WO2021132057A1

WO2021132057A1 - Water absorption-preventing agent and paperboard

Info

Publication number: WO2021132057A1
Application number: PCT/JP2020/047361
Authority: WO
Inventors: 優太濱嶋
Original assignee: 信越化学工業株式会社
Priority date: 2019-12-24
Filing date: 2020-12-18
Publication date: 2021-07-01
Also published as: JPWO2021132057A1; TW202132416A; CN114846097A; KR20220119135A; JP7414079B2

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°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

Water absorption inhibitor and paperboard

The present invention relates to a water absorption inhibitor made of an amino-modified silicone emulsion and a paperboard using the same. More specifically, the present invention relates to a water absorption inhibitor which is highly effective as a water repellent for paper and has a low environmental load.

Conventionally, a large amount of gypsum board has been used as a building material. As is well known, a gypsum board is a plate-like body in which multi-layered paperboard is firmly bonded and fixed on both sides of a hydration-cured gypsum board, and the paperboard used in this case has a high strength of the paperboard itself. It is required to have various characteristics such as moisture absorption resistance, small dimensional change during wetting, and as high air permeability as possible.

Among these properties, moisture absorption resistance and dimensional stability during wetness are particularly important, and water absorption is prevented on the surface of the paperboard for the purpose of improving moisture absorption resistance and suppressing dimensional changes during wetness. Processing has been performed to impart sex. As a treatment method in this case, the treatment with a silicone resin is widely performed in combination with the fact that the air permeability is less likely to be impaired. As the silicone resin in this treatment, various modified silicone oils including dimethyl silicone oil are considered to be effective, and many emulsions using these have been proposed as suitable surface treatment agents.

However, for example, a method using an epoxy-modified silicone oil disclosed in US Pat. No. 3,389,042 cannot obtain a sufficient water absorption prevention effect, and is disclosed in Japanese Patent Publication No. 56-47994. When a mercapto group-containing silicone oil is used as the main agent, a high water absorption prevention effect can be obtained, but there is a drawback that it is not preferable in the working environment because the offensive odor peculiar to the mercapto group is extremely strong.

Japanese Patent Publication No. 08-022555 proposes a technique for obtaining a water-repellent effect by using an amino-modified silicone having a specific viscosity and amine equivalent. However, polyoxyethylene nonylphenol ether is used as an emulsifier, and octamethylcyclotetrasiloxane is used as a diluent. Polyoxyethylene nonylphenyl ether is listed as a substance of very high concern in the EU's REACH regulation. In recent years, cyclic low-molecular-weight siloxanes (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane) have become a concern as environmentally hazardous substances, and regulations are being tightened in each country. Products with reduced contents of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane have been demanded. From the above background, it has been required to provide both high water absorption prevention property and low environmental load.

U.S. Pat. No. 3,389,042 Special Publication No. 56-47994 Special Fair 08-025255

In view of the above problems of the prior art, an object of the present invention is to provide a water absorption inhibitor having an excellent effect of preventing water absorption, having good dilution stability, and having a reduced content of environmentally hazardous substances. In addition, "good dilution stability" means the stability after diluting the water absorption inhibitor with a certain amount of water and storing it, as described in the evaluation method of Examples described later.

As a result of diligent studies to achieve the above object, the present inventor has provided an amino-modified silicone emulsion composition containing the following components (A) to (C) with excellent water absorption prevention properties and dilution stability. We have found that it is good and can reduce the content of environmentally hazardous substances, and have come to the present invention.

Therefore, the present invention provides the following water absorption inhibitor and paperboard.
1. 1. (A) The following average composition formula (1)

[In the formula, R ¹ is an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other, and R ² is independent of each other in the general formula (2).
^{^{-R 4 - (NH-R 5}} -) p NH 2 (2)
(R ⁴ and R ⁵ are divalent organic groups having 1 to 6 carbon atoms independently of each other, and p is 0 or 1.)
R ³ is ^{a group selected from the choices of R 1} and R ² , or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , and a, b. , C, d and e are numbers that satisfy the ranges of 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 . ]
Amino-modified silicone having a viscosity at 25 ° C. of 800 to 100,000 mPa · s and an amino group equivalent of 500 to 20,000 g / mol, and having an octamethylcyclotetrasiloxane content of 1% by mass. Amino-modified silicone: 100 parts by mass,
(B) One or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants (provided that polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether are used. Excludes): A water absorption inhibitor comprising an amino-modified silicone emulsion composition containing 5 to 100 parts by mass and (C) water: 10 to 2,000 parts by mass.
2. (A) The water absorption inhibitor according to 1, wherein the content of decamethylcyclopentasiloxane in the component is 1% by mass or less.
3. 3. (A) The water absorption inhibitor according to 1 or 2, wherein the content of dodecamethylcyclohexanesiloxane in the component is 1% by mass or less.
4. The water absorption inhibitor according to any one of 1 to 3, wherein the component (B) is a surfactant containing a nonionic surfactant.
5. (B) The water absorption inhibitor according to 4, wherein the nonionic surfactant is a nonionic surfactant having an HLB value of 15.0 or less.
6. The water absorption inhibitor according to any one of 1 to 5, wherein the component (B) is a surfactant that does not contain a cationic surfactant.
7. The water absorption inhibitor according to any one of 1 to 6, which is a water absorption inhibitor for paper.
A paperboard that has been subjected to a water absorption prevention treatment, which is obtained by applying the water absorption inhibitor according to any one of 8.1 to 6 to at least one surface of a paperboard base material and then heat-treating the paperboard.

The amino-modified silicone emulsion composition of the present invention has an excellent water absorption prevention effect, good dilution stability, can reduce the content of environmentally hazardous substances, and has a small environmental load. When this composition is used as a waterproofing agent, it is possible to impart excellent water absorption prevention properties to paperboard and the like.

Hereinafter, the present invention will be described in detail.
[(A) component]
(A) The following average composition formula (1)

[In the formula, R ¹ is an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other, and R ² is independent of each other in the general formula (2).
^{^{-R 4 - (NH-R 5}} -) p NH 2 (2)
(R ⁴ and R ⁵ are divalent organic groups having 1 to 6 carbon atoms independently of each other, and p is 0 or 1.)
R ³ is ^{a group selected from the choices of R 1} and R ² , or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ , and a, b. , C, d and e are numbers that satisfy the ranges of 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 . ]
Amino-modified silicone having a viscosity at 25 ° C. of 800 to 100,000 mPa · s and an amino group equivalent of 500 to 20,000 g / mol, and having an octamethylcyclotetrasiloxane content of 1% by mass. The following amino-modified silicones can be used alone or in combination of two or more.

R ¹ is an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other. For example, alkyl groups such as 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 and octadecyl group: Alkenyl groups such as vinyl group, allyl group, 5-hexenyl group and oleyl group: aryl groups such as phenyl group, tolyl group and naphthyl group can be mentioned. Of these, a methyl group, a long-chain (6 to 20 carbon atoms) alkyl group, and a phenyl group are preferable, and a methyl group is more preferable.

R ² are independent of each other, and the general formula (2)
^{^{-R 4 - (NH-R 5}} -) p NH 2 (2)
(R ⁴ and R ⁵ are divalent organic groups having 1 to 6 carbon atoms independently of each other, and p is 0 or 1.)
It is a group represented by. Examples of the divalent organic group having 1 to 6 carbon atoms include a divalent hydrocarbon group such as an alkylene group, an alkaneylene group and an arylene group. Examples of the group represented by the general formula (2) include a 2-aminoethyl group, a 3-aminopropyl group, a 6-aminohexyl group, an N- (2-aminoethyl) -3-aminopropyl group, and an N-. (3-Aminopropyl) -3-aminopropyl group, N- (2-aminoethyl) -6-aminohexyl group and the like can be mentioned. Of these, a 3-aminopropyl group or an N- (2-aminoethyl) -3-aminopropyl group is preferable from the viewpoint of easy availability of raw materials.

R ³ ^{is a group selected from the choices of R 1} and R ² or a group selected from -OH, -OCH ₃ and -OC ₂ H ₅ independently of each other, and when c = 0, R ³ is R ² . is there. 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 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. Further, it is preferable that the content 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. If 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 may be too small and the emulsion stability may be deteriorated. 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, and d = 0 is preferable. When d exceeds 5, the viscosity of the amino-modified silicone becomes too high and the emulsion stability deteriorates.

E is 0 ≦ e ≦ 5, and e = 0 is preferable. When e exceeds 5, the viscosity of the amino-modified silicone becomes too high and the emulsion stability deteriorates.

The viscosity of the component (A) 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 is less than the above lower limit, the water absorption prevention property deteriorates. Further, if the above upper limit value is exceeded, the emulsification stability deteriorates. In the present invention, the viscosity is a value measured by a BM type viscometer (for example, manufactured by Tokyo Keiki Co., Ltd.). The rotor, rotation speed, and rotation time are appropriately selected based on a conventional method according to the viscosity.

The amino group equivalent of the component (A) is 500 to 20,000 g / mol, preferably 800 to 15,000 g / mol, and even more preferably 1,000 to 13,000 g / mol. If the amino group equivalent is less than the lower limit, there are too many amino groups, and the water absorption prevention property is deteriorated. On the other hand, when the amino group equivalent exceeds the above upper limit value, the number of amino groups is too small, so that the hydrophilicity to be given as the amino-modified silicone is insufficient, which deteriorates the emulsion stability. The amino group equivalent in the present invention is the number of grams of the amino-modified silicone to be neutralized with 1 mol of hydrochloric acid, and theoretically, it is the molecular weight / the number of nitrogen atoms. The amine equivalent can be measured by a neutralization titration method, for example, an automatic titration device manufactured by Hiranuma Sangyo Co., Ltd.

The content of octamethylcyclotetrasiloxane in the component (A) 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 further preferably 0.1% by mass or less.
The content of dodecamethylcyclohexanesiloxane is preferably 1% by mass or less. It is more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less. The amounts of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the component (A) can be measured by gas chromatography. Specifically, 0.1 g of a measurement sample is added to 10 mL of acetone, and the mixture is shaken for about 2 hours. After extracting the cyclic low molecular weight siloxane into the acetone solution by shaking, the supernatant acetone solution is measured by gas chromatography.

(A) Amino-modified silicone can be easily obtained by a known synthetic 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 an equilibrium reaction with aminopropyldimethoxymethylsilane or a hydrolyzate thereof, and a compound selected from hexamethyldisiloxane or the like as another raw material.

When the component (A) is synthesized, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane are produced as by-products depending on the production method. Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethyl In order to reduce the content of cyclohexasiloxane to 1% by mass or less, it is preferable to carry out a step of removing the volatile component of the obtained component (A). Octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane in the component (A) can be removed by a known method. For example, octamethylcyclotetrasiloxane and decamethyl in the component (A) are distilled off under reduced pressure at 80 to 150 ° C. for 5 to 40 hours under the condition of 30 mmHg or less while blowing nitrogen gas into the component (A). Cyclopentasiloxane and dodecamethylcyclohexasiloxane can be contained in an amount of 1% by mass or less in the component (A).

[(B) component]
The component (B) is one or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants (provided that polyoxyethylene nonylphenyl ether and polyoxyethylene octyl). (Excluding phenyl ether), and one type can be used alone or two or more types can be used in combination as appropriate.

Examples of the nonionic surfactant include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ether and polyoxyethylene propylene alkyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Examples of the polyoxyethylene alkyl ether include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and the like. Examples of the oxyethylene propylene alkyl ether include polyoxyethylene propylene decyl ether, polyoxyethylene propylene lauryl ether, and polyoxyethylene propylene tridecyl ether. Of these, polyoxyalkylene alkyl ethers are preferable, and polyoxyethylene alkyl ethers and polyoxyethylene propylene alkyl ethers are more preferable.

Examples of cationic surfactants include quaternary ammonium salts and alkylamine acetates. Examples of the anionic surfactant include alkyl sulfates, alkylbenzene sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates and the like.

As the surfactant of the component (B), a nonionic surfactant is essential and preferably contains a nonionic surfactant from the viewpoint of ease of emulsification of the amino-modified silicone. 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 further preferably an HLB value of 1.40 or less. The surfactant may be only a nonionic surfactant, or may be a combination of a nonionic surfactant and a surfactant selected from an anionic surfactant, a cationic surfactant and an amphoteric surfactant, but water absorption prevention. From the viewpoint of sex, it is preferable that the component (B) is only a nonionic surfactant, and from the viewpoint of water absorption prevention, it is preferable that the component (B) does not contain a cationic surfactant. HLB is a value calculated by the Griffin method.

The content of the component (B) is 5 to 100 parts by mass with respect to 100 parts by mass of the component (A), preferably 2 to 80 parts by mass, more preferably 3 to 70 parts by mass, and 4 to 60 parts by mass. More preferred. If the content of the component (B) is less than the above lower limit value, the dilution stability is deteriorated, and if it exceeds the above upper limit value, the water absorption prevention property is deteriorated.

[(C) component]
The component (C) is water, and all water such as ion-exchanged 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 with respect to 100 parts by mass of the component (A).

[Production method]
The amino-modified silicone emulsion composition of the present invention can be prepared, for example, by the following method.
It can be prepared by mixing the component (C) with the components (A) and (B) and emulsifying and dispersing them according to a conventional method. Of these, oil droplet (O / W type) emulsions in water are preferable. Further, water can be further added to the emulsion to dilute it, and the emulsion can be used for the purposes described later. The amount of water for dilution is not particularly limited and may be appropriately adjusted according to the intended use.

In the amino-modified silicone emulsion composition of the present invention, in addition to the above-mentioned components (A) to (C), various arbitrary components can be blended, if necessary, in an appropriate amount as long as the object of the present invention is not impaired. Examples of such an optional component include a silicone component other than the component (A), an additive, and the like.

Specific examples of the silicone component other than the component (A) include silicone oils such as dimethyl silicone oil, methylhydrogen silicone oil, methylphenyl silicone oil, and alkyl-modified silicone oil. When a silicone component other than the component (A) is blended, the amount thereof is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the component (A).

As an additive, for example, an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, stearic acid, lactic acid, or citric acid can be blended in order to improve emulsion stability. The amount of the additive can be set arbitrarily, but it is preferably an amount that adjusts the pH of the emulsion composition of the present invention to 3 to 7. Examples of other additives include thickeners, antifreeze agents, preservatives, rust inhibitors, antioxidants, ultraviolet absorbers and the like.

[Water absorption inhibitor]
Since the amino-modified silicone emulsion composition has an excellent water absorption-preventing effect and water-repellent effect, it is used as a water-absorbing inhibitor comprising the amino-modified silicone emulsion composition. Examples of the water absorption inhibitor include a water absorption inhibitor for paperboard, a water absorption inhibitor for fibers (fiber treatment agent), and the like. The paperboard is not particularly limited, and is also effective for corrugated cardboard base paper, paperboard for paper containers, miscellaneous paperboard and the like. The fibers are not particularly limited, and can be applied to natural fibers such as cotton, silk, linen, wool, angora and mohair, synthetic fibers such as polyester, polyethylene, polypropylene, nylon, acrylic and spandex, and blended fibers combining these. All are valid. Further, the form and shape are not limited, and the fiber of the present invention is not limited to the shape of raw materials such as staples, filaments, tows, threads, etc. It becomes a treatable target of the treatment agent.

As a method of using the water absorption inhibitor, the amino-modified silicone emulsion composition may be applied to the subject as it is, or it may be diluted with water and then applied. When diluting, the concentration is not particularly limited, but it is preferable to dilute so that the content of the amino-modified silicone of the component (A) is 0.05 to 5% by mass. If this content is less than 0.05% by mass, it may not be possible to impart sufficient waterproofness to the subject. As for the coating amount, it is preferable that the silicone oil content is 0.001 to 5 g with respect to ^{1 m 2 of the base material.} It is preferable to heat-treat the water absorption inhibitor after coating, and the heating temperature may be appropriately selected from 50 to 200 ° C. and the heating time may be appropriately selected from 10 seconds to 5 minutes.

[Paperboard]
The paperboard of the present invention is a paperboard that has been heat-treated after applying a water absorption inhibitor made of the amino-modified silicone emulsion composition to at least one surface of the paperboard base material. The method of treating the paperboard and the water absorption inhibitor is as described above.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The blending amount is the blending amount of the blended product when the blended product name is described.

The raw materials used in Examples and Comparative Examples are shown.
(A) Amino-modified silicone The viscosity at 25 ° C. is a value measured by a BM type viscometer (manufactured by Tokyo Keiki Co., Ltd.).
The amino group equivalent is a value measured by an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd.).
The amount of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane was obtained by adding 0.1 g of a measurement sample to 10 mL of acetone and shaking for about 2 hours. After extracting the cyclic low molecular weight siloxane into the acetone solution by shaking, the supernatant acetone solution was measured by gas chromatography (Agilent 7890B (manufactured by Agilent Technologies)). A DB-5MS (manufactured by Agilent Technologies) was used for the gas chromatography column, the temperature inside the column at the time of measurement was 300 ° C., and tetradecane was used as an internal standard 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) Amount of octamethylcyclotetrasiloxane in the component: less than 0.01% by mass (below the detection limit)
(A-1) Amount of decamethylcyclopentasiloxane in the component: 0.01% by mass
(A-1) Amount of dodecamethylcyclohexasiloxane in the component: 0.04% by mass

(A-1) Manufacturing Method In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, 92.61 parts by mass of octamethylcyclotetrasiloxane, 2- (aminoethyl) -3-amino. 4.49 parts by mass of the hydrolyzate of propylmethyldimethoxysilane, 2.80 parts by mass of dimethylsilicone represented by the following formula (3), and 0.07 parts by mass of potassium silicate are heated at 120 ° C. for 8 hours to equilibrate. The reaction was carried out. Then, 0.03 part by mass of epichlorohydrin was added, and the mixture was heated at 70 ° C. for 2 hours to carry out a neutralization reaction.
Then, a reduced pressure strip was carried out for 20 hours under the conditions of 130 ° C. and 15 mmHg or less to remove the low boiling point fraction to obtain an oily compound (A-1).

(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
Amount of octamethylcyclotetrasiloxane in the component (A-2): less than 0.01% by mass Amount of decamethylcyclopentasiloxane in the component (A-2): 0.02% by mass
(A-2) Amount of dodecamethylcyclohexasiloxane in the component: 0.03% by mass

(A-2) Production method According to the production method of (A-1), the raw materials are mixed with 94.11 parts by mass of octamethylcyclotetrasiloxane and 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. Amino-modified silicone (A-2) was prepared by the same method as in (A-1) except that the decomposition product was 2.19 parts by mass and 3.60 parts by mass of dimethyl silicone represented by the above formula (3). Obtained. The amounts of potassium silicate and epichlorohydrin are the same as in (A-1).

(A-3) 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 = 280, c = 6, d = 0, e = 0, viscosity: 1,500 mPa · s, amino group equivalent: 1,700 g / mol.
(A-3) Amount of octamethylcyclotetrasiloxane in the component: 0.02% by mass
(A-3) Amount of decamethylcyclopentasiloxane in the component: 0.04% by mass
(A-3) Amount of dodecamethylcyclohexasiloxane in the component: 0.06% by mass

(A-3) Production method According to the production method of (A-1), the raw materials are mixed with 91.20 parts by mass of octamethylcyclotetrasiloxane and 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. Amino-modified silicone (A-3) was prepared by the same method as in (A-1) except that the decomposition product was made 4.40 parts by mass and 4.30 parts by mass of dimethyl silicone represented by the above formula (3). Obtained. The amounts of potassium silicate and epichlorohydrin are the same as in (A-1).

(A-4) Amino Modified Silicone (A-4) 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 = 300, c = 1, d = 0, e = 0. , Viscosity: 1,660 mPa · s, Amino group equivalent: 11,000 g / mol
(A-4) Amount of octamethylcyclotetrasiloxane in the component: 0.02% by mass
(A-4) Amount of decamethylcyclopentasiloxane in the component: 0.03% by mass
(A-4) Amount of dodecamethylcyclohexasiloxane in the component: 0.03% by mass

(A-4) Production Method According to the production method of (A-1), the raw materials are mixed with 95.81 parts by mass of octamethylcyclotetrasiloxane and 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. Amino-modified silicone (A-4) was prepared by the same method as in (A-1) except that 0.71 parts by mass of the decomposed product and 3.38 parts by mass of dimethyl silicone represented by the above formula (3) were used. Obtained. The amounts of potassium silicate and epichlorohydrin are the same as in (A-1).

(A-5) 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 = 650, c = 14, d = 0, e = 0. , Viscosity: 13,000 mPa · s, Amino group equivalent: 1,800 g / mol
(A-5) Amount of octamethylcyclotetrasiloxane in the component: 0.03% by mass
(A-5) Amount of decamethylcyclopentasiloxane in the component: 0.05% by mass
(A-5) Amount of dodecamethylcyclohexasiloxane in the component: 0.06% by mass

(A-5) Production method According to the production method of (A-1), the raw materials are mixed with 93.88 parts by mass of octamethylcyclotetrasiloxane and 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. Amino-modified silicone (A-5) was prepared by the same method as in (A-1) except that the decomposition product was made 4.27 parts by mass and 1.84 parts by mass of dimethyl silicone represented by the above formula (3). Obtained. The amounts of potassium silicate and epichlorohydrin are the same as in (A-6).

(A-6) Amino-modified silicone (comparison)
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) Amount of octamethylcyclotetrasiloxane in the component: 2.5% by mass
(A-6) Amount of decamethylcyclopentasiloxane in the component: 2.0% by mass
(A-6) Amount of dodecamethylcyclohexasiloxane in the component: 1.5% by mass

(A-6) Manufacturing Method In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, 59.50 parts by mass of octamethylcyclotetrasiloxane, 2- (aminoethyl) -3-amino. 5.81 parts by mass of the hydrolyzate of propylmethyldimethoxysilane, 34.59 parts by mass of dimethylsilicone represented by the above formula (3), and 0.07 part by mass of potassium silicate are heated at 110 ° C. for 8 hours for an equilibrium reaction. Was done. Then, 0.03 part by mass of epichlorohydrin was added, and the mixture was heated at 80 ° C. for 3 hours to carry out a neutralization reaction to obtain an oily compound (A-6).

(A-7) Amino-modified silicone (comparison)
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) Amount of octamethylcyclotetrasiloxane in the component: 0.01% by mass
(A-7) Amount of decamethylcyclopentasiloxane in the component: 0.02% by mass
(A-7) Amount of dodecamethylcyclohexasiloxane in the component: 0.02% by mass

(A-7) Manufacturing method In a separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, 59.50 parts by mass of octamethylcyclotetrasiloxane, 2- (aminoethyl) -3-amino. 5.81 parts by mass of the hydrolyzate of propylmethyldimethoxysilane, 34.59 parts by mass of dimethylsilicone represented by the above formula (3), and 0.07 part by mass of potassium silicate are heated at 110 ° C. for 8 hours for an equilibrium reaction. Was done. Then, 0.03 part by mass of epichlorohydrin was added, and the mixture was heated at 80 ° C. for 3 hours to carry out a neutralization reaction. Then, a reduced pressure strip was carried out at 110 ° C. and 15 mmHg or less for 10 hours to remove the low boiling point fraction to obtain an oily compound (A-7).

(A-8) Amino-modified silicone (comparison)
It is represented by the above 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
Amount of octamethylcyclotetrasiloxane in the component (A-8): 3.5% by mass
(A-8) Amount of decamethylcyclopentasiloxane in the component: 2.8% by mass
(A-8) Amount of dodecamethylcyclohexasiloxane in the component: 2.1% by mass

(A-8) Production method According to the production method of (A-6), the raw materials were mixed in an amount of 98.03 parts by mass of octamethylcyclotetrasiloxane and 0.37 parts by mass of a hydrolyzate of 3-aminopropylmethyldiethoxysilane. Amino-modified silicone (A-8) was obtained in the same manner as in the production method of (A-6) except that the amount of dimethyl silicone represented by the above formula (3) was 1.50 parts by mass. The amounts of potassium silicate and epichlorohydrin are the same as in (A-6).

(A-9) Amino-modified silicone (comparison)
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
Amount of octamethylcyclotetrasiloxane in the component (A-9): 1.6% by mass
(A-9) Amount of decamethylcyclopentasiloxane in the component: 1.6% by mass
Amount of dodecamethylcyclohexasiloxane in the component (A-9): 1.3% by mass

(A-9) Production Method According to the production method of (A-6), the raw materials are mixed with 92.61 parts by mass of octamethylcyclotetrasiloxane and 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane. Amino-modified silicone (A-8) was prepared by the same method as in (A-6) except that the decomposition product was 4.49 parts by mass and 2.80 parts by mass of dimethyl silicone represented by the above formula (3). Obtained. The amounts of potassium silicate and epichlorohydrin are the same as in (A-6).

(B) Surfactant Newcol 1310 (trade name): Polyoxyethylene tridecyl ether manufactured by Nippon Emulsifier, HLB value = 13.7
Newcol 1004 (trade name): Made by Nippon Emulsifier, 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) Neucol 1310: 16.7 parts by mass, (C) ion Exchanged water: 213.9 parts by mass and acetic acid: 2.8 parts by mass are mixed using a homomixer to emulsify and disperse, and have an amino-modified silicone emulsion composition having a non-volatile content of 35% by mass at 105 ° C. for 3 hours. The thing (I-1) was obtained.

[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) Neucol 1310:10 parts by mass, (C) ion Exchanged water: 220.5 parts by mass and acetic acid: 2.8 parts by mass are mixed using a homomixer to emulsify and disperse, and have an amino-modified silicone emulsion composition having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. The thing (I-2) was obtained.

[Example 3]
(A) Amino-modified silicone (A-2) (viscosity: 2,600 mPa · s, amino group equivalent: 3,600 g / mol): 100 parts by mass, (B) Neucol 1310: 10.0 parts by mass, (C) ) Ion-exchanged water: 222.1 parts by mass and acetic acid: 1.3 parts by mass are mixed using a homomixer to emulsify and disperse, and an amino-modified silicone having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. An emulsion composition (I-3) was obtained.

[Example 4]
(A) Amino-modified silicone (A-3) (viscosity: 1,500 mPa · s, amino group equivalent: 1,700 g / mol): 100 parts by mass, (B) Neucol 1310: 10.0 parts by mass, (C) ) Ion-exchanged water: 220.6 parts by mass and acetic acid: 2.7 parts by mass are mixed using a homomixer to emulsify and disperse, and an amino-modified silicone having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. An emulsion composition (I-4) was obtained.

[Example 5]
(A) Amino-modified silicone (A-4) (viscosity: 1,660 mPa · s, amino group equivalent: 11,000 g / mol): 100 parts by mass, (B) Neucol 1310: 10.0 parts by mass, (C) ) Ion-exchanged water: 222.9 parts by mass and acetic acid: 0.4 parts by mass are mixed using a homomixer to emulsify and disperse, and an amino-modified silicone having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. An emulsion composition (I-5) was obtained.

[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) Neucol 1310: 10.0 parts by mass, (C) ) Ion-exchanged water: 220.8 parts by mass and acetic acid: 2.6 parts by mass are mixed using a homomixer to emulsify and disperse, and an amino-modified silicone having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. An emulsion composition (I-6) was obtained.

[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) Neucol 1004: 50.0 parts by mass, (C) ) Ion-exchanged water: 180.53 parts by mass and acetic acid: 2.8 parts by mass are mixed using a homomixer to emulsify and disperse, and an amino-modified silicone having a non-volatile content of 45% by mass at 105 ° C. for 3 hours. An emulsion composition (I-6) was obtained.

[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) Neucol 1310: 10.0 parts by mass, (C) ion Exchanged water: 220.3 parts by mass and acetic acid: 3.1 parts by mass are mixed using a homomixer to emulsify and disperse, and have an amino-modified silicone emulsion composition having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. The product (II-1) was obtained.

[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) Neucol 1310: 10.0 parts by mass, (C) ion Exchanged water: 220.3 parts by mass and acetic acid: 3.1 parts by mass are mixed using a homomixer to emulsify and disperse, and have an amino-modified silicone emulsion composition having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. The thing (II-2) was obtained.

[Comparative Example 3]
(A) Amino-modified silicone (A-8) (viscosity: 18,000 mPa · s, amino group equivalent: 33,000 g / mol): 100 parts by mass, (B) Neucol 1310: 10.0 parts by mass, (C) ) Ion-exchanged water: 223.2 parts by mass and acetic acid: 0.1 parts by mass are mixed using a homomixer to emulsify and disperse, and an amino-modified silicone having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. An emulsion composition (II-3) was obtained.

[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) Neucol 1310: 10.0 parts by mass, (C) ) Ion-exchanged water: 220.5 parts by mass and acetic acid: 2.8 parts by mass are mixed using a homomixer to emulsify and disperse, and an amino-modified silicone having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. An emulsion composition (II-4) was obtained.

[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) Neucol 1004: 50.0 parts by mass, (C) ) Ion-exchanged water: 180.5 parts by mass and acetic acid: 2.8 parts by mass are mixed using a homomixer to emulsify and disperse, and an amino-modified silicone having a non-volatile content of 33% by mass at 105 ° C. for 3 hours. An emulsion composition (II-5) was obtained.

[Comparative Example 6]
(A) The following formula (4)

Silicone oil having no amino group in the molecule (viscosity: 10,000 mPa · s, content of octamethylcyclotetrasiloxane: 0.01% by mass or less): 100 parts by mass, (B) Neucol 1310: 15.0 parts by mass, (C) ion-exchanged water: 218.3 parts by mass are mixed using a homomixer, emulsified and dispersed, and has a non-volatile content of 34.5% by mass at 105 ° C. for 3 hours. An emulsion composition (II-6) was obtained.

The obtained silicone emulsion composition was evaluated for "water absorption" and "dilution stability" by the following methods. (A) Amino-modified silicone The results are shown in the table together with the physical characteristics.

[Water 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 100 mm × 100 mm thick work paperboard using paper gauze. Next, this paperboard was heated and dried at 120 ° C. for 5 minutes, and the weight thereof was measured (weight A). After floating on the water surface for 1 minute with the silicone-treated surface facing down, water droplets were wiped off and the weight of the paperboard was measured (weight A). Weight B) The water absorption rate was determined according to the following formula. It can be said that the smaller the value of the water absorption rate, the better the water absorption prevention property. The results are shown in the table below.
Water absorption rate (%) = 100 (BA) / A

[Dilution stability]
A solution obtained by diluting the silicone emulsion composition 100 times (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 was evaluated as "dilution stability" based on the following indicators. The results are shown in the table below.
◯: No precipitate Δ: Slightly precipitated ×: With precipitate

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

The water absorption inhibitor of the present invention has excellent water absorption prevention properties and good dilution stability. Furthermore, the content of cyclic low molecular weight siloxane is low, and the burden on the environment is low. It is useful as a water absorption inhibitor for paperboard.

Claims

(A) The following average composition formula (1)

[In the formula, R 1 is an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms independently of each other, and R 2 is independent of each other in the general formula (2).
-R 4 - (NH-R 5 -) p NH 2 (2)
(R 4 and R 5 are divalent organic groups having 1 to 6 carbon atoms independently of each other, and p is 0 or 1.)
R 3 is a group selected from the choices of R 1 and R 2 , or a group selected from -OH, -OCH 3 and -OC 2 H 5 , and a, b. , C, d and e are numbers that satisfy the ranges of 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 . ]
Amino-modified silicone having a viscosity at 25 ° C. of 800 to 100,000 mPa · s and an amino group equivalent of 500 to 20,000 g / mol, and having an octamethylcyclotetrasiloxane content of 1% by mass. Amino-modified silicone: 100 parts by mass,
(B) One or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants (provided that polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether are used. Excludes): A water absorption inhibitor comprising an amino-modified silicone emulsion composition containing 5 to 100 parts by mass and (C) water: 10 to 2,000 parts by mass.
The water absorption inhibitor according to claim 1, wherein the content of decamethylcyclopentasiloxane in the component (A) is 1% by mass or less.
The water absorption inhibitor according to claim 1 or 2, wherein the content of dodecamethylcyclohexanesiloxane in the component (A) is 1% by mass or less.
The water absorption inhibitor according to any one of claims 1 to 3, wherein the component (B) is a surfactant containing a nonionic surfactant.
(B) The water absorption inhibitor according to claim 4, wherein the nonionic surfactant is a nonionic surfactant having an HLB value of 15.0 or less.
The water 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 water absorption inhibitor according to any one of claims 1 to 6, which is a water absorption inhibitor for paper.
A paperboard that has been heat-treated after applying the water absorption inhibitor according to any one of claims 1 to 6 to at least one surface of the paperboard base material.