ° C. for 10 minutes. The reaction product is added to tap water (about 10
When diluted with 0 g), they were aggregated and could not be dispersed or dissolved in water.

<Comparative Production Example 2> Pentaethylenehexamine (n = 5, manufactured by Tokyo Chemical Industry Co., Ltd.) as an alkyleneamine (H ₂ N— (CH ₂ CH ₂ NH) _n —H) of Comparative Production Example-1
0.033 g (1 mmo in active hydrogen molarity of primary and secondary amines)
l) In the same manner as in Comparative Production Example 1 except for changing to l),
It was agglomerated and it was impossible to disperse or dissolve in water as in Comparative Production Example 1. As mentioned above,
The hybridized product of alkyleneamines with a low molecular weight and one-terminal epoxy-modified silicone having a similar structure to BPEI, which is the raw material of the internal additive of the present invention, cannot be dispersed or dissolved in water and aggregates in water. Therefore, the significance of specifying the amine group-containing water-soluble polymer as the BPEI / silicone hybrid internalizing agent of the present invention as BPEI was confirmed.

<Comparative Production Example 3> A commercially available fluorine-based water-repellent and oil-resistant internal additive AG-530 (Asahi Glass Co., Ltd.) having a track record of being widely used from food wrapping paper to industrial wrapping paper
N .; V. = 15 wt%) and mixed with 140 g of water and stirred. V. = 1 wt% of a transparent aqueous solution was prepared. Since AG-530 is anionic, S-45 (manufactured by Asahi Glass Co., Ltd .; NV = 1) is a special cationic fixing agent.
5 wt%) and mixed with 140 g of water and stirred. V.
= 1 wt% of a transparent aqueous solution was prepared.

Next, the internal paper with the internal additive of the present invention will be described. The raw pulp is deflocculated from hardwood kraft pulp (LBKP) papermaking material in accordance with JIS-P8209 "Handbook preparation method for pulp test".
According to the Canadian standard freeness test method based on "Pulp freeness test method", a pulp slurry having a beating degree of 350 cc was diluted with water to prepare a 0.4% by weight pulp slurry. Then, internal papers with the PEI / silicone hybridized internal chemicals of the present invention of Examples 1 and 2 shown below and internal chemicals with the internal chemicals of Comparative Examples 1 to 4 were prepared. An example will be described below.

<Example 1> A 1 wt% aqueous solution of the internal additive of the present invention prepared in Production Example 1 was added to a 0.4 wt% pulp slurry prepared in the application example at a weight ratio of absolute dry pulp in terms of solid content. After mixing 2 wt%, 4 wt%, 10 wt%, and 20 wt%, and stirring for 5 minutes, a standard handmade square paper machine was used to make an internally-added paper having a basis weight of about 60 g / m ² and a dewatering press (3.5 kgf / cm ² ) For 5 minutes and dried with a Yankee dryer (surface temperature = about 120 ° C).

<Example 2> Internal additives prepared in Production Example 2
A 1 wt% aqueous solution was mixed with the 0.4 wt% pulp slurry prepared in the application example in a weight ratio of absolute dry pulp of 10 wt% in terms of solid content, stirred for 5 minutes, and then weighed using a standard handmade square paper machine.
60g / m2 of internal paper is made and dewatered (3.5kgf / c
m ² ) for 5 minutes, and use a Yankee dryer (surface temperature =
(About 120 ° C.).

<Comparative Example 1> As Comparative Example 1, non-added paper without any internal addition was produced with the same basis weight.

<Comparative Example 2> As Comparative Example 2, BPEI
(Nippon Shokubai Co., Ltd., trade name; Epomin SP-200, molecular weight: about 10,000) NV = 20 wt% isopropanol solution was converted to 0.4 wt% pulp slurry prepared in the application example in terms of solid content. 10 wt% was mixed in a weight ratio to absolute dry pulp, and an internal paper was prepared in the same manner as in the following examples.

Comparative Example 3 A 1 wt% aqueous solution of the commercially available fluorine-based water-repellent oil-resistant internal additive AG-530 prepared in Comparative Production Example 1 and a 1 wt% aqueous solution of the cationic fixing agent S-45 were mixed with the technical data of the manufacturer. Was prepared by the paper making procedure based on the above. In other words, 0.4 wt% of the pulp slurry prepared in the application example is added to the absolute dry pulp weight ratio of 0.3 wt% in terms of solid content.
S-45 aqueous solution (N.V. = 1.0 wt.
%), And after stirring (about 1.5 minutes), an aqueous solution of AG-530 (N.V. = 1.0% by weight) was added so that the weight ratio to absolute dry pulp was 0.5% by weight. The mixture was stirred for about 1.5 minutes, and an internal paper was prepared in the same manner as in the following examples.

Comparative Example 4 In Comparative Production Example 3, AG-53
The same operation as in Comparative Example 3 was carried out, except that the internal addition amount of the 0 aqueous solution (N.V. = 1.0 wt%) was changed to 1.0 wt% based on the absolute dry pulp weight ratio, to prepare an internal paper. Also, the internal addition amount in this example is
According to the manufacturer's technical data, it is considered to be general.

Prior to each physical property evaluation, JIS standard
-Based on P8111, humidity was controlled for 24 hours or more in a 20 ° C-65% RH environment.

<Test Example 1> The water absorption was measured for the purpose of evaluating the water resistance of each of the internally added papers. The measuring method was as follows: each internal paper was cut into a shape of 50 × 50 mm, and was immersed in distilled water for 1 hour. Calculated. Table 1 shows the results.
Shown in

[0044]

(Equation 1)

[0045]

[Table 1]

From the results shown in Table 1, the BPEI of the present invention was obtained.
As the internal additive amount increased, the water absorption decreased, and the silicone / hybridized internal additive showed high water repellency. This indicates that the BPEI structural site in the internal additive of the present invention has an effect of improving the fixing amount. Also, in Examples 1 and 2 where 10 wt% was added internally with respect to the absolute dry pulp weight ratio, Example 1 had lower water absorption and higher water repellency.
It was found that in the reaction between I and the epoxy-modified silicone with one terminal, the more completely hybridized by heating, the higher the water repellency. Further, from the measurement results of Comparative Example 3 and Comparative Example 4 in which a commercially available fluorine-based water-repellent and oil-resistant internal additive AG-530 was added, Comparative Example 4 in which 1.0 wt% was added to absolutely dry pulp was compared. Although the internal additive of the present invention had low water absorption and paper strength with an increase in the amount of the additive, the commercially available fluorine-based additive used in Comparative Examples 3 and 4 had a low water absorption. The following shows that the additive cannot improve the paper strength.

<Test Example-2> Next, each of the internal papers was subjected to JIS-P8
Based on 113, Autograph (manufactured by Shimadzu Corporation,
Using a Shimadzu Autograph AG-500 A), dry (20 ° C-65% RH) and wet (1
(Water immersion time), and the wet rupture strength / dry rupture strength (wet / dry) was calculated from the following formula 2 to evaluate the water resistance. Table 2 shows the evaluation results.

[0048]

(Equation 2)

[0049]

[Table 2]

From the results shown in Table 2, the BPEI of the present invention was obtained.
The wet / dry and wet strength of the internal additive / silicone hybridizing agent increased with the increase of the internal additive amount, and showed high water resistance. The improvement in wet / dry was mainly due to the improvement in wet strength, and it was found that the internal additive of the present invention had a high effect as a wet enhancer. This is evident from the fact that the wet / dry of the internal paper reinforced with the BPEI alone of Comparative Example 2 is higher than the wet / dry. Further, the improvement in wet / dry with the increase in the amount of internal addition indicates that the BPEI structural site in the internal additive of the present invention has an effect of improving the fixing amount. Example 1 and Example 2 in which 10 wt% was added internally based on the absolute dry pulp weight ratio.
In Example 1, since wet / dry was higher and water resistance was higher, it was found that in the reaction between BPEI and one-terminal epoxy-modified silicone, the more completely hybridized by heating, the higher the water resistance. . Furthermore, from the measurement results of Comparative Examples 3 and 4 in which the commercially available fluorine internal additive AG-530 was internally added, if the internal addition amount was increased, the wet / dry was improved, but this was because the dry strength was significantly reduced. , The wet strength is slightly reduced. Therefore, commercially available fluorine additives include:
No effect of imparting both low water absorption and paper strength was observed.

<Test Example 3> Next, the BPEI /
In order to measure the fixability of the silicone hybrid internal additive to paper, qualitative analysis of Si (silicone) in each internal additive paper was performed. The detailed measurement method is shown below.

Each internal paper sample was pulverized with a freeze grinder (Sample Mill SK-500, manufactured by Kyoritsu Riko Co., Ltd.).
The grinding time was 10 minutes.

Next, a pellet forming machine (MAEKAWA.TESTING.M
ACHINE.MFG.CO., LTD), put 1.0g of each powdered internal paper sample into the sample, compress (20tf -5 minutes), and pellet (Φ =
40mm). After molding, in order to remove moisture in the pellets, the pellets were allowed to stand in a desiccator for 24 hours or more to prepare a sample for X-ray fluorescence analysis. A qualitative analysis of Si (silicone) was performed on the pellets of each of the prepared internal papers using a fluorescent X-ray apparatus (Rigaku system 3270). The measurement wavelength is S
i-K α. Table 3 shows the measurement results.

[0054]

[Table 3]

From the results shown in Table 3, the BPEI of the present invention was obtained.
It was found from the amount of increase in X-ray intensity that the amount of Si fixation of the / silicone hybridized internal additive increased almost in proportion to the increase of the internal additive amount. And, in Example 1 and Example 2 in which 10 wt% was added internally with respect to the absolute dry pulp weight ratio, Example 1 had higher X-ray intensity.
In the reaction between the epoxy-modified silicone and the one-terminal epoxy-modified silicone, it was confirmed that the more completely hybridized by heating, the higher the fixing property.

[0056]

As described above, the functional compound of the present invention and its internal additive are branched polyethyleneimine (BPEI), which is used for a wet paper strength enhancer or a highly cationic fixing agent, and the like. One-terminal epoxy-modified silicone with properties such as low abrasion, slip, antistatic and flexibility
It is a water-soluble polymer obtained by a graft reaction by the addition reaction between primary and secondary amino groups of PEI and epoxy groups of modified silicone. The functional compound of the present invention is a water-soluble polymer, and when used as an internal additive for papermaking prepared by dissolving the compound in water, particularly with respect to water repellency, BPEI takes on an anionic property on pulp fibers. It functions very effectively because it blocks the hydrophilic oxygen atoms by the electric adsorption force and the grafted silicone molecular chains exhibit water repellency at the site. Furthermore, in addition to its water repellent effect, BP
EI has the advantage of increasing the wet paper strength enhancing effect. In addition, the BPEI structural portion of the BPEI / silicone hybrid internal additive of the present invention has the property of a highly cationic fixing agent, so that it has good fixability to pulp fibers during papermaking and controls the fixing amount. It is possible to provide an internal additive that is easy and does not leak into white water.

Therefore, the internal paper with the BPEI / silicone hybrid internalizing agent of the present invention imparts properties such as water resistance and oil resistance over the entire paper layer, and is resistant to water and oil immersion from the surface and the end face of the paper. It has strong resistance to various kinds of wrapping paper,
It can be used for food wrapping paper, building paper, specifically for frozen food or take-out food paper trays, paper cups, water-resistant cardboard, instant food paper containers, decorative paper, and the like.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Atsuko Harasawa 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd. F-term (reference) 4J035 BA02 CA07M CA07U CA071 CA081 CA11M CA111 CA18M CA181 GA06 GB01 GB05 LA07 LB07 LB08 LB14 LB20 4J038 DL141 NA03 NA07 NA10 NA11 NA20 PB04 PC10 4L055 AG77 AG86 AG87 AG92 AH16 AH23 AH24 AH27 EA29 FA11 FA19 GA05 GA06 GA30 GA47 GA48

Claims (5)

[Claims] 1. A branched polyethyleneimine represented by the following general formula 1 having a structure in which a secondary amino group, or both primary and secondary amino groups, and an epoxy-modified silicone at one end are grafted. A water-soluble functional compound characterized by the following. Embedded image Formula 1 (where x, y, and p are integers of 1 or more, n is an integer of 1 or more, m is an integer of 0 or more and 2 or less, R ₁ represents hydrogen or alkyl, and R ₂ has 1 carbon atom. The above alkyl group is represented by R
R ₁ may combine with the carbon atom in ₂ to form a saturated carbocyclic ring. R ₃ and R ₄ are the same or different and each represent an alkyl group having 1 or more carbon atoms, and Z represents a direct bond or an oxygen atom. ) 2. A secondary amino group, or a primary and secondary amino group of a branched polyethyleneimine represented by the following general formula 2, and an epoxy group of a one-terminal epoxy-modified silicone represented by the following general formula 3: The water-soluble functional compound according to claim 1, wherein the compound is obtained by performing a ring-opening addition reaction to graft a silicone represented by the following general formula 4. Embedded image General formula 2 (where x, y, and p are integers of 1 or more) Formula 3 (wherein, n is an integer of 1 or more, R ₁ represents hydrogen or an alkyl group, R ₂ represents an alkyl group having 1 or more carbon atoms,
The carbon atom in R ₂ and R ₁ may combine to form a saturated carbocyclic ring. R ₃ and R ₄ are the same or different and each have 1 carbon atom.
The above alkyl groups are shown, and Z represents a direct bond or an oxygen atom. ) General formula 4 (wherein, x, y, and p are integers of 1 or more, n is an integer of 1 or more, m is an integer of 0 or more, 2 or less, R ₁ represents hydrogen or alkyl, and R ₂ represents 1 carbon atom. The above alkyl group is represented by R
R ₁ may combine with the carbon atom in ₂ to form a saturated carbocyclic ring. R ₃ and R ₄ are the same or different and represent an alkyl group having 1 or more carbon atoms, and Z represents a direct bond or an oxygen atom. ) 3. The mixing ratio of the branched polyethyleneimine of the general formula 2 and the one-terminal epoxy-modified silicone of the general formula 3 is determined based on the active hydrogen of the primary amino group and the secondary amino group in the branched polyethyleneimine. 3. The water-soluble functional compound according to claim 1, wherein the number of moles and the number of moles of the epoxy group are in the range of 1: 0.5 to 1.0. 4. An internal additive for papermaking, wherein the water-soluble functional compound according to claim 1 is dissolved in water. 5. An internal paper, wherein the internal additive for papermaking according to claim 4 is internally added to contain the water-soluble functional compound.