KR20220119135A - Absorbent and cardboard - Google Patents

Abstract

(A) An amino-modified silicone having a viscosity of 800 to 100,000 mPa·s at 25°C and an amino group equivalent of 500 to 20,000 g/mol, an amino-modified silicone having an octamethylcyclotetrasiloxane content of 1% by mass or less: 100 mass Part, (B) at least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants and cationic surfactants (except polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether) (C): 5 to 100 parts by mass, (C) Water: 10 to 2,000 parts by mass, an amino-modified silicone emulsion having an excellent absorption prevention imparting effect, good dilution stability, and a reduced content of environmental impact substances. Absorption inhibitor comprising the composition.

Description

Absorbent and cardboard

The present invention relates to an anti-absorption agent comprising an amino-modified silicone emulsion and a paperboard using the same. Specifically, it relates to an anti-absorption agent that is highly effective as a water repellent for paper and has a low environmental load.

BACKGROUND ART Conventionally, gypsum boards have been used in large quantities as a building material. As is well known, the gypsum board is a plate-shaped body in which multi-layered cardboard is strongly bonded and fixed on both sides of the hydration-hardened gypsum board. Various characteristics such as a small change in the size of the city and as much air permeability as possible are required.

Among these various properties, moisture absorption resistance and dimensional stability when wet are particularly important, and conventionally, for the purpose of improving moisture absorption resistance and suppressing dimensional change during wetness, it is a method for imparting water absorption prevention to the surface of cardboard processing has been done. As a treatment method in this case, the treatment with a silicone resin is widely performed with less impairing the air permeability. As the silicone resin in this treatment, various modified silicone oils including dimethyl silicone oil are said to be effective, and many emulsions using these are proposed as suitable surface treatment agents.

However, by the method using the epoxy-modified silicone oil disclosed in, for example, U.S. Patent No. 3,389,042, sufficient absorption preventing effect cannot be obtained, and the mercapto group-containing silicone disclosed in Japanese Patent Application Laid-Open No. 56-47994. When oil is used as a main ingredient, a high absorption prevention effect can be obtained, but there is a drawback that it is not preferable in terms of working environment because the odor peculiar to the mercapto group is very strong.

Japanese Patent Application Laid-Open No. Hei 08-025255 proposes a technique for obtaining a water repellent effect by using an amino-modified silicone having a specific viscosity and an amine equivalent. However, polyoxyethylene nonyl phenol ether is used as an emulsifier, and octamethylcyclotetrasiloxane is used as a diluent. Polyoxyethylene nonylphenyl ether is mentioned as a substance of high concern in EU REACH regulation. In addition, in recent years, cyclic low molecular weight siloxanes (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane) have become concerned as environmentally hazardous substances, and regulations are being strengthened in each country, octamethylcyclotetrasiloxane, The product which suppressed content of decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane is calculated|required. From the above background, coexistence of high water absorption prevention properties and low environmental load has been demanded.

U.S. Patent No. 3,389,042 Japanese Special Air Force No. 56-47994 Gazette Japanese Special Attack Hei 08-025255 Gazette

An object of the present invention is to provide an anti-absorption agent having an excellent absorption prevention imparting effect, good dilution stability, and a reduced content of environmental load substances in view of the problems of the prior art. In addition, "good dilution stability" refers to stability after diluting the absorption inhibitor with a certain amount of water and storing, as described in the evaluation method of Examples to be described later.

As a result of intensive studies to achieve the above object, the present inventors have found that an amino-modified silicone emulsion composition containing the following components (A) to (C) provides excellent absorption prevention properties, has good dilution stability, and is environmentally friendly. It discovered that content of a load substance could be reduced, and came to achieve this invention.

Accordingly, the present invention provides the following anti-absorption agent and paperboard.

1.(A) The following average composition formula (1)

[Wherein, R ¹ is independently of each other an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is each independently of the general formula (2)

(R ⁴ and R ⁵ are each independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1.)

is a group represented by , and R ³ is a group independently selected from R ¹ and R ² , or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , a, b, c, d and e is a number satisfying the following ranges: 2≤a≤10, 10≤b≤1,000, 0≤c≤50, 0≤d≤5, and 0≤e≤5. However, when c=0, R ³ is R ² ]

An amino-modified silicone having an amino group equivalent of 500 to 20,000 g/mol and an octamethylcyclotetrasiloxane content of 1% by mass or less: 100 mass part,

(B) At least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants and cationic surfactants (however, polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether are excluded. ): 5 to 100 parts by mass, and

(C) Water: 10 to 2,000 parts by mass

An anti-absorption agent comprising an amino-modified silicone emulsion composition containing

2. (A) The water absorption inhibitor as described in 1 whose content of decamethylcyclopentasiloxane in component is 1 mass % or less.

3.(A) The water absorption inhibitor as described in 1 or 2 whose content of dodecamethylcyclohexasiloxane in component is 1 mass % or less.

4. (B) The absorption inhibitor in any one of 1-3 which is surfactant containing a nonionic surfactant.

5. (B) The absorption inhibitor according to 4, wherein the nonionic surfactant is a nonionic surfactant having an HLB value of 15.0 or less.

6. (B) The absorption inhibitor in any one of 1-5 whose component is surfactant which does not contain a cationic surfactant.

7. The absorption inhibitor according to any one of 1 to 6, which is an absorption inhibitor for paper.

A paperboard subjected to absorption prevention treatment, wherein the absorption inhibitor according to any one of 8.1 to 6 is applied to at least one surface of a paperboard substrate and then heat-treated.

The amino-modified silicone emulsion composition of the present invention is excellent in absorption prevention effect, has good dilution stability, and can reduce the content of environmentally harmful substances, so that the environmental load is small. When this composition is used as a waterproofing agent, excellent water absorption prevention properties can be imparted to paperboard or the like.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

[(A) component]

(A) The following average composition formula (1)

[Wherein, R ¹ is independently of each other an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is each independently of the general formula (2)

(R ⁴ and R ⁵ are each independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1.)

is a group represented by , and R ³ is a group independently selected from R ¹ and R ² , or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , a, b, c, d and e is a number satisfying the following ranges: 2≤a≤10, 10≤b≤1,000, 0≤c≤50, 0≤d≤5, and 0≤e≤5. However, when c=0, R ³ is R ² ]

It is an amino-modified silicone having a viscosity of 800 to 100,000 mPa s at 25° C. and an amino group equivalent of 500 to 20,000 g/mol, an amino-modified silicone having an octamethylcyclotetrasiloxane content of 1% by mass or less, It can be used individually by 1 type or in combination of 2 or more types.

R ¹ is each independently an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group, decyl group, tetradecyl group, octadecyl group, etc. Alkyl group: Alkenyl groups, such as a vinyl group, an allyl group, 5-hexenyl group, and an oleyl group: Aryl groups, such as a phenyl group, a tolyl group, and a naphthyl group, etc. are mentioned. Among these, a methyl group, a long-chain (C6-20) alkyl group, and a phenyl group are preferable, and a methyl group is more preferable.

R ² are each independently of the general formula (2)

(R ⁴ and R ⁵ are each independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1.)

is a group indicated by As a C1-C6 divalent organic group, divalent hydrocarbon groups, such as an alkylene group, an alkenylene group, and an arylene group, are mentioned. Examples of the group represented by the general formula (2) include 2-aminoethyl group, 3-aminopropyl group, 6-aminohexyl group, N-(2-aminoethyl)-3-aminopropyl group, N-(3- aminopropyl)-3-aminopropyl group, N-(2-aminoethyl)-6-aminohexyl group, and the like. Among them, 3-aminopropyl group or N-(2-aminoethyl)-3-aminopropyl group is preferable from the viewpoints of the availability of raw materials and the like.

R ³ is independently of each other 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 , and when c=0, R ³ is R ² . a is 2≤a≤10, preferably 2≤a≤5, more preferably a=2. When a is less than 2, the viscosity of the amino-modified silicone becomes too high, and the emulsion stability (stability of the emulsion itself) deteriorates. On the other hand, when a exceeds 10, the viscosity of the amino-modified silicone becomes too low and the water absorption prevention property deteriorates. Moreover, it is preferable that the content rate of the methyl group with respect to the total number of R< ¹ >, R< ² > and R< ³ > is 70% or more.

b is 10≤b≤1,000, preferably 200≤b≤800. When b is less than 150, the viscosity of the amino-modified silicone becomes too low and the water absorption prevention property deteriorates. On the other hand, when b exceeds 1,000, the viscosity of the amino-modified silicone becomes too high, and the emulsion stability deteriorates.

c is 0≤c≤50, preferably 1 to 30. If c is less than 1, the amount of amino groups in the amino-modified silicone is too small, and there is a possibility that the emulsion stability may deteriorate. However, when R ³ =R ² , c may be less than 1 and c=0. On the other hand, when c exceeds 50, the amount of amino groups in the amino-modified silicone is too large, and the water absorption prevention property deteriorates.

d is 0≤d≤5, preferably d=0. When d exceeds 5, the viscosity of amino-modified silicone becomes high too much, and emulsion stability worsens.

e is 0≤e≤5, and e=0 is preferable. When e exceeds 5, the viscosity of amino-modified silicone becomes high too much, and emulsion stability worsens.

(A) The viscosity in 25 degreeC of component is 800-100,000 mPa*s, 1,000-50,000 mPa*s is preferable, and 1,000-30,000 mPa*s is more preferable. Water absorption prevention property worsens that a viscosity is less than the said lower limit. Moreover, when the said upper limit is exceeded, emulsion stability will worsen. In addition, in this invention, a viscosity is the value measured with the BM type|mold viscometer (For example, the Tokyo Keiki company make). In addition, depending on the viscosity, the rotor, the number of rotations, and the rotation time are appropriately selected based on a commercial method.

(A) The amino group equivalent of component is 500-20,000 g/mol, 800-15,000 g/mol is preferable, and 1,000-13,000 g/mol is more preferable. Since there are too many amino groups when an amino group equivalent is less than the said lower limit, water absorption prevention property worsens. On the other hand, since there are too few amino groups when an amino group equivalent exceeds the said upper limit, the hydrophilicity which should be given as an amino-modified silicone runs short, and emulsion stability worsens by this. In addition, the amino group equivalent in this invention is the number of grams of the amino-modified silicone used as the object which can be neutralized with 1 mol hydrochloric acid, and is molecular weight/number of nitrogen atoms theoretically. The amine equivalent can be measured by a neutralization titration method, for example, an automatic titration apparatus manufactured by Hiranuma Sangyo Co., Ltd.

(A) Content of octamethylcyclotetrasiloxane in a component is 1 mass % or less, It is preferable that it is 0.5 mass % or less, It is more preferable that it is 0.1 mass % or less.

1 mass % or less is preferable, as for content of decamethylcyclopentasiloxane, it is more preferable that it is 0.5 mass % or less, It is more preferable that it is 0.1 mass % or less.

As for content of dodecamethylcyclohexasiloxane, 1 mass % or less is preferable. 0.5 mass % or less is more preferable, and it is still more preferable that it is 0.1 mass % or less. (A) The amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in a component can be measured 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 siloxane is extracted from the acetone solution by shaking, the acetone solution of the supernatant is measured by gas chromatography.

(A) The amino-modified silicone can be easily obtained by a known synthesis method. For example, in the presence of a catalyst such as alkali metal hydroxide or tetramethylammonium hydroxide, cyclic siloxane such as octamethylcyclotetrasiloxane and 3-aminopropyldiethoxymethylsilane or N-(2-aminoethyl)-3- It is obtained by equilibrating a compound selected from aminopropyldimethoxymethylsilane or a hydrolyzate thereof, and other raw materials such as hexamethyldisiloxane.

(A) When synthesizing component, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane are by-produced depending on the manufacturing method, but octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethyl In order to make content of cyclohexasiloxane into 1 mass % or less, it is preferable to perform the process of removing the volatile component of the obtained (A) component. (A) Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in a component can be removed by a well-known method. For example, octamethylcyclotetrasiloxane in (A) component, decamethylcyclopentasiloxane by vacuum-distilling on 80-150 degreeC, 5-40 hours, and 30 mmHg or less conditions, blowing nitrogen gas into (A) component, for example. , dodecamethylcyclohexasiloxane can be made into 1 mass % or less in (A) component.

[(B) component]

(B) component is at least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants and cationic surfactants (except polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether) ), and can be used alone or in combination of two or more.

As a nonionic surfactant, polyoxyalkylene alkyl ethers, such as polyoxyethylene alkyl ether and polyoxyethylene propylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. are mentioned, for example. Examples of the polyoxyethylene alkyl ether include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether. As oxyethylene propylene alkyl ether, polyoxyethylene propylene decyl ether, polyoxyethylene propylene lauryl ether, polyoxyethylene propylene tridecyl ether, etc. are mentioned. Among these, polyoxyalkylene alkyl ether is preferable, and polyoxyethylene alkyl ether and polyoxyethylene propylene alkyl ether are more preferable.

Examples of cationic surfactants include quaternary ammonium salts and alkylamine acetate salts. Examples of the anionic surfactants include alkyl sulfates, alkylbenzenesulfonates, alkylsulfosuccinates, polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkylphenyl ether sulfates.

(B) As surfactant of component, it is a point of the easiness of emulsification of an amino-modified silicone to make nonionic surfactant essential, and it is preferable to contain nonionic surfactant. From the viewpoint of dilution stability, the nonionic surfactant is preferably an HLB value of 15.0 or less, more preferably an HLB value of 14.5 or less, and still more preferably an HLB value of 1.40 or less. The surfactant may be only a nonionic surfactant, or a combination of a nonionic surfactant and a surfactant selected from anionic surfactants, cationic surfactants and cationic surfactants, but from the viewpoint of absorption prevention (B) It is preferable that a component is only a nonionic surfactant, and it is preferable not to contain a cationic surfactant from the point of water absorption prevention property. In addition, HLB is a value calculated by the Griffin method.

(B) Content of component is 5-100 mass parts with respect to 100 mass parts of (A) component, 2-80 mass parts is preferable, 3-70 mass parts is more preferable, 4-60 mass parts is still more preferable. (B) When content of a component is less than the said lower limit, dilution stability will worsen, and when the said upper limit is exceeded, water absorption prevention property will worsen.

[(C)component]

(C) A component is water, and all water, such as ion-exchange water and purified water, can be used. (C) Content of component is 10-2,000 mass parts with respect to 100 mass parts of (A) component, and 50-1,000 mass parts is preferable.

[Manufacturing method]

The amino-modified silicone emulsion composition of the present invention can be prepared, for example, by the following method.

(C) It can prepare by mixing a component with (A) component and (B) component, and emulsifying and dispersing it according to a conventional method. Among them, oil-in-water (O/W type) emulsions are preferable. Further, the emulsion can be further diluted by adding water, and used for the purpose described later. The amount of water for dilution is not particularly limited, and may be appropriately adjusted according to the use.

In the amino-modified silicone emulsion composition of the present invention, in addition to the components (A) to (C), an appropriate amount of various optional components may be blended as needed within a range that does not impair the object of the present invention. As such an arbitrary component, silicone components other than (A) component, an additive, etc. are mentioned.

Specific examples of the silicone component other than the component (A) include silicone oils such as dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, and alkyl-modified silicone oil. (A) When mix|blending silicone components other than component, it is preferable that the quantity is 5-50 mass parts with respect to 100 mass parts of (A) component.

As an additive, acids, such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, stearic acid, lactic acid, and citric acid, can be mix|blended, for example, in order to improve emulsion stability. Although the amount of the additive can be set arbitrarily, it is preferable that it is an amount which adjusts the pH of the emulsion composition of this invention to 3-7. As other additives, a thickener, a cryoprotectant, an antiseptic|preservative, a rust preventive agent, antioxidant, an ultraviolet absorber, etc. are mentioned.

[Absorptive agent]

Since the amino-modified silicone emulsion composition has an excellent anti-absorption effect and water-repellent effect, it is used as an anti-absorption agent comprising the amino-modified silicone emulsion composition. Examples of the absorption inhibitor include an absorption inhibitor for paperboard, an absorption inhibitor for fibers (fiber treatment agent), and the like. The cardboard is not particularly limited, and it is effective also for a corrugated cardboard base, a paperboard for paper, miscellaneous cardboard, and the like. The fibers are not particularly limited, and natural fibers such as cotton, silk, hemp, wool, angora, and mohair, synthetic fibers such as polyester, polyethylene, polypropylene, nylon, acrylic, spandex, and blended fibers combining these are all Valid. In addition, there is no limitation in its form and shape, and it is not limited to the shape of raw materials such as staples, filaments, etc. becomes this

As a method of using the anti-absorption agent, the amino-modified silicone emulsion composition may be applied to the target as it is, or may be applied after dilution with water. When diluting, although there is no restriction|limiting in particular in a density|concentration, What is necessary is just to dilute so that content of the amino-modified silicone of (A) component may be set to 0.05-5 mass %. When this content is less than 0.05 mass %, there exists a possibility that it may become impossible to provide sufficient waterproofness to an object. As an application amount, it is preferable that the silicone oil content is 0.001-5g with respect to 1m< ² > of a base material. It is preferable to heat-treat the absorption inhibitor after application, and the heating temperature may be appropriately selected from 50 to 200° C. and the heating time from 10 seconds to 5 minutes.

[cardboard]

The paperboard of the present invention is a paperboard treated for absorption prevention, which is obtained by applying an absorption inhibitor comprising the amino-modified silicone emulsion composition to at least one surface of a paperboard substrate and then heat-treating it. The paperboard, the treatment method of the absorbent agent, etc. are as described above.

(Example)

Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples. In addition, when a compounding product name is described, a compounding quantity is the compounding quantity of a compounding product.

The raw materials used for the Example and the comparative example are shown.

(A) amino-modified silicone

The viscosity in 25 degreeC is the value measured with the BM type|mold viscometer (made by Tokyo Keiki Corporation).

The amino group equivalent is a value measured by an automatic titration device (manufactured by Hiranuma Sangyo Co., Ltd.).

For the amounts of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane, 0.1 g of a measurement sample was added to 10 mL of acetone, followed by shaking for about 2 hours. After extracting the cyclic low molecular weight siloxane into the acetone solution by shaking, the acetone solution of the supernatant was measured by gas chromatography (Agilent 7890B (made by Agilent Technologies)). For the column of gas chromatography, DB-5MS (manufactured by Agilent Technologies) was used, and the column internal temperature at the time of measurement was 300°C, and tetradecane was used as a label-resistant substance.

(A-1) amino-modified silicone

Amino-modified silicone 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: 4,900 mPa·s, amino group equivalent: 1,650 g/mol

(A-1) The amount of octamethylcyclotetrasiloxane in a component: Less than 0.01 mass % (less than a detection limit)

(A-1) Amount of decamethylcyclopentasiloxane in component: 0.01 mass %

(A-1) Amount of dodecamethylcyclohexasiloxane in component: 0.04 mass %

(A-1) Manufacturing method

92.61 parts by mass of octamethylcyclotetrasiloxane, 4.49 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, to a separable flask equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen gas inlet tube; 2.80 mass parts of dimethyl silicone represented by Formula (3), and 0.07 mass parts of potassium siliconate were heated at 120 degreeC for 8 hours, and equilibration reaction was performed. Then, 0.03 mass parts of epichlorohydrin was added, it heated at 70 degreeC for 2 hours, and neutralized reaction.

Then, under the conditions of 130 degreeC and 15 mmHg or less, the pressure reduction strip was implemented for 20 hours, the low boiling point oil component was removed, and the oily compound (A-1) was obtained.

(A-2) amino-modified silicone

Amino-modified silicone 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=350, c=3.5, d=0, e=0, Viscosity: 2,600 mPa·s, amino group equivalent: 3,600 g/mol

(A-2) The amount of octamethylcyclotetrasiloxane in a component: Less than 0.01 mass %

(A-2) Amount of decamethylcyclopentasiloxane in component: 0.02 mass %

(A-2) Amount of dodecamethylcyclohexasiloxane in component: 0.03 mass %

(A-2) Manufacturing method

According to the production method of (A-1), 94.11 parts by mass of octamethylcyclotetrasiloxane, 2.19 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and the formula (3 ), amino-modified silicone (A-2) was obtained in the same manner as in the production method of (A-1) except that the amount was 3.60 parts by mass of dimethyl silicone. In addition, the amounts of potassium siliconate and epichlorohydrin are the same as in (A-1).

(A-3) amino-modified silicone

It is expressed by the above average formula (1) and

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: 1,500 mPa s, Amino equivalent: 1,700 g/mol

(A-3) Amount of octamethylcyclotetrasiloxane in component: 0.02 mass %

(A-3) Amount of decamethylcyclopentasiloxane in component: 0.04 mass %

(A-3) Amount of dodecamethylcyclohexasiloxane in component: 0.06 mass %

(A-3) Manufacturing method

According to the production method of (A-1), 91.20 parts by mass of octamethylcyclotetrasiloxane, 4.40 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and the formula (3 ), amino-modified silicone (A-3) was obtained in the same manner as in the production method of (A-1) except that it was set to 4.30 parts by mass of dimethyl silicone. In addition, the amounts of potassium siliconate and epichlorohydrin are the same as in (A-1).

(A-4) amino-modified silicone

(A-4) amino-modified silicone

It is expressed 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: 1,660 mPa·s, amino group equivalent: 1,000 g/mol

(A-4) The amount of octamethylcyclotetrasiloxane in a component: 0.02 mass %

(A-4) Amount of decamethylcyclopentasiloxane in component: 0.03 mass %

(A-4) Amount of dodecamethylcyclohexasiloxane in component: 0.03 mass %

(A-4) Manufacturing method

According to the manufacturing method of (A-1), 95.81 mass parts of octamethylcyclotetrasiloxane, 0.71 mass parts of hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, said formula (3 ), amino-modified silicone (A-4) was obtained in the same manner as in the production method of (A-1) except that it was 3.38 parts by mass of dimethyl silicone. In addition, the amounts of potassium siliconate and epichlorohydrin are the same as in (A-1).

(A-5) amino-modified silicone

It is expressed 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: 13,000 mPa·s, Amino group equivalent: 1,800 g/mol

(A-5) The amount of octamethylcyclotetrasiloxane in a component: 0.03 mass %

(A-5) Amount of decamethylcyclopentasiloxane in component: 0.05 mass %

(A-5) Amount of dodecamethylcyclohexasiloxane in component: 0.06 mass %

(A-5) Manufacturing method

According to the production method of (A-1), 93.88 parts by mass of octamethylcyclotetrasiloxane, 4.27 parts by mass of hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and the formula (3 ), amino-modified silicone (A-5) was obtained in the same manner as in the production method of (A-1) except that it was 1.84 parts by mass of dimethyl silicone. In addition, the amounts of potassium silicate and epichlorohydrin are the same as in (A-6).

(A-6) amino-modified silicone (comparative)

It is expressed 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=37, c=1.1, d=0, e=0, Viscosity: 40 mPa s, amino group equivalent: 1,500 g/mol

(A-6) The amount of octamethylcyclotetrasiloxane in a component: 2.5 mass %

(A-6) Amount of decamethylcyclopentasiloxane in component: 2.0 mass %

(A-6) Amount of dodecamethylcyclohexasiloxane in component: 1.5 mass %

(A-6) Manufacturing method

59.50 parts by mass of octamethylcyclotetrasiloxane, 5.81 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, to a separable flask equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen gas inlet tube; 34.59 mass parts of dimethyl silicones represented by Formula (3), and 0.07 mass parts of potassium siliconate were heated at 110 degreeC for 8 hours, and equilibration reaction was performed. Then, 0.03 mass parts of epichlorohydrin was added, it heated at 80 degreeC for 3 hours, neutralization reaction was performed, and the oily compound (A-6) was obtained.

(A-7) amino-modified silicone (comparative)

It is expressed 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=37, c=1.1, d=0, e=0, Viscosity: 55 mPa·s, amino group equivalent: 1,500 g/mol

(A-7) The amount of octamethylcyclotetrasiloxane in a component: 0.01 mass %

(A-7) Amount of decamethylcyclopentasiloxane in component: 0.02 mass %

(A-7) Amount of dodecamethylcyclohexasiloxane in component: 0.02 mass %

(A-7) Manufacturing method

59.50 parts by mass of octamethylcyclotetrasiloxane, 5.81 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, to a separable flask equipped with a thermometer, a stirring device, a reflux condenser and a nitrogen gas inlet tube; 34.59 mass parts of dimethyl silicones represented by Formula (3), and 0.07 mass parts of potassium siliconate were heated at 110 degreeC for 8 hours, and equilibration reaction was performed. Then, 0.03 mass parts of epichlorohydrin was added, it heated at 80 degreeC for 3 hours, and neutralized reaction. Then, under the conditions of 110 degreeC and 15 mmHg or less, the pressure reduction strip was implemented for 10 hours, the low boiling point oil component was removed, and the oily compound (A-7) was obtained.

(A-8) amino-modified silicone (comparative)

It is represented by the average composition formula (1),

R ¹ :-CH ₃ , R ² :-C ₃ H ₆ NH ₂ , R ³ :-CH ₃ , a=2, b=900, c=2, d=0, e=0, viscosity: 18,000 mPa s, amino group equivalent: 33,000 g/mol

(A-8) The amount of octamethylcyclotetrasiloxane in a component: 3.5 mass %

(A-8) Amount of decamethylcyclopentasiloxane in component: 2.8 mass %

(A-8) Amount of dodecamethylcyclohexasiloxane in component: 2.1 mass %

(A-8) Manufacturing method

According to the production method of (A-6), 98.03 parts by mass of octamethylcyclotetrasiloxane, 0.37 parts by mass of a hydrolyzate of 3-aminopropylmethyldiethoxysilane, and 1.50 parts by mass of dimethyl silicone represented by the formula (3) Amino-modified silicone (A-8) was obtained by the method similar to the manufacturing method of (A-6) except having set it as parts by mass. In addition, the amounts of potassium siliconate and epichlorohydrin are the same as in (A-6).

(A-9) amino-modified silicone (comparative)

It is expressed 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=600, c=15, d=0, e=0, Viscosity: 3,600 mPa·s, amino group equivalent: 1,650 g/mol

(A-9) The amount of octamethylcyclotetrasiloxane in a component: 1.6 mass %

(A-9) The amount of decamethylcyclopentasiloxane in a component: 1.6 mass %

(A-9) Amount of dodecamethylcyclohexasiloxane in component: 1.3 mass %

(A-9) Manufacturing method

According to the production method of (A-6), 92.61 parts by mass of octamethylcyclotetrasiloxane, 4.49 parts by mass of a hydrolyzate of 2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and the formula (3 ), amino-modified silicone (A-8) was obtained in the same manner as in the production method of (A-6), except that it was set to 2.80 parts by mass of dimethyl silicone. In addition, the amounts of potassium siliconate and epichlorohydrin are the same as in (A-6).

(B) Surfactant

Nucol 1310 (brand name): Nippon New Chemical Co., Ltd. make, polyoxyethylene tridecyl ether, HLB value = 13.7

Nucol 1004 (brand name): Nippon New Chemicals Co., Ltd. make, polyoxyethylene octyl ether, HLB value = 11.5

[Example 1]

(A) amino-modified silicone A-1 (viscosity: 4,900 mPa·s, amino group equivalent: 1,650 g/mol): 100 parts by mass, (B) Nucol 1310: 16.7 parts by mass, (C) ion-exchanged water: 213.9 parts by mass , acetic acid: 2.8 parts by mass were mixed using a homomixer and emulsified and dispersed to obtain an amino-modified silicone emulsion composition (I-1) having a non-volatile content of 35% by mass at 105°C and 3 hours.

[Example 2]

(A) amino-modified silicone (A-1) (viscosity: 4,900 mPa·s, amino group equivalent: 1,650 g/mol): 100 parts by mass, (B) Nucol 1310: 10 parts by mass, (C) ion-exchanged water: 220.5 An amino-modified silicone emulsion composition (I-2) having a non-volatile content of 33 mass % at 105° C. and 3 hours was obtained by mixing and emulsifying and dispersing 2.8 parts by mass of acetic acid using a homomixer.

[Example 3]

(A) amino-modified silicone (A-2) (viscosity: 2,600 mPa·s, amino equivalent: 3,600 g/mol): 100 parts by mass, (B) Nucol 1310: 10.0 parts by mass, (C) ion-exchanged water: 222.1 An amino-modified silicone emulsion composition (I-3) was obtained by mixing and emulsifying and dispersing 1.3 parts by mass of acetic acid: 1.3 parts by mass using a homomixer, and having a non-volatile content of 33% by mass at 105°C and 3 hours.

[Example 4]

(A) amino-modified silicone (A-3) (viscosity: 1,500 mPa s, amino equivalent: 1,700 g/mol): 100 parts by mass, (B) Nucol 1310: 10.0 parts by mass, (C) ion-exchanged water: 220.6 An amino-modified silicone emulsion composition (I-4) having 33 mass % of a non-volatile matter at 105° C. and 3 hours was obtained by mixing and emulsifying and dispersing parts by mass, acetic acid: 2.7 parts by mass using a homomixer.

[Example 5]

(A) amino-modified silicone (A-4) (viscosity: 1,660 mPa·s, amino equivalent: 11,000 g/mol): 100 parts by mass, (B) Nucol 1310: 10.0 parts by mass, (C) ion-exchanged water: 222.9 An amino-modified silicone emulsion composition (I-5) was obtained by mixing and emulsifying and dispersing an acetic acid: 0.4 parts by mass using a homomixer, and having a non-volatile content of 33% by mass at 105°C for 3 hours.

[Example 6]

(A) amino-modified silicone (A-5) (viscosity: 13,000 mPa·s, amino group equivalent: 1,800 g/mol): 100 parts by mass, (B) Nucol 1310: 10.0 parts by mass, (C) ion-exchanged water: 220.8 An amino-modified silicone emulsion composition (I-6) having a non-volatile content of 33 mass% at 105°C and 3 hours was obtained by mixing and emulsifying and dispersing 2.6 parts by mass of acetic acid using a homomixer.

[Example 7]

(A) amino-modified silicone (A-1) (viscosity: 4,900 mPa·s, amino group equivalent: 1,650 g/mol): 100 parts by mass, (B) Nucol 1004: 50.0 parts by mass, (C) ion-exchanged water: 180.53 An amino-modified silicone emulsion composition (I-6) having a non-volatile content of 45% by mass at 105°C and 3 hours by mass was mixed and emulsified and dispersed using a homomixer to obtain an amino-modified silicone emulsion composition (I-6).

[Comparative Example 1]

(A) amino-modified silicone (A-6) (viscosity: 40 mPa·s, amino group equivalent: 1,500 g/mol): 100 parts by mass, (B) Nucol 1310: 10.0 parts by mass, (C) ion-exchanged water: 220.3 mass Parts, acetic acid: 3.1 parts by mass were mixed using a homomixer and emulsified and dispersed to obtain an amino-modified silicone emulsion composition (II-1) having a nonvolatile content of 33% by mass at 105°C and 3 hours.

[Comparative Example 2]

(A) amino-modified silicone (A-7) (viscosity: 55 mPa·s, amino group equivalent: 1,500 g/mol): 100 parts by mass, (B) Nucol 1310: 10.0 parts by mass, (C) ion-exchanged water: 220.3 mass Parts and acetic acid: 3.1 parts by mass were mixed using a homomixer and emulsified and dispersed to obtain an amino-modified silicone emulsion composition (II-2) having a non-volatile content of 33% by mass at 105°C and 3 hours.

[Comparative Example 3]

(A) amino-modified silicone (A-8) (viscosity: 18,000 mPa·s, amino equivalent: 33,000 g/mol): 100 parts by mass, (B) Nucol 1310: 10.0 parts by mass, (C) ion-exchanged water: 223.2 An amino-modified silicone emulsion composition (II-3) having a non-volatile content of 33 mass % at 105° C. and 3 hours was obtained by mixing and emulsifying and dispersing 0.1 parts by mass of acetic acid using a homomixer.

[Comparative Example 4]

(A) amino-modified silicone (A-9) (viscosity: 3,600 mPa·s, amino group equivalent: 1,650 g/mol): 100 parts by mass, (B) Nucol 1310: 10.0 parts by mass, (C) ion-exchanged water: 220.5 An amino-modified silicone emulsion composition (II-4) having a non-volatile content of 33 mass% at 105°C and 3 hours was obtained by mixing and emulsifying and dispersing 2.8 parts by mass of acetic acid using a homomixer.

[Comparative Example 5]

(A) amino-modified silicone (A-9) (viscosity: 3,600 mPa·s, amino group equivalent: 1,650 g/mol): 100 parts by mass, (B) Nucol 1004: 50.0 parts by mass, (C) ion-exchanged water: 180.5 An amino-modified silicone emulsion composition (II-5) having 33 mass % of a non-volatile matter at 105° C. and 3 hours was obtained by mixing and emulsifying and dispersing 2.8 parts by mass of acetic acid using a homomixer.

[Comparative Example 6]

(A) the following formula (4)

Silicone oil having no amino group in the molecule (viscosity: 10,000 mPa s, containing octamethylcyclotetrasiloxane content: 0.01 mass % or less): 100 parts by mass, (B) Nucol 1310: 15.0 parts by mass, (C) ) Ion-exchanged water: 218.3 parts by mass were mixed using a homomixer and emulsified and dispersed to obtain a silicone emulsion composition (II-6) having 34.5 mass% of nonvolatile matter at 105°C and 3 hours.

About the obtained silicone emulsion composition, "water absorption" and "dilution stability" were evaluated by the following method. (A) The result is written together in a table together with the amino-modified silicone physical property.

[Absorption rate]

The silicone emulsion composition was further diluted with water so that the silicone content was 0.5% by mass, and then applied to the surface of a work paperboard having a size of 100 mm × 100 mm and a thickness of 0.38 mm using a paper gauze. Then, the cardboard was dried by heating at 120° C. for 5 minutes, and the weight was measured (weight A), then floated on the water surface for 1 minute with the silicone-treated side down, and then the water droplets were wiped off and the weight of the cardboard was measured (weight B). ) The water absorption was calculated according to the following formula. In terms of water absorption, it can be said that the smaller the value, the better the water absorption prevention property. The results are shown in the table below.

Absorption rate (%)=100(B-A)/A

[dilution stability]

A solution obtained by diluting the silicone emulsion composition 100 times (by mass) with tap water was placed in a glass beaker, and the presence or absence of separation when stored at 25°C for 20 hours was visually confirmed. It evaluated as "dilution stability" based on the following index|index. The results are shown in the table below.

○: No precipitate

△: Slightly precipitated

×: There is a precipitate

As is clear from the above results, the amino-modified silicone emulsion composition of the present invention has excellent absorption prevention properties and good dilution stability. Moreover, there is little content of cyclic low molecular weight siloxane, and the load on the environment is low.

(Industrial Applicability)

The absorption inhibitor of the present invention has excellent absorption prevention properties and good dilution stability. Moreover, there is little content of cyclic low molecular weight siloxane, and the load on the environment is low. It is useful as an absorbent inhibitor for cardboard.

Claims (8)

(A) The following average composition formula (1)

[Wherein, R ¹ is independently of each other an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ² is each independently of the general formula (2)

(R ⁴ and R ⁵ are each independently a divalent organic group having 1 to 6 carbon atoms, and p is 0 or 1.)
is a group represented by , and R ³ is a group independently selected from R ¹ and R ² , or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , a, b, c, d and e is a number satisfying the following ranges: 2≤a≤10, 10≤b≤1,000, 0≤c≤50, 0≤d≤5, and 0≤e≤5. However, when c=0, R ³ is R ² ]
An amino-modified silicone having an amino group equivalent of 500 to 20,000 g/mol and an octamethylcyclotetrasiloxane content of 1% by mass or less: 100 mass part,
(B) At least one surfactant selected from nonionic surfactants, anionic surfactants, cationic surfactants and cationic surfactants (however, polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether are excluded. ): 5 to 100 parts by mass, and
(C) Water: 10 to 2,000 parts by mass
An anti-absorption agent comprising an amino-modified silicone emulsion composition containing The absorption inhibitor according to claim 1, wherein the content of decamethylcyclopentasiloxane in component (A) is 1% by mass or less. The absorption inhibitor according to claim 1 or 2, wherein the content of dodecamethylcyclohexasiloxane in component (A) is 1% by mass or less. The absorption inhibitor according to any one of claims 1 to 3, wherein the component (B) is a surfactant containing a nonionic surfactant. The absorption inhibitor according to claim 4, wherein (B) the nonionic surfactant is a nonionic surfactant having an HLB value of 15.0 or less. The absorption inhibitor according to any one of claims 1 to 5, wherein the component (B) is a surfactant that does not contain a cationic surfactant. The absorption inhibitor according to any one of claims 1 to 6, which is an absorption inhibitor for paper. A paperboard subjected to absorption prevention treatment, wherein the absorption inhibitor according to any one of claims 1 to 6 is applied to at least one surface of a paperboard substrate and then heat-treated.