TW202132416A - Water absorption-preventing agent and paperboard - Google Patents

Abstract

This water absorption-preventing agent comprises an amino-modified silicone emulsion composition containing: (A) 100 parts by mass of an amino-modified silicone having a viscosity of 800-100,000 mPa.s at 25 DEG C, an amino group equivalent of 500-20,000 g/mol, and an octamethylcyclotetrasiloxane content of 1 mass% or less; (B) 5-100 parts by mass of one or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants (note that polyoxyethylenenonylphenyl ethers and polyoxyethyleneoctylphenyl ethers are excluded); and (C) 10-2,000 parts by mass of water. The amino-modified silicone emulsion composition has an excellent water absorption prevention-imparting effect and good dilution stability, and contains a reduced amount of environmental impact substances.

Description

Anti-absorbent and cardboard

The present invention relates to an anti-absorbent made of amine modified silicone emulsion and the paperboard using the same. In detail, it relates to a water-absorbing agent with high effect as a water-repellent agent for paper and low environmental load.

In the past, plasterboard was used extensively as a building material. As we all know, gypsum board is a plate-shaped body that firmly combines and fixes multi-layer papermaking paperboard on both sides of the gypsum board after hydration and hardening. The paperboard used in this case requires the paperboard itself to be strong, have moisture resistance, and have small dimensional changes when wet. Various characteristics such as air permeability as large as possible.

Among these properties, moisture resistance and dimensional stability when wet are particularly important. In the past, based on the purpose of improving moisture resistance and suppressing dimensional changes when wet, treatments to add water absorption resistance to the surface of the cardboard have been carried out. As a treatment method for this situation, the addition of silicone resin treatment will less damage the air permeability and is widely implemented. As the silicone resin for this treatment, various modified silicone oils represented by dimethyl silicone oil have been proposed to be effective, and most of these emulsions are suitable as surface treatment agents.

However, for example, the method of using epoxy modified silicone oil disclosed in U.S. Patent No. 3,389,042 cannot obtain sufficient anti-water absorption effect. The case of using mercapto-containing silicone oil as the main agent disclosed in Japanese Patent Publication No. 56-47994 is used. , Although high water absorption resistance can be obtained, the special odor of sulfhydryl is extremely strong, so it has the disadvantage of poor working environment.

In Japanese Patent Publication No. 08-025255, it is proposed to obtain a water-repellent technology by using amine groups with specific viscosity and amine equivalent to modify silica. However, polyoxyethylene nonylphenol ether is used as an emulsifier, and octamethylcyclotetrasiloxane is used as a diluent. Polyoxyethylene nonylphenol ether is an example of a high concern substance in the EU REACH specification. In addition, in recent years, cyclic low-molecular-weight silicones (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane) have become considered as environmentally hazardous substances. With strong regulations in various countries, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane are required to be suppressed products. Based on the above background, it is required to have both high water absorption resistance and low environmental load. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] US Patent No. 3,389,042 [Patent Document 2] Japanese Patent Publication No. 56-47994 [Patent Document 3] Japanese Patent Publication No. 08-025255

[The problem to be solved by the invention]

In view of the above-mentioned problems of the past technology, the present invention aims to provide a water-absorbing agent with excellent anti-water absorption effect, good dilution stability, and a reduced content of environmental load substances. In addition, "good dilution stability" refers to the stability after storage by diluting the anti-absorbent with a certain amount of water as described in the evaluation method of the examples described later. [Means to solve the problem]

In order to achieve the above-mentioned object, the inventors actively reviewed the results and found that the amino-modified silicone emulsion composition containing the following components (A) to (C) can impart excellent water absorption resistance and at the same time have good dilution stability. And can reduce the content of environmental load substances, thus completing the present invention.

[式中，R¹ 相互獨立為碳數1~20之非取代一價烴基，R² 相互獨立為以下述式(2)表示之基，

(R⁴ 及R⁵ 相互獨立為碳數1~6之二價有機基，p為0或1) R³ 相互獨立為選自R¹ 及R² 之選項中之基或選自-OH、-OCH₃ 及-OC₂ H₅ 之基，a、b、c、d及e係滿足2≦a≦10，10≦b≦1,000，0≦c≦50，0≦d≦5，0≦e≦5之範圍之數，但c=0時R³ 為R² ]， (B)選自非離子界面活性劑、陰離子界面活性劑、陽離子界面活性劑及兩離子界面活性劑之1種以上的界面活性劑(但，聚氧乙烯壬基苯基醚及聚氧乙烯辛基苯基醚除外)：5~100質量份 (C)水：10~2,000質量份。 2. 如1之抗吸水劑，其中(A)成分中之十甲基環五矽氧烷之含量為1質量%以下。 3. 如1或2之抗吸水劑，其中(A)成分中之十二甲基環六矽氧烷之含量為1質量%以下。 4. 如1至3中任一項之抗吸水劑，其中(B)成分係包含非離子界面活性劑之界面活性劑。 5. 如4之抗吸水劑，其中(B)非離子界面活性劑係HLB值15.0以下之非離子系界面活性劑。 6.如1至5中任一項之抗吸水劑，其中(B)成分係不含陽離子界面活性劑之界面活性劑。 7.如1至6中任一項之抗吸水劑，其係紙用抗吸水劑。 8.一種經抗吸水處理之紙板，係於紙板基材之至少一面塗佈如1~6中任一項之抗吸水劑後，進行加熱處理而成。 [發明效果]Therefore, the present invention provides the following water-absorbing agent and paperboard. 1. An anti-absorbent agent, which is made of an amine-modified silicone emulsion composition, which contains: (A) The following average composition formula (1) is expressed, and the viscosity at 25°C is 800~100,000 mPa・S, amine modified silica with an amine equivalent of 500~20,000g/mol and an octamethylcyclotetrasiloxane content of 1% by mass or less: 100 parts by mass,

[In the formula, R ^{1 is} mutually independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^{2 is} mutually independently a group represented by the following formula (2),

(R ⁴ and R ⁵ are independently a divalent organic group with 1 to 6 carbon atoms, and p is 0 or 1) R ^{3 is} independently a group selected from ^{the options of R 1} and R ² or selected from -OH,- The base of OCH ₃ and -OC ₂ H ₅ , a, b, c, d and e satisfy 2≦a≦10, 10≦b≦1,000, 0≦c≦50, 0≦d≦5, 0≦e≦ A number in the range of 5, but when c=0, R ³ is R ² ], (B) One or more interface selected from non-ionic surfactants, anionic surfactants, cationic surfactants and two-ionic surfactants Active agent (except polyoxyethylene nonyl phenyl ether and polyoxyethylene octyl phenyl ether): 5 to 100 parts by mass (C) Water: 10 to 2,000 parts by mass. 2. The anti-absorbent agent of 1, wherein the content of decamethylcyclopentasiloxane in component (A) is less than 1% by mass. 3. The water-absorbing agent of 1 or 2, wherein the content of dodecamethylcyclosiloxane in component (A) is 1% by mass or less. 4. The water-absorbing agent according to any one of 1 to 3, wherein component (B) is a surfactant containing a non-ionic surfactant. 5. The water-absorbing agent as in 4, wherein (B) the non-ionic surfactant is a non-ionic surfactant with an HLB value of 15.0 or less. 6. The water-absorbing agent according to any one of 1 to 5, wherein component (B) is a surfactant that does not contain a cationic surfactant. 7. The water-absorbing agent according to any one of 1 to 6, which is a water-absorbing agent for paper. 8. A paperboard with anti-absorption treatment, which is formed by applying an anti-absorption agent such as any one of 1 to 6 on at least one side of the cardboard substrate and then performing heat treatment. [Effects of the invention]

The amino-modified silicone emulsion composition of the present invention has excellent anti-water absorption effect, good dilution stability, can reduce the content of environmental load substances, and has a small load on the environment. If this composition is used as an anti-water absorption treatment agent, it can impart excellent water absorption resistance to paperboards and the like.

[式中，R¹ 相互獨立為碳數1~20之非取代一價烴基，R² 相互獨立為以下述式(2)表示之基，

(R⁴ 及R⁵ 相互獨立為碳數1~6之二價有機基，p為0或1) R³ 相互獨立為選自R¹ 及R² 之選項中之基或選自-OH、-OCH₃ 及-OC₂ H₅ 之基，a、b、c、d及e係滿足2≦a≦10，10≦b≦1,000，0≦c≦50，0≦d≦5，0≦e≦5之範圍之數，但c=0時R³ 為R² ]。Hereinafter, the present invention will be described in detail. [(A) Component] (A) is represented by the following average composition formula (1), the viscosity at 25°C is 800~100,000 mPa·s, the amine equivalent is 500~20,000g/mol and octamethylcyclotetrasiloxane Amino-modified silica with an oxane content of 1% by mass or less can be used alone or in a proper combination of two or more:

[In the formula, R ^{1 is} mutually independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^{2 is} mutually independently a group represented by the following formula (2),

(R ⁴ and R ⁵ are independently a divalent organic group with 1 to 6 carbon atoms, and p is 0 or 1) R ^{3 is} independently a group selected from ^{the options of R 1} and R ² or selected from -OH,- The base of OCH ₃ and -OC ₂ H ₅ , a, b, c, d and e satisfy 2≦a≦10, 10≦b≦1,000, 0≦c≦50, 0≦d≦5, 0≦e≦ A number in the range of 5, but when c=0, R ³ is R ² ].

R ¹ is an unsubstituted monovalent hydrocarbon group with 1 to 20 carbon atoms independently of each other. Examples are for example methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, tetradecyl, octadecyl Alkyl groups such as vinyl, allyl, 5-hexenyl, and oleyl; aryl groups such as phenyl, tolyl and naphthyl. Among them, methyl, long-chain (carbon number 6-20) alkyl, and phenyl are preferred, and methyl is more preferred.

(R⁴ 及R⁵ 相互獨立為碳數1~6之二價有機基，p為0或1)。作為碳數1~6之二價有機基，舉例為伸烷基、伸烯基、伸芳基等之二價烴基。作為以通式(2)表示之基，可舉例為例如2-胺基乙基、3-胺基丙基、6-胺基己基、N-(2-胺基乙基)-3-胺基丙基、N-(3-胺基丙基)-3-胺基丙基、N-(2-胺基乙基)-6-胺基己基等。其中，基於原料取得容易之方面，較佳為3-胺基丙基或N-(2-胺基乙基)-3-胺基丙基。R ² is a base represented by the following formula (2) independently of each other,

(R ⁴ and R ⁵ are independently a divalent organic group with 1 to 6 carbon atoms, and p is 0 or 1). The divalent organic group having 1 to 6 carbon atoms is exemplified by divalent hydrocarbon groups such as alkylene, alkenylene, and arylene. As the group represented by the general formula (2), for example, 2-aminoethyl, 3-aminopropyl, 6-aminohexyl, N-(2-aminoethyl)-3-amino Propyl, N-(3-aminopropyl)-3-aminopropyl, N-(2-aminoethyl)-6-aminohexyl, etc. Among them, 3-aminopropyl or N-(2-aminoethyl)-3-aminopropyl is preferred from the viewpoint of easy availability of raw materials.

R ^{3 is} independently a group selected from ^{the options of R 1} and R ² or a group selected from -OH, -OCH ₃ and -OC ₂ H _{5. When} c=0, R ³ is R ² . a is 2≦a≦10, preferably 2≦a≦5, and more preferably a=2. If a is less than 2, the viscosity of the amino-modified silica becomes too high, and the emulsion stability (the stability of the emulsion itself) deteriorates. On the other hand, if a exceeds 10, the viscosity of the amino-modified silica becomes too low and the water absorption resistance deteriorates. And, preferably methyl relative to R ^1, R ² and R ³ contain a total number of more than 70% of.

b is 10≦b≦1,000, preferably 200≦b≦800. If b is less than 150, the viscosity of the amino-modified silica becomes too low and the water absorption resistance deteriorates. On the other hand, if b exceeds 1,000, the viscosity of the amino-modified silica becomes too high and the emulsion stability deteriorates.

c is 0≦c≦50, preferably 1-30. If c is less than 1, the amount of amine groups in the amine-modified silica may be too small and the emulsification stability may deteriorate. However, in the case of R ³ =R ² , c may be less than 1, and c=0. On the other hand, when c exceeds 50, the amount of amine groups in the amine-modified silica is excessive and the water absorption resistance deteriorates.

d is 0≦d≦5, preferably d=0. If d exceeds 5, the viscosity of the amino-modified silica becomes too high and the emulsion stability deteriorates.

e is 0≦e≦5, preferably e=0. If e exceeds 5, the viscosity of the amino-modified silica becomes too high and the emulsion stability deteriorates.

(A) The viscosity of the component at 25°C is 800 to 100,000 mPa·s, preferably 1,000 to 50,000 mPa·s, and more preferably 1,000 to 30,000 mPa·s. If the viscosity does not reach the above lower limit, the water absorption resistance deteriorates. If it exceeds the above upper limit, the emulsion stability deteriorates. In addition, in the present invention, the viscosity is a value measured with a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.). And, corresponding to the viscosity, the rotor, the number of rotations, and the rotation time are appropriately selected based on common methods.

(A) The amine equivalent of the component is 500 to 20,000 g/mol, preferably 800 to 15,000 g/mol, more preferably 1,000 to 13,000 g/mol. If the amine group equivalent does not reach the aforementioned lower limit value, there are too many amine groups, which deteriorates the water absorption resistance. On the other hand, if the amine group equivalent exceeds the aforementioned upper limit, there are too few amine groups, and therefore, the hydrophilicity that should be imparted to the modified silica as the amine group is insufficient, thereby deteriorating the emulsion stability. In addition, the amine equivalent in the present invention refers to the number of grams of amine modified silica that can be neutralized with 1 mol of hydrochloric acid, and theoretically is the molecular weight/the number of nitrogen atoms. The amine equivalent can be measured by a neutralization titration method, for example, by an automatic titration device manufactured by Hiranuma Sangyo Co., Ltd.

(A) The content of octamethylcyclotetrasiloxane in the component is 1% by mass or less, preferably 0.5% by mass or less, and more preferably 0.1% by mass or less. The content of decamethylcyclopentasiloxane is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less. The content of dodecamethylcyclohexasiloxane is preferably 1% by mass or less. It is more preferably 0.5% by mass or less, and still more preferably 0.1% by mass or less. (A) The amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane in component (A) can be determined by gas chromatography. Specifically, 0.1 g of the measurement sample is added to 10 ml of acetone, and shaken for about 2 hours. After the cyclic low-molecular-weight silicone is extracted into the acetone solution by vibration, the acetone solution of the supernatant is determined by gas chromatography.

(A) Amino-modified silica can be easily obtained by conventional synthetic methods. For example, in the presence of catalysts such as alkali metal hydroxides, tetramethylammonium hydroxide, etc., by making cyclic siloxanes such as octamethylcyclotetrasiloxane and 3-aminopropyldiethyl Oxymethylsilane or N-(2-aminoethyl)-3-aminopropyldimethoxymethylsilane or its hydrolysate, and other raw materials such as hexamethyldisiloxy and other compounds Obtained by equilibrium reaction.

When the component (A) is synthesized, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are by-produced according to the manufacturing method. In order to make octamethylcyclotetrasiloxane The content of oxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane is 1% by mass or less, and it is preferable to implement the step of removing the volatile components of the obtained component (A). (A) The octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in component (A) can be removed by conventional methods. For example, while blowing nitrogen gas on component (A), under the conditions of 80~150℃, 5~40 hours, 30mmHg or less under reduced pressure, the octamethylcyclotetrasiloxane and decamethyl in component (A) can be reduced Cyclopentasiloxane and dodecamethylcyclohexasiloxane are 1% by mass or less in the component (A).

[(B) Ingredient] (B) Component is one or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants and zwitterionic surfactants (but, polyoxyethylene nonylphenyl ether and polyoxyethylene Except for vinyl octyl phenyl ether), one type can be used alone or two or more types can be used in appropriate combination.

Examples of nonionic surfactants include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers and polyoxyethylene propylene alkyl ethers, polyoxyethylene fatty acid esters, and polyoxyethylene sorbitol. Anhydride fatty acid esters, etc. Examples of polyoxyethylene alkyl ethers include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene Ethylene oleyl ether and the like. Examples of polyoxyethylene propylene alkyl ethers include polyoxyethylene propylene decyl ether, polyoxyethylene propylene lauryl ether, polyoxyethylene propylene tridecyl ether, and the like. Among them, polyoxyalkylene alkyl ethers are preferred, and polyoxyethylene alkyl ethers and polyoxyethylene propylene alkyl ethers are more preferred.

Examples of cationic surfactants include quaternary ammonium salts, alkylamine acetates, and the like. As an anionic surfactant, alkyl sulfate, alkylbenzene sulfonate, alkylsulfosuccinate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkylphenyl ether sulfate, etc. are mentioned, for example.

As the surfactant of the component (B), based on the ease of emulsification of amine-modified silica, a nonionic surfactant is necessary and it is preferable to include a nonionic surfactant. From the viewpoint of dilution stability, the nonionic surfactant preferably has an HLB value of 15.0 or less, more preferably an HLB value of 14.5 or less, and even more preferably an HLB value of 1.40 or less. The surfactant can be only a nonionic surfactant, or a combination of a nonionic surfactant and a surfactant selected from anionic surfactants, cationic surfactants and two-ionic surfactants, but based on water absorption resistance From this point of view, the component (B) is preferably only a non-ionic surfactant, and from the viewpoint of water absorption resistance, it is preferable not to contain a cationic surfactant. And, HLB is the value calculated by Griffin method.

The content of (B) component is 5-100 parts by mass relative to 100 parts by mass of component (A), preferably 2 to 80 parts by mass, more preferably 3 to 70 parts by mass, and still more preferably 4-60 parts by mass . If the content of the component (B) does not reach the above lower limit, the dilution stability will deteriorate, and if it exceeds the above upper limit, the water absorption resistance will deteriorate.

[(C) Ingredient] (C) Component water, all types of water such as ion exchange water and purified water can be used. The content of the component (C) is 10 to 2,000 parts by mass, preferably 50 to 1,000 parts by mass relative to 100 parts by mass of the component (A).

[Production method] The amino-modified silicone emulsion composition of the present invention can be prepared by, for example, the following method. The (C) component is mixed with the (A) component and (B) component, and it is prepared by emulsifying and dispersing according to a common method. Among them, oil droplets in water (O/W type) emulsions are preferred. Furthermore, it can be diluted by adding water to the emulsion, and can be used for the purposes described later. The amount of water used for dilution is not particularly limited, and can be appropriately adjusted according to the application.

In addition to the above-mentioned components (A) to (C), the amine-modified silicone emulsion composition of the present invention can be blended with various optional components in appropriate amounts as needed without detracting from the purpose of the present invention. Examples of these optional components include silicone components and additives other than the (A) component.

Specific examples of silicone components other than the component (A) include silicone oils such as dimethyl silicone oil, methylhydrosilicone oil, methylphenyl silicone oil, and alkyl modified silicone oil. In the case of blending silica components other than the (A) component, the amount is preferably 5 to 50 parts by mass relative to 100 parts by mass of the (A) component.

As additives, for example, in order to improve the stability of emulsification, acids such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, stearic acid, lactic acid, and citric acid can be formulated. The amount of additives can be set arbitrarily, but it is preferable to adjust the pH of the emulsion composition of the present invention to an amount of 3-7. Examples of other additives include thickeners, antifreeze agents, antiseptics, rust inhibitors, antioxidants, ultraviolet absorbers, and the like.

[Anti-absorbent] The amino-modified silicone emulsion composition has excellent anti-water absorption and water repellent effects, so it is used as an anti-water absorption agent formed from the amino-modified silicone emulsion composition. Examples of water-absorbing agents include water-absorbing agents for paperboard, water-absorbing agents for fibers (fiber treatment agents), and the like. The cardboard is not particularly limited, and it is also effective for corrugated base paper, paperboard paper, miscellaneous paperboard, and the like. The fiber is not particularly limited. For natural fibers such as cotton, silk, linen, wool, angora wool, and mohair, synthetic fibers such as polyester, polyethylene, polypropylene, nylon, acrylic, spandex, etc. The combined blended fibers are also all effective. In addition, its form and shape are not limited, and are not limited to raw material shapes such as staple fiber (stsaple), filament (filament), tow (tow), yarn (yarn), etc., fabric, weaving, cotton wadding, Various processing forms such as non-woven fabrics can also be processed objects of the fiber processing agent of the present invention.

As an anti-water absorption agent, it can be directly applied to the target with an amino-modified silica emulsion composition, or it can be applied after being diluted with water. In the case of dilution, although the concentration is not particularly limited, it is advisable to dilute the content of the amino-modified silicone emulsion composition of component (A) to 0.05-5 mass%. If the content is less than 0.05% by mass, there is a possibility that sufficient waterproofness cannot be provided to the object. The coating amount is preferably ^{0.001 to 5 g for a 1 m 2} substrate, and the silicone oil component is 0.001 to 5 g. It is better to heat the anti-absorbent after coating, the heating temperature is 50~200℃, and the heating time can be appropriately selected from 10 seconds to 5 minutes.

[cardboard] The paperboard of the present invention is a paperboard that is treated with water-absorption resistance after coating the water-absorbent agent made of the above-mentioned amine-modified silicone emulsion composition on at least one side of the paperboard substrate and then heat-treating it. The processing methods of paperboard and anti-absorbent are as described above. [Example]

Hereinafter, examples and comparative examples are shown to specifically explain the present invention, but the present invention is not limited to the following examples. In addition, the blending amount is the blending amount of the blended product when the name of the blended product is recorded.

The raw materials used in the examples and comparative examples are shown. (A) Amine modified silica The viscosity at 25°C is a value measured with a BM type viscometer (manufactured by Tokyo Keiki Co., Ltd.). The amine equivalent is a value measured with an automatic titration device (manufactured by Hiranuma Sangyo Co., Ltd.). The measurement of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane is performed by adding 0.1g of the measurement sample to 10mL of acetone, and shaking for 2 hours. After the cyclic low-molecular-weight silica is extracted into the acetone solution by vibration, the acetone solution of the supernatant is measured by gas chromatography (Agilent 7890B (manufactured by Agilent Technology)). The column system of the gas chromatography method is used DB-5MS (manufactured by Agilent Technology), the temperature inside the column was 300°C during the measurement, and tetradecane was used as the internal standard substance.

R¹ :-CH₃ ，R² :-C₃ H₆ NHC₂ H₄ NH₂ ，R³ :-CH₃ ，a=2，b=600，c=15，d=0，e=0，黏度：4,900mPa‧s，胺基當量：1,650g/mol (A-1)成分中之八甲基環四矽氧烷量：未達0.01質量%(檢測界限以下) (A-1)成分中之十甲基環五矽氧烷量：0.01質量% (A-1)成分中之十二甲基環六矽氧烷量：0.04質量%(A-1) Amino-modified silica is represented by the following average formula (1)

R ¹ :-CH ₃ , R ² :-C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ :-CH ₃ , a=2, b=600, c=15, d=0, e=0, viscosity ：4,900mPa‧s, amine equivalent: 1,650g/mol (A-1) The amount of octamethylcyclotetrasiloxane in the component: less than 0.01% by mass (below the detection limit) (A-1) Among the components The amount of decamethylcyclopentasiloxane: 0.01% by mass (A-1) The amount of dodecamethylcyclohexasiloxane in the component: 0.04% by mass

(A-1) Production method In a separable flask equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen introduction tube, 92.61 parts by mass of octamethylcyclotetrasiloxane and 2-(aminoethyl)-3 -4.49 parts by mass of the hydrolyzate of aminopropylmethyldimethoxysilane, 2.80 parts by mass of dimethylsiloxane represented by the following formula (3), and 0.07 parts by mass of potassium siliconate, heated at 120°C The equilibrium reaction was carried out for 8 hours. Subsequently, 0.03 parts by mass of epichlorohydrin was added, and the mixture was heated at 70°C for 2 hours to carry out a neutralization reaction. Subsequently, under conditions of 130° C. and 15 mmHg or less, vacuum stripping was performed for 20 hours to remove low-boiling fractions to obtain an oily compound (A-1).

^{(A-2) Amino-modified silica R 1} :-CH ₃ , R ² :-C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ The amine-modified silica represented by the above average formula (1) :-CH ₃ , a=2, b=350, c=3.5, d=0, e=0, viscosity: 2,600mPa‧s, amine equivalent: 3,600g/mol (A-2) The amount of cyclotetrasiloxane: less than 0.01% by mass (A-2) The amount of decamethylcyclopentasiloxane in component: 0.02% by mass (A-2) The amount of dodecamethylcyclohexasiloxane in component (A-2) Alkane amount: 0.03% by mass

(A-2) Manufacturing method According to the manufacturing method of (A-1), except that the blending of raw materials is 94.11 parts by mass of octamethylcyclotetrasiloxane, 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Except for 2.19 parts by mass of the hydrolyzate of the above formula (3) and 3.60 parts by mass of the dimethylsiloxane represented by the above formula (3), the amine modified silica (A- 2). In addition, the amounts of potassium silicate and epichlorohydrin are the same as (A-1).

(A-3) Amino modified silica is represented by the above average formula (1) R ¹ :-CH ₃ , R ² :-C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ :-CH ₃ , a= 2. b=280, c=6, d=0, e=0, viscosity: 1,500mPa‧s, amine equivalent: 1,700g/mol (A-3) The amount of octamethylcyclotetrasiloxane in the component ：0.02% by mass (A-3) The amount of decamethylcyclopentasiloxane in the component: 0.04% by mass (A-3) The amount of dodecamethylcyclohexasiloxane in the component: 0.06% by mass

(A-3) Manufacturing method According to the manufacturing method of (A-1), except for the blending of raw materials, 91.20 parts by mass of octamethylcyclotetrasiloxane, 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Except for 4.40 parts by mass of the hydrolyzate and 4.30 parts by mass of the dimethylsiloxane represented by the above formula (3), the amine modified silica (A- 3). In addition, the amounts of potassium silicate and epichlorohydrin are the same as (A-1).

(A-4) Amino modified silica is represented by the above average formula (1) R ¹ :-CH ₃ , R ² :-C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ :-CH ₃ , a= 2. b=300, c=1, d=0, e=0, viscosity: 1,660mPa‧s, amine equivalent: 11,000g/mol (A-4) The amount of octamethylcyclotetrasiloxane in the component ：0.02% by mass (A-4) The amount of decamethylcyclopentasiloxane in the component: 0.03% by mass (A-4) The amount of dodecamethylcyclohexasiloxane in the component: 0.03% by mass

(A-4) Manufacturing method According to the manufacturing method of (A-1), except for the blending of raw materials, 95.81 parts by mass of octamethylcyclotetrasiloxane, 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Except 0.71 parts by mass of the hydrolyzate of the above formula (3) and 3.38 parts by mass of the dimethylsiloxane represented by the above formula (3), the amine modified silica (A- 4). In addition, the amounts of potassium silicate and epichlorohydrin are the same as (A-1).

(A-5) Amino modified silica is represented by the above average formula (1) R ¹ :-CH ₃ , R ² :-C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ :-CH ₃ , a= 2. b=650, c=14, d=0, e=0, viscosity: 13,000mPa‧s, amine equivalent: 1,800g/mol (A-5) The amount of octamethylcyclotetrasiloxane in the component ：0.03% by mass (A-5) The amount of decamethylcyclopentasiloxane in the component: 0.05% by mass (A-5) The amount of dodecamethylcyclohexasiloxane in the component: 0.06% by mass

(A-5) Manufacturing method According to the manufacturing method of (A-1), except that the blending of raw materials is 93.88 parts by mass of octamethylcyclotetrasiloxane, 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Except for 4.27 parts by mass of the hydrolyzate of the above formula (3) and 1.84 parts by mass of the dimethylsiloxane represented by the above formula (3), the amine modified silica (A- 5). In addition, the amounts of potassium silicate and epichlorohydrin are the same as (A-6).

(A-6) Amino modified silica (comparison) R ¹ :-CH ₃ , R ² :-C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ :-CH _{3 represented by the above average formula (1)} , A=2, b=37, c=1.1, d=0, e=0, viscosity: 40mPa‧s, amine equivalent: 1,500g/mol (A-6) octamethylcyclotetrasiloxane Amount of alkane: 2.5% by mass (A-6) Amount of decamethylcyclopentasiloxane in component: 2.0% by mass (A-6) Amount of dodecamethylcyclosiloxane in component: 1.5% by mass

(A-6) Manufacturing method In a separable flask equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen introduction tube, 59.50 parts by mass of octamethylcyclotetrasiloxane, 2-(aminoethyl)-3-aminopropylmethyl 5.81 parts by mass of the hydrolyzate of dimethoxysilane, 34.59 parts by mass of dimethylsiloxane represented by the above formula (3), and 0.07 parts by mass of potassium silicate were heated at 110°C for 8 hours to perform an equilibrium reaction. Subsequently, 0.03 parts by mass of epichlorohydrin was added, and the mixture was heated at 80°C for 3 hours to perform a neutralization reaction to obtain an oily compound (A-6).

(A-7) Amino-modified silica (comparison) R ¹ :-CH ₃ , R ² :-C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ :-CH _{3 represented by the above average formula (1)} , A=2, b=37, c=1.1, d=0, e=0, viscosity: 55mPa‧s, amine equivalent: 1,500g/mol (A-7) octamethylcyclotetrasiloxane in the component Amount of alkane: 0.01% by mass (A-7) Amount of decamethylcyclopentasiloxane in component: 0.02% by mass (A-7) Amount of dodecamethylcyclohexasiloxane in component: 0.02% by mass

(A-7) Manufacturing method In a separable flask equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen introduction tube, 59.50 parts by mass of octamethylcyclotetrasiloxane, 2-(aminoethyl)-3-aminopropylmethyl 5.81 parts by mass of the hydrolyzate of dimethoxysiloxane, 34.59 parts by mass of dimethylsiloxane represented by the above formula (3), and 0.07 parts by mass of potassium silicate were heated at 110°C for 8 hours to perform an equilibrium reaction. Subsequently, 0.03 parts by mass of epichlorohydrin was added, and the mixture was heated at 80°C for 3 hours to carry out a neutralization reaction. Subsequently, under the conditions of 110° C. and 15 mmHg or less, vacuum stripping was performed for 10 hours to remove low-boiling fractions to obtain an oily compound (A-7).

(A-8) Amino modified silica (comparison) R ¹ :-CH ₃ , R ² :-C ₃ H ₆ NH ₂ , R ³ :-CH ₃ , a=2 represented by the above average formula (1) , B=900, c=2, d=0, e=0, viscosity: 18,000mPa‧s, amine equivalent: 33,000g/mol (A-8) The amount of octamethylcyclotetrasiloxane in the component: 3.5% by mass (A-8) The amount of decamethylcyclopentasiloxane in the component: 2.8% by mass (A-8) The amount of dodecamethylcyclohexasiloxane in the component: 2.1% by mass

(A-8) Manufacturing method According to the manufacturing method of (A-6), except that the blending of raw materials is 98.03 parts by mass of octamethylcyclotetrasiloxane, 0.37 parts by mass of hydrolysate of 3-aminopropylmethyldiethoxysilane, and the above Except for 1.50 parts by mass of dimethylsiloxane represented by the formula (3), an amino-modified silica (A-8) was obtained by the same method as the production method of (A-6). In addition, the amounts of potassium silicate and epichlorohydrin are the same as (A-6).

(A-9) Amino modified silica (comparison) R ¹ : -CH ₃ , R ² : -C ₃ H ₆ NHC ₂ H ₄ NH ₂ , R ³ : -CH _{3 represented by the above average formula (1)} , A=2, b=600, c=15, d=0, e=0, viscosity: 3,600mPa‧s, amine equivalent: 1,650g/mol (A-9) octamethylcyclotetrasiloxane in the component Oxyane amount: 1.6% by mass (A-9) Decamethylcyclopentasiloxane amount in component: 1.6% by mass (A-9) Dodecamethylcyclohexasiloxane amount in component: 1.3% by mass

(A-9) Manufacturing method According to the manufacturing method of (A-6), except that the blend of raw materials is 92.61 parts by mass of octamethylcyclotetrasiloxane and 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane Except for 4.49 parts by mass of the hydrolyzate and 2.80 parts by mass of the dimethylsiloxane represented by the above formula (3), by the same method as the production method of (A-6), an amino-modified silica (A-8) ). In addition, the amounts of potassium silicate and epichlorohydrin are the same as (A-6).

(B) Surfactant Newcol 1310 (trade name): manufactured by Japan Emulsifier Company, polyoxyethylene tridecyl ether, HLB value = 13.7 Newcol 1004 (trade name): manufactured by Japan Emulsifier Company, polyoxyethylene octyl ether, HLB value = 11.5

[Example 1] Use a homogenizer to mix (A) amine modified silica A-1 (viscosity: 4,900mPa‧s, amine equivalent: 1,650g/mol): 100 parts by mass, (B) Newcol 1310: 16.7 parts by mass, (C ) Ion-exchanged water: 213.9 parts by mass, acetic acid: 2.8 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (I-1) having a non-volatile content of 35% at 105°C for 3 hours.

[Example 2] Use a homogenizer to mix (A) amine modified silica (A-1) (viscosity: 4,900mPa‧s, amine equivalent: 1,650g/mol): 100 parts by mass, (B) Newcol 1310: 10 parts by mass, (C) Ion-exchanged water: 220.5 parts by mass, acetic acid: 2.8 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (I-2) with 33% by mass of non-volatile content at 105°C for 3 hours .

[Example 3] Use a homogenizer to mix (A) amine modified silica (A-2) (viscosity: 2,600mPa‧s, amine equivalent: 3,600g/mol): 100 parts by mass, (B) Newcol 1310: 10.0 parts by mass, (C) Ion-exchanged water: 222.1 parts by mass, acetic acid: 1.3 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (I-3) with 33% by mass of non-volatile content at 105°C for 3 hours .

[Example 4] Use a homogenizer to mix (A) amine modified silica (A-3) (viscosity: 1,500mPa‧s, amine equivalent: 1,700g/mol): 100 parts by mass, (B) Newcol 1310: 10.0 parts by mass, (C) Ion exchanged water: 220.6 parts by mass, acetic acid: 2.7 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (I-4) with 33% by mass of non-volatile content at 105°C for 3 hours .

[Example 5] Use a homogenizer to mix (A) amine modified silica (A-4) (viscosity: 1,660mPa‧s, amine equivalent: 11,000 g/mol): 100 parts by mass, (B) Newcol 1310: 10.0 parts by mass, (C) Ion-exchanged water: 222.9 parts by mass, acetic acid: 0.4 parts by mass and emulsified and dispersed to obtain an amine-modified silica emulsion composition (I-5) having 33% by mass of non-volatile content at 105°C for 3 hours.

[Example 6] Use a homogenizer to mix (A) amine modified silica (A-5) (viscosity: 13,000 mPa‧s, amine equivalent: 1,800g/mol): 100 parts by mass, (B) Newcol 1310: 10.0 parts by mass, (C) Ion-exchanged water: 220.8 parts by mass, acetic acid: 2.6 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (I-6) with 33% by mass of non-volatile content at 105°C for 3 hours .

[Example 7] Use a homogenizer to mix (A) amine modified silica (A-1) (viscosity: 4,900mPa‧s, amine equivalent: 1,650g/mol): 100 parts by mass, (B) Newcol 1004: 50.0 parts by mass, (C) Ion-exchanged water: 180.53 parts by mass, acetic acid: 2.8 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (I-6) with 45% by mass of non-volatile content at 105°C for 3 hours .

[Comparative Example 1] Use a homogenizer to mix (A) amine modified silica (A-6) (viscosity: 40mPa‧s, amine equivalent: 1,500g/mol): 100 parts by mass, (B) Newcol 1310: 10.0 parts by mass, ( C) Ion-exchanged water: 220.3 parts by mass, acetic acid: 3.1 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (II-1) having 33% by mass of non-volatile content at 105°C for 3 hours.

[Comparative Example 2] Use a homogenizer to mix (A) amine modified silica (A-7) (viscosity: 55mPa‧s, amine equivalent: 1,500g/mol): 100 parts by mass, (B) Newcol 1310: 10.0 parts by mass, ( C) Ion-exchanged water: 220.3 parts by mass, acetic acid: 3.1 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (II-2) having 33% by mass of non-volatile content at 105°C for 3 hours.

[Comparative Example 3] Use a homogenizer to mix (A) amine modified silica (A-8) (viscosity: 18,000mPa‧s, amine equivalent: 33,000g/mol): 100 parts by mass, (B) Newcol 1310: 10.0 parts by mass, (C) Ion-exchanged water: 223.2 parts by mass, acetic acid: 0.1 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (II-3) with 33% by mass of non-volatile content at 105°C for 3 hours .

[Comparative Example 4] Use a homogenizer to mix (A) amine modified silica (A-9) (viscosity: 3,600mPa‧s, amine equivalent: 1,650g/mol): 100 parts by mass, (B) Newcol 1310: 10.0 parts by mass, (C) Ion-exchanged water: 220.5 parts by mass, acetic acid: 2.8 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (II-4) with 33% by mass of non-volatile content at 105°C for 3 hours .

[Comparative Example 5] Use a homogenizer to mix (A) amine modified silica (A-9) (viscosity: 3,600mPa‧s, amine equivalent: 1,650g/mol): 100 parts by mass, (B) Newcol 1004: 50.0 parts by mass, (C) Ion-exchanged water: 180.5 parts by mass, acetic acid: 2.8 parts by mass and emulsified and dispersed to obtain an amino-modified silica emulsion composition (II-5) with 33% by mass of non-volatile content at 105°C for 3 hours .

表示之於分子中不具有胺基之矽氧油(黏度：10,000 mPa‧s，含八甲基環四矽氧烷量：0.01質量%以下)：100質量份、(B)Newcol 1310：15.0質量份、(C)離子交換水：218.3質量份並乳化分散，獲得具有於105℃・3小時之不揮發成分34.5質量%之矽氧乳液組成物(II-6)。[Comparative Example 6] Mixing with a homogenizer (A) The following formula (4)

It means silicone oil without amine group in the molecule (viscosity: 10,000 mPa‧s, content of octamethylcyclotetrasiloxane: 0.01% by mass or less): 100 parts by mass, (B) Newcol 1310: 15.0 mass (C) Ion-exchanged water: 218.3 parts by mass and emulsified and dispersed to obtain a silicone emulsion composition (II-6) with 34.5 mass% of non-volatile content at 105°C for 3 hours.

For the obtained silicone emulsion composition, the "water absorption" and "dilution stability" were evaluated by the following methods. The results are described in the table together with the physical properties of (A) amino-modified silica.

[Water Absorption] After further diluting the silicone emulsion composition with water to a silica content of 0.5% by mass, use paper gauze to coat it on the surface of a work board of 100mm×100mm and a thickness of 0.38mm. Next, the cardboard was heated and dried at 120°C for 5 minutes, and its weight was measured (weight A). The silicon-oxygen treated surface was floated on the water surface for 1 minute, and the water droplets were wiped off. The weight of the cardboard was measured (weight B) and calculated according to the following formula Water absorption. With regard to water absorption, the smaller the value, the better the water absorption resistance. The results are shown in the table below. Water absorption (%)=100(B-A)/A

[Dilution stability] Pour a solution of the silicone emulsified composition diluted 100 times (mass) with tap water into a glass beaker, and visually confirm whether there is separation when stored at 25°C for 20 hours. The "dilution stability" was evaluated based on the following indicators. The results are shown in the table below. ○: No precipitate △: Slightly precipitated ╳: There are precipitates

Based on the above results, it can be understood that the amino-modified silicone emulsion composition of the present invention has excellent water absorption resistance and good dilution stability. Furthermore, the content of cyclic low-molecular-weight siloxanes is small, and the load on the environment is low. [Industrial availability]

The anti-absorbent agent of the present invention has excellent water absorption resistance and good dilution stability. Furthermore, the content of cyclic low-molecular-weight siloxanes is small, and the load on the environment is low. It is useful as an anti-absorbent for paperboard.

Claims (8)

An anti-absorbent agent, which is made of an amine-modified silicone emulsion composition, the composition contains: (A) Expressed by the following average composition formula (1), with a viscosity of 800~100,000mPa·s at 25°C , Amino modified silica with an amine equivalent of 500~20,000g/mol and an octamethylcyclotetrasiloxane content of 1% by mass or less: 100 parts by mass,

[In the formula, R ^{1 is} mutually independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ^{2 is} mutually independently a group represented by the following formula (2),

(R ⁴ and R ⁵ are independently a divalent organic group with 1 to 6 carbon atoms, and p is 0 or 1) R ^{3 is} independently a group selected from ^{the options of R 1} and R ² or selected from -OH,- The base of OCH ₃ and -OC ₂ H ₅ , a, b, c, d and e satisfy 2≦a≦10, 10≦b≦1,000, 0≦c≦50, 0≦d≦5, 0≦e≦ A number in the range of 5, but when c=0, R ³ is R ² ], (B) One or more interface selected from non-ionic surfactants, anionic surfactants, cationic surfactants and two-ionic surfactants Active agent (except polyoxyethylene nonyl phenyl ether and polyoxyethylene octyl phenyl ether): 5 to 100 parts by mass (C) Water: 10 to 2,000 parts by mass. Such as the water-absorbing agent of claim 1, wherein the content of decamethylcyclopentasiloxane in component (A) is 1% by mass or less. Such as the water-absorbing agent of claim 1 or 2, wherein the content of dodecamethylcyclohexasiloxane in component (A) is 1% by mass or less. The water-absorbing agent of claim 1 or 2, wherein component (B) is a surfactant containing a nonionic surfactant. Such as the water-absorbing agent of claim 4, wherein (B) the non-ionic surfactant is a non-ionic surfactant with an HLB value of 15.0 or less. Such as the water-absorbing agent of claim 1 or 2, wherein component (B) is a surfactant that does not contain a cationic surfactant. Such as the water-absorbent agent of claim 1 or 2, which is a water-absorbent agent for paper. A paperboard subjected to anti-absorption treatment, which is formed by coating the anti-absorption agent according to any one of claims 1 to 6 on at least one side of a paperboard substrate and then performing heat treatment.