JP4471105B2 - Hygiene softener composition - Google Patents

Description

  The present invention improves the flexibility and slipperiness of sanitary materials such as tissue paper, toilet paper, sanitary paper used in contact with the skin of disposable diapers, feminine hygiene products, sanitary nonwoven fabric, pulp filler for paper diapers, etc. In particular, the present invention relates to a sanitary softener composition that imparts superior flexibility and slipperiness without impairing the water absorption of the sanitary material.

  The sanitary paper or sanitary nonwoven fabric used in contact with the skin, such as tissue paper or toilet paper, is generally preferably soft. Sanitary paper is made by thinly processing paper to make it soft. The paper as a whole becomes soft, but the fibers on the surface cannot be treated, so the softness is inferior.

  As a method for solving these problems, a method of calendering the paper surface (Japanese Patent Laid-Open No. 5-76464: Patent Document 1) is known, but the volume is lowered and the volume feeling is impaired. In addition, a method of making paper soft by adding a hygroscopic agent (JP-A-5-156596: Patent Document 2) has been proposed, but has a drawback that the hygroscopicity changes greatly seasonally. Furthermore, a method for improving flexibility and smoothness by treatment with an emulsion composition comprising an amino group-containing organopolysiloxane, a surfactant and water (JP-A-2-224626: Patent Document 3, JP-A-3-900). Publication No .: Patent Document 4) has been proposed, but this composition has a disadvantage of poor storage stability, and imparting flexibility to tissue paper or toilet paper is not sufficient.

  As an improvement, a composition comprising an amino group-containing organopolysiloxane and a polyhydric alcohol has been proposed (Japanese Patent Laid-Open No. 7-145596: Patent Document 5). Moreover, a silicone oil emulsion (average particle size: 0.05 to 100 μm) containing crosslinked silicone particles has been proposed (Japanese Patent Laid-Open No. 2000-328486: Patent Document 6). Furthermore, a treatment agent comprising a crosslinked silicone particle-containing emulsion and an amino group-containing organopolysiloxane emulsion has been proposed (Japanese Patent Laid-Open No. 2000-154495: Patent Document 7). However, each of these treatment agents has a problem that improvement in the flexibility and slipperiness of sanitary paper such as tissue paper and toilet paper is insufficient.

JP-A-5-76464 JP-A-5-156596 JP-A-2-224626 Japanese Patent Laid-Open No. 3-900 JP-A-7-145596 JP 2000-328486 A JP 2000-154495 A

  The present invention has been made in view of the above circumstances, and sanitary paper such as tissue paper, toilet paper, paper diapers, and sanitary paper used in contact with the skin of feminine sanitary products, sanitary nonwoven fabrics, pulp fillers for paper diapers, and the like. It aims at providing the softening agent composition which can provide the softness | flexibility and slipperiness which were excellent in the material.

  As a result of intensive studies to achieve the above object, the present inventors have obtained (A) an amino-polyoxyalkylene group-containing organopolysiloxane, (B) a polyoxyalkylene group-containing organopolysiloxane, and (C) a surface activity. Sanitary paper, sanitary non-woven fabric, pulp for paper diapers used in contact with the skin of tissue paper, toilet paper, paper diapers, feminine hygiene products, etc., with a softener composition comprising an emulsion containing an agent and (D) water By treating sanitary materials such as fillers, it has been found that excellent flexibility and slipperiness can be imparted without impairing these water absorption properties, and the present invention has been made.

｛式中、Ｒは炭素数１〜２０の１価炭化水素基であり、Ａは下記一般式（２）
−Ｒ ¹ −（ＮＲ ² −Ｒ ³ ） _a −ＮＲ ⁴ Ｒ ⁵ （２）
［式中、Ｒ ¹ は炭素数１〜８の２価炭化水素基であり、Ｒ ² ，Ｒ ⁴ ，Ｒ ⁵ は水素原子又は下記一般式（３）
−ＣＨ ₂ ＣＨ（ＯＨ）ＣＨ ₂ Ｏ（Ｃ ₂ Ｈ ₄ Ｏ） _b （Ｃ ₃ Ｈ ₆ Ｏ） _c Ｒ ⁶ （３）
（式中、Ｒ ⁶ は水素原子、炭素数１〜８の１価炭化水素基又は炭素数２〜８のアシル基であり、ｂは２〜２０の整数、ｃは０〜１０の整数である。）
で示される１価の基で、式（３）で示される基をＲ ² ，Ｒ ⁴ 及びＲ ⁵ の全体の３０ｍｏｌ％以上含有するものであり、Ｒ ³ は炭素数１〜４の２価炭化水素基であり、ａは０〜４の整数である。］
で示される１価の基である。ＸはＲ，Ａ又は−ＯＲ ⁷ （但し、Ｒ ⁷ は水素原子又は炭素数１〜８の１価炭化水素基である。）であり、ｍは５〜５００の整数、ｎは０〜１００の整数であるが、ｎ＝０の場合、Ｘの少なくとも１個はＡである。｝
（Ｂ）ポリオキシアルキレン基含有オルガノポリシロキサン、
（Ｃ）界面活性剤、
（Ｄ）水
を含有することを特徴とする衛生材用柔軟剤組成物。
〔２〕（Ａ）成分のアミノ・ポリオキシアルキレン基含有オルガノポリシロキサンが、下記一般式（４）で示されるオルガノポリシロキサンと、下記一般式（５）で示されるポリオキシアルキレングリシジルエーテルとの反応により得られるものである〔１〕記載の衛生材用柔軟剤組成物。

［式中、Ｒは前記と同じであり、Ｂは下記一般式（６）
−Ｒ ¹ −（ＮＨ−Ｒ ³ ） _a ＮＨ ₂ （６）
（式中、Ｒ ¹ ，Ｒ ³ ，ａは前記と同じである。）で示される基であり、ＺはＲ，Ｂ又は−ＯＲ ⁷ （但し、Ｒ ⁷ は前記と同じである。）であり、ｍ，ｎは前記と同じであるが、ｎ＝０の場合、Ｚの少なくとも１個はＢである。］

（式中、Ｒ ⁶ ，ｂ，ｃは前記と同じである。）
〔３〕（Ｂ）成分のポリオキシアルキレン基含有オルガノポリシロキサンが、下記一般式（７）で示されるオルガノポリシロキサンである〔１〕又は〔２〕記載の衛生材用柔軟剤組成物。
Ｒ⁸ ₂ＸＳｉＯ−（Ｒ⁸ ₂ＳｉＯ）_r−（Ｒ⁸ＹＳｉＯ）_s−ＳｉＲ⁸ ₂Ｘ （７）
［但し、Ｒ⁸は炭素数１〜６の１価炭化水素基であり、Ｙは下記式（８）
−Ｒ⁹Ｏ−（Ｃ_pＨ_2pＯ）_q−Ｒ¹⁰ （８）
（式中、Ｒ⁹は炭素数３〜６の２価炭化水素基であり、Ｒ¹⁰は水素原子、炭素数１〜４の１価炭化水素基又は炭素数２〜４のアシル基であり、ｐは２〜４の整数、ｑは５〜５０の整数である。）
で表わされるポリオキシアルキレン含有基であり、Ｘは炭素数１〜４のアルコキシ基、水酸基、Ｒ⁸又はＹであり、ｒは１０〜２００の整数、ｓは０〜５０の整数であるが、ｓ＝０の場合、Ｘの少なくとも１個はＹである。］
〔４〕処理される基材が、紙又は不織布である〔１〕，〔２〕又は〔３〕記載の衛生材用柔軟剤組成物。

Therefore, this invention provides the softener composition for sanitary materials shown below.
[1] (A) An aminopolyoxyalkylene group-containing organopolysiloxane represented by the following general formula (1) :

{Wherein R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is the following general formula (2)
-R ^1- (NR ² -R ³ ) _a -NR ⁴ R ⁵ (2)
[Wherein, R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ² , R ⁴ and R ⁵ are hydrogen atoms or the following general formula (3)
—CH ₂ CH (OH) CH ₂ O (C ₂ H ₄ O) _b (C ₃ H ₆ O) _c R ⁶ (3)
(Wherein R ⁶ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms or an acyl group having 2 to 8 carbon atoms, b is an integer of 2 to 20, and c is an integer of 0 to 10). .)
Is a monovalent group represented by formula (3) and contains at least 30 mol% of R ² , R ⁴ and R ⁵ , and R ³ is a divalent carbon atom having 1 to 4 carbon atoms. A hydrogen group, a is an integer of 0-4. ]
It is a monovalent group shown by these. X is R, A or —OR ⁷ ( wherein R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms), m is an integer of 5 to 500, and n is 0 to 100. An integer, but when n = 0, at least one of X is A. }
(B) a polyoxyalkylene group-containing organopolysiloxane,
(C) a surfactant,
(D) A sanitizer softener composition comprising water.
[2] The amino / polyoxyalkylene group-containing organopolysiloxane (A) is composed of an organopolysiloxane represented by the following general formula (4) and a polyoxyalkylene glycidyl ether represented by the following general formula (5). The softener composition for sanitary materials according to [1], which is obtained by reaction.

[Wherein, R is the same as defined above, and B represents the following general formula (6)
—R ¹ — (NH—R ³ ) _a NH ₂ (6)
Wherein R ¹ , R ³ and a are the same as defined above, and Z is R, B or —OR ⁷ (where R ⁷ is the same as defined above). , M and n are the same as above, but when n = 0, at least one of Z is B. ]

(In the formula, R ⁶ , b and c are the same as above.)
[3] The sanitary softener composition according to [1] or [2], wherein the polyoxyalkylene group-containing organopolysiloxane of component (B) is an organopolysiloxane represented by the following general formula (7).
R ⁸ ₂ XSiO— (R ⁸ ₂ SiO) _r — (R ⁸ YSiO) _s —SiR ⁸ ₂ X (7)
[However, R ⁸ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and Y is the following formula (8)
_{^{-R 9 O- (C p H 2p}} O) q -R 10 (8)
(In the formula, R ⁹ is a divalent hydrocarbon group having 3 to 6 carbon atoms, R ¹⁰ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, p is an integer of 2 to 4, and q is an integer of 5 to 50.)
X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, R ⁸ or Y, r is an integer of 10 to 200, and s is an integer of 0 to 50, When s = 0, at least one of X is Y. ]
[4] The sanitary softener composition according to [1], [2] or [3], wherein the substrate to be treated is paper or non-woven fabric.

  The softener composition for sanitary materials of the present invention can impart excellent flexibility and slipperiness to the sanitary material without impairing the water absorption of the sanitary material.

Component (A) Component (A) The amino / polyoxyalkylene group-containing organopolysiloxane has an effect of imparting excellent flexibility and water absorption to a sanitary material, and is preferably represented by the following general formula (1). The organopolysiloxane shown.

｛式中、Ｒは炭素数１〜２０の１価炭化水素基であり、Ａは下記一般式（２）
−Ｒ¹−（ＮＲ²−Ｒ³）_a−ＮＲ⁴Ｒ⁵ （２）
［式中、Ｒ¹は炭素数１〜８の２価炭化水素基であり、Ｒ²，Ｒ⁴，Ｒ⁵は水素原子又は下記一般式（３）
−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂Ｏ（Ｃ₂Ｈ₄Ｏ）_b（Ｃ₃Ｈ₆Ｏ）_cＲ⁶ （３）
（式中、Ｒ⁶は水素原子、炭素数１〜８の１価炭化水素基又は炭素数２〜８のアシル基であり、ｂは２〜２０の整数、ｃは０〜１０の整数である。）
で示される１価の基で、式（３）で示される基をＲ²，Ｒ⁴及びＲ⁵の全体の３０ｍｏｌ％以上含有するものであり、Ｒ³は炭素数１〜４の２価炭化水素基であり、ａは０〜４の整数である。］
で示される１価の基である。ＸはＲ，Ａ又は−ＯＲ⁷（但し、Ｒ⁷は水素原子又は炭素数１〜８の１価炭化水素基である。）であり、ｍは５〜５００の整数、ｎは０〜１００の整数であるが、ｎ＝０の場合、Ｘの少なくとも１個はＡである。｝

{Wherein R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is the following general formula (2)
-R ^1- (NR ² -R ³ ) _a -NR ⁴ R ⁵ (2)
[Wherein, R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ² , R ⁴ and R ⁵ are hydrogen atoms or the following general formula (3)
—CH ₂ CH (OH) CH ₂ O (C ₂ H ₄ O) _b (C ₃ H ₆ O) _c R ⁶ (3)
(Wherein R ⁶ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms or an acyl group having 2 to 8 carbon atoms, b is an integer of 2 to 20, and c is an integer of 0 to 10). .)
Is a monovalent group represented by formula (3) and contains at least 30 mol% of R ² , R ⁴ and R ⁵ , and R ³ is a divalent carbon atom having 1 to 4 carbon atoms. A hydrogen group, a is an integer of 0-4. ]
It is a monovalent group shown by these. X is R, A or —OR ⁷ (wherein R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms), m is an integer of 5 to 500, and n is 0 to 100. An integer, but when n = 0, at least one of X is A. }

  In said formula (1), R is a C1-C20, Preferably it is a 1-10 monovalent hydrocarbon group, As a specific example of R, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group Alkyl groups such as hexyl, heptyl, octyl and decyl, alkenyl such as vinyl and allyl, cycloalkyl such as cyclopentyl and cyclohexyl, aryl such as phenyl, tolyl and naphthyl Or a group in which a hydrogen atom bonded to a carbon atom of these groups is partially substituted with a halogen atom or the like. Among these, a methyl group is particularly preferable.

X is R, A or —OR ⁷ (where R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms). Here, specific examples of the monovalent hydrocarbon group of R ⁷ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and octyl group, and aryl groups such as phenyl group. One having 1 to 8 carbon atoms, preferably 1 to 3 carbon atoms is mentioned.

  Further, if m is less than 5, the flexibility is insufficient, and if it is more than 500, the water absorption is lowered, so that it is an integer of 5 to 500, preferably an integer of 10 to 100. When n is larger than 100, the viscosity increases and it becomes difficult to handle. Therefore, n is an integer of 0 to 100, preferably an integer of 1 to 50. However, in the present invention, it has at least one monovalent group (A) represented by the general formula (2). When n = 0, at least one of X is A.

A is a monovalent group represented by the general formula (2). In the above formula (2), R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, preferably 2 to 4 carbon atoms. Specifically, alkylene groups such as a methylene group, a dimethylene group, a trimethylene group, and a tetramethylene group are preferable, and a trimethylene group is particularly preferable. R ³ is a divalent hydrocarbon group having 1 to 4 carbon atoms. Specifically, an alkylene group such as a methylene group, a dimethylene group, a trimethylene group, or a tetramethylene group is preferable, and a dimethylene group is particularly preferable.

R ² , R ⁴ and R ⁵ are each a hydrogen atom or a monovalent group represented by the general formula (3). In order to improve water absorption, the group represented by the general formula (3) is represented by R ² , R The total content of ⁴ and R ⁵ is 30 mol% or more, preferably 50 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 100 mol%.

Here, in the general formula (3), R ⁶ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms, particularly 1 to 5 carbon atoms, or an acyl group having 2 to 8 carbon atoms, particularly 2 to 4 carbon atoms, Specifically, an alkyl group such as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and an acyl group such as an acetyl group, a butyryl group, and a benzoyl group are preferable. . Further, if b is smaller than 2, water absorption is insufficient, and if it is larger than 20, flexibility is insufficient, so it is an integer of 2 to 20, and preferably an integer of 3 to 10. When c is larger than 10, the water absorption becomes insufficient, so that it is an integer of 0 to 10, and preferably an integer of 0 to 5.

  Moreover, in said General formula (2), since manufacture is difficult when a is 5 or more, a is an integer of 0-4, especially an integer of 0-2.

  The amino-polyoxyalkylene group-containing organopolysiloxane represented by the above general formula (1) includes an organopolysiloxane represented by the following general formula (4), a polyoxyalkylene glycidyl ether represented by the following general formula (5), It can be easily obtained by this reaction.

［式中、Ｒは前記と同じであり、Ｂは下記一般式（６）
−Ｒ¹−（ＮＨ−Ｒ³）_aＮＨ₂ （６）
（式中、Ｒ¹，Ｒ³，ａは前記と同じである。）で示される基であり、ＺはＲ，Ｂ又は−ＯＲ⁷（但し、Ｒ⁷は前記と同じである。）であり、ｍ，ｎは前記と同じであるが、ｎ＝０の場合、Ｚの少なくとも１個はＢである。］

[Wherein, R is the same as defined above, and B represents the following general formula (6)
—R ¹ — (NH—R ³ ) _a NH ₂ (6)
Wherein R ¹ , R ³ and a are the same as defined above, and Z is R, B or —OR ⁷ (where R ⁷ is the same as defined above). , M and n are the same as above, but when n = 0, at least one of Z is B. ]

（式中、Ｒ⁶，ｂ，ｃは前記と同じである。）

(In the formula, R ⁶ , b and c are the same as above.)

Examples of R in the above formula (4) are the same as those in R in the above general formula (1), and a methyl group is particularly preferable. M and n are the same as m and n. When n = 0, at least one of Z is B.
Moreover, B is a group represented by the formula (6), R ¹ in the formula ^{(6), R 3, a} , R, R R 7 is exemplified above ^{1, R 3, a, R} , R ⁷ and are exemplified the same ones as, especially trimethylene group as R ^1, in particular dimethylene group is preferable as R ^3.

R ⁶ , b and c in the above formula (5) can also be exemplified by the same as R ⁶ , b and c exemplified above.

  Specific examples of the organopolysiloxane represented by the general formula (4) used in the present invention include the following, but are not limited thereto.

（式中、ｎ，ｍは前記と同じである。）

(In the formula, n and m are the same as described above.)

（式中、ｂ，ｃは前記と同じである。） Moreover, as a polyoxyalkylene glycidyl ether shown by the said General formula (5) used by this invention, the following are mentioned as a specific example, However, It is not limited to these.

(Wherein b and c are the same as above)

  The organopolysiloxane represented by the general formula (4) and the polyoxyalkylene glycidyl ether represented by the general formula (5) react according to the following reaction formula (1).

Further, as described above, in order to improve water absorption, the polyoxyalkylene-containing organic group represented by the general formula (3) in R ² , R ⁴ and R ⁵ in the general formula (2) should be 30 mol% or more. From 30 to 100 mol%, preferably 50 to 100 mol% of the polyoxyalkylene glycidyl ether represented by the general formula (5) with respect to all NH groups in the organopolysiloxane represented by the general formula (4). More preferably, the reaction is carried out so as to be 70 to 100 mol%, more preferably 100 mol%. The reaction between the NH group-containing organopolysiloxane and the polyoxyalkylene glycidyl ether is sufficient if the addition reaction is carried out at 50 ° C. to 100 ° C. for 1 to 5 hours in the absence of a solvent or in a solvent such as lower alcohol, toluene or xylene. It is.

The (B) component (B) component polyoxyalkylene group-containing organopolysiloxane not only provides the sanitary material with flexibility, smoothness and water absorption, but also has an effect as an emulsification aid for the (A) component. Is. As a polyoxyalkylene group containing organopolysiloxane used by this invention, what is shown by following General formula (7) is preferable.

R ⁸ ₂ XSiO— (R ⁸ ₂ SiO) _r — (R ⁸ YSiO) _s —SiR ⁸ ₂ X (7)
[However, R ⁸ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and Y is the following formula (8)
_{^{-R 9 O- (C p H 2p}} O) q -R 10 (8)
(In the formula, R ⁹ is a divalent hydrocarbon group having 3 to 6 carbon atoms, R ¹⁰ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, p is an integer of 2 to 4, and q is an integer of 5 to 50.)
X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, R ⁸ or Y, r is an integer of 10 to 200, and s is an integer of 0 to 50, When s = 0, at least one of X is Y. ]

In the above formula (7), R ⁸ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, specifically, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or a hexyl group, or a phenyl group. And the like, and particularly preferred is a methyl group.

Y is a polyoxyalkylene-containing group represented by the formula (8). Here, R ⁹ in the formula (8) is a divalent hydrocarbon group having 3 to 6 carbon atoms, and specific examples thereof include trimethylene group, tetramethylene group, pentamethylene group and hexamethylene group. Of these, a trimethylene group is preferred. R ¹⁰ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, specifically, as a monovalent hydrocarbon group having 1 to 4 carbon atoms, methyl Group, an alkyl group such as an ethyl group, a propyl group, and a butyl group, an alkenyl group such as a vinyl group, and an allyl group. Specific examples of the acyl group having 2 to 4 carbon atoms include an acetyl group, a butyryl group, A propionyl group etc. are mentioned. Among these, a methyl group, a butyl group, and an acetyl group are preferable.

p is an integer of 2-4. Here, examples of the polyoxyalkylene group represented by C _p H _2p O include polyoxyethylene (p = 2), polyoxypropylene (p = 3), and polyoxybutylene (p = 4) units, Among them, one kind of polymer or two or more kinds of copolymers may be used, and a block polymer or a random polymer may be used. In particular, an organopolysiloxane containing a polyoxyethylene-containing organic group with p = 2 is preferred for improving water absorption.

  Moreover, q is an integer of 5-50. When q is less than 5, slipperiness and water absorption are poor, and when it exceeds 50, workability decreases due to high viscosity. Particularly, it is preferably an integer of 7 to 40 in terms of water absorption and dispersibility.

In said formula (7), X is a C1-C4 alkoxy group, a hydroxyl group, said R < ¹ > or Y. Here, examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and a tert-butoxy group.

  Moreover, r is an integer of 10 to 200, and if it is less than 10, the slipperiness is poor due to low viscosity, and if it exceeds 200, the viscosity becomes too high and the workability deteriorates. A particularly preferable range of r is an integer of 15 to 150. Furthermore, s is preferably an integer of 0 to 50, more preferably an integer of 0 to 30, but when s is 0, a polyoxyalkylene-containing group of the formula (8) is present at the terminal (that is, X At least one is Y). On the other hand, when s exceeds 50, the siloxane portion is reduced as a whole, resulting in poor water absorption.

  Specific examples of the polyoxyalkylene group-containing organopolysiloxane represented by the above formula (7) include compounds represented by the following formula. In the following formulae, Me represents a methyl group, EO represents an oxyethylene group, and PO represents an oxypropylene group.

  The amount of the component (B) is preferably 5 to 200 parts by weight, more preferably 5 to 100 parts per 100 parts by weight of the component (A) in order to improve water absorption or improve the stability of the emulsion. Part by mass. If the blending amount is too small, the water absorption is poor and the emulsion stability may be deteriorated, and if it is too large, the texture may be deteriorated.

Component (C) Surfactant of component (C) is for uniformly dispersing components (A) and (B) in water, and uniformly disperses components (A) and (B) in water. The nonionic surfactant is not particularly limited as long as it is, for example, ethoxylated higher alcohol, polyhydric alcohol fatty acid ester, ethoxylated polyhydric alcohol fatty acid ester, ethoxylated fatty acid, ethoxylated fatty acid. Amides, sorbitols, sorbitan fatty acid esters, ethoxylated sorbitan fatty acid esters, sucrose fatty acid esters and the like can be mentioned, and the HLB is preferably in the range of 5 to 20, particularly preferably in the range of 10 to 16. . Examples of the anionic surfactant include higher alcohol sulfates, alkylphenyl ether sulfates, alkylbenzene sulfonates, higher alcohol phosphates, ethoxylated higher alcohol sulfates, and ethoxylated alkyl phenyl ethers. Examples of the cationic surfactant include alkyl trimethyl ammonium chloride, alkyl amine hydrochloride, coconut amine acetate, alkyl amine acetate, alkyl benzene dimethyl ammonium chloride, and the like. Is mentioned. Examples of amphoteric surfactants include N-acylamidopropyl-N, N-dimethylammoniobetaines, N-acylamidopropyl-N, N′-dimethyl-N′-β-hydroxypropylammoniobetaines, and the like. Is exemplified.

  Among these, nonionic surfactant ethoxylated higher alcohol, polyhydric alcohol fatty acid ester, ethoxylated polyhydric alcohol fatty acid ester, ethoxylated fatty acid, ethoxylated fatty acid amide, sorbitol, sorbitan fatty acid ester, ethoxylated sorbitan fatty acid ester, Sucrose fatty acid esters and the like are preferred.

  (C) As a compounding quantity of a component, it is preferable that it is 1-100 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, More preferably, it is 5-50 mass parts. It is desirable to improve water absorption or increase the stability of the emulsion. If the amount is too small, emulsification may be difficult, and if it is too large, the performance of the emulsion may be impaired.

The softener composition of the present invention is prepared, for example, by adding and mixing a surfactant to the aminopolyoxyalkylene group-containing organopolysiloxane and the polyoxyalkylene group-containing organopolysiloxane, and then adding ion-exchanged water to the entire composition. Of 20 to 80% by mass, particularly 40 to 60% by mass, and emulsification with an emulsifier.
In this case, if the amount of ion-exchanged water is too small, the prepared emulsion has a high finished viscosity and may be difficult to handle. If it is too large, the active ingredient may have a low concentration, which may be disadvantageous in terms of cost.

  In addition, a conventionally known method can be used as an emulsification method, for example, emulsification using an emulsifier such as a homomixer, a homogenizer, a colloid mill, a line mixer, a universal mixer, an ultra mixer, a planetary mixer, or a combination mix. can do.

  The softener composition of the present invention is prepared in the form of an O / W emulsion. By treating the base material, the softness excellent in the base material is obtained without impairing the water absorption of the base material. , Slipperiness can be imparted.

  Here, the substrate to be treated with the composition of the present invention is preferably a sanitary substrate using paper or non-woven fabric. Specifically, sanitary paper such as tissue paper and toilet paper, and paper diapers Examples of sanitary substrates such as PP, PE, rayon, cellulose, and other sanitary nonwoven fabrics and pulp fillers for paper diapers used in feminine sanitary products and the like can be given.

  In this case, as a method of treating the softener composition with a sanitary substrate, for example, the softener composition is diluted with ion-exchanged water so that the active ingredient is about 1 to 5% by mass, and then commercially available. A simple type cosmetic spray or the like can be applied uniformly to the substrate and air-dried.

  The amount of the softener composition of the present invention attached to the sanitary substrate is preferably 0.1 to 5.0% by mass of the sanitary substrate, more preferably 0. It is 3-3.0 mass%. If the adhesion amount is too small, the effect of imparting flexibility and slipperiness may be small, and if too much, the water absorption may be impaired.

  EXAMPLES Hereinafter, although a manufacture example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, “%” indicates mass%, the viscosity indicates a value at 25 ° C. measured with a B-type viscometer (type BH, manufactured by Tokyo Keiki), and the average particle diameter is N4plus submicron particle analyzer (Beckman The value measured by Coulter) is shown.

[Production Example 1]
In a 500 ml separable flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas inlet tube, 100 g of an aminoalkyl group-containing organopolysiloxane (molecular weight 3,326) represented by the following formula (A), 48 g of polyoxyalkylene glycidyl ether (molecular weight 333) represented by (B) (100 mol% with respect to the total NH in the aminoalkyl group-containing organopolysiloxane) and 14.8 g of isopropyl alcohol were charged and sealed after nitrogen gas was introduced. Then, the reaction was performed at 80 ° C. for 4 hours. After completion of the reaction, the low-boiling fraction was removed at 80 ° C. for 1 hour under reduced pressure of 10 mmHg. The viscosity was 497 mPa · s, the amine equivalent was 2,990 g / mol (about 1.5 g of the product was added to toluene and isopropyl A value measured with an automatic titrator using a 0.01N hydrochloric acid aqueous solution dissolved in about 50 ml of a 1: 1 mixture of alcohol, even after the epoxy group represented by the following formula (C) has been completely consumed. In the measuring method, it is detected as an amine equivalent. The following amine equivalent measured values are also the same.), An oily substance (amino-polyoxyalkylene group-containing organo) represented by the following formula (C) having a volatile content of 2.5% 135 g of polysiloxane was obtained.

[Production Example 2]
100 g of an aminoalkyl group-containing organopolysiloxane represented by the following formula (D) (molecular weight 2,146), 79.7 g of a polyoxyalkylene glycidyl ether (molecular weight 570) represented by the following formula (E) (aminoalkyl group-containing organopoly) 100 mol% with respect to the total NH in the siloxane) and 18.0 g of isopropyl alcohol were introduced. After introducing nitrogen gas, the mixture was sealed and reacted at 80 ° C. for 4 hours. After completion of the reaction, the low-boiling fraction was removed at 80 ° C. for 1 hour under reduced pressure of 10 mmHg. The following formula (F) with a viscosity of 680 mPa · s, an amine equivalent of 3,050 g / mol, and a volatile content of 1.3% was obtained. 181 g of an oily product (amino-polyoxyalkylene group-containing organopolysiloxane) represented by

[Production Example 3]
100 g of an aminoalkyl group-containing organopolysiloxane represented by the following formula (G) (molecular weight 1,981), 57.5 g of a polyoxyalkylene glycidyl ether represented by the above formula (E) (total in the aminoalkyl group-containing organopolysiloxane) 100 mol% with respect to NH) and 15.8 g of isopropyl alcohol were introduced, nitrogen gas was introduced and the mixture was sealed and reacted at 80 ° C. for 4 hours. After completion of the reaction, the low-boiling fraction was removed at 80 ° C. under a reduced pressure of 10 mmHg for 1 hour. As a result, a viscosity of 345 mPa · s, an amine equivalent of 5,550 g / mol, and a volatile content of 1.3% (H 181 g of an oily product (amino-polyoxyalkylene group-containing organopolysiloxane) represented by

[Example 1]
150 g of the amino-polyoxyalkylene group-containing organopolysiloxane (C) obtained in Production Example 1, polyoxyalkylene group-containing organopolysiloxane (in formula (7), R ⁸ is a methyl group, X is a methyl group, Y is C ₃ H ₆ O (C ₂ H ₄ O) ₁₀ CH ₃ , r is 10 and s is 5) 200 g and polyoxyethylene decyl ether (C ₁₀ H ₂₁ O (C ₂ H ₄ O) ₁₀ H) Mixing using a mixer, 600 g of ion-exchanged water was added to prepare a microemulsion having an organopolysiloxane concentration (active ingredient) of 35%. The obtained emulsion was colorless and transparent, had an average particle diameter of 20 nm, and no change was observed after standing at room temperature for 1 month. The emulsion is diluted to 1% with ion-exchanged water, and a pair of tissue papers (Napier Soft Slim: Oji Napier Co., Ltd., Vertical 197 mm x Wide 229 mm) marketed as a simple cosmetic spray. , Two sheets, mass: 1.0 g) was spray-applied from 15 cm away. Then, after air-drying at room temperature for 6 hours, the adhesion amount, flexibility, slipperiness, water absorption, and storage stability of the emulsion were evaluated. These results are shown in Table 1.

[Example 2]
An emulsion was prepared in the same manner as in Example 1 except that the aminopolyoxyalkylene group-containing organopolysiloxane (F) obtained in Production Example 2 was used. Using this emulsion, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 3]
In Example 1, an emulsion was prepared in the same manner as in Example 1 except that the aminopolyoxyalkylene group-containing organopolysiloxane (H) obtained in Production Example 3 was used. Using this emulsion, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Example 4]
150 g of the amino-polyoxyalkylene group-containing organopolysiloxane (C) obtained in Production Example 1, 50 g of the polyoxyalkylene group-containing organopolysiloxane used in Example 1, and polyoxyethylene decyl ether (C ₁₀ H ₂₁ O ( 200 g of C ₂ H ₄ O) ₁₀ H) was mixed using a homomixer, and 600 g of ion-exchanged water was added to prepare a microemulsion having an organopolysiloxane concentration (active ingredient) of 20%. Evaluation was performed in the same manner as in Example 1 using the obtained emulsion. The evaluation results are shown in Table 1.

[Example 5]
The emulsion obtained in Example 1 was diluted to 1% with ion-exchanged water, and an industrial wiper (Kuraflex “Clean”), which was a non-woven fabric marketed in a simple type cosmetic spray as in Example 1. Wiper ": Vertical 250 mm x width 250 mm, manufactured by Kuraray Co., Ltd., mass: 2.1 g, folded in half) was spray-applied from 15 cm away. Then, after air-drying at room temperature for 6 hours, the adhesion amount, flexibility, slipperiness, water absorption, and storage stability of the emulsion were evaluated. The number of samples was 2. These results are shown in Table 1.

[Comparative Example 1]
In Example 1, an emulsion was prepared in the same manner as in Example 1 except that the aminopolyoxyalkylene group-containing organopolysiloxane (C) obtained in Production Example 1 was not blended. Using this emulsion, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 2]
In Example 1, an emulsion was prepared in the same manner as in Example 1 except that the polyoxyalkylene group-containing organopolysiloxane was not blended. Using this emulsion, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 3]
An emulsion was prepared in the same manner as in Example 1 except that polyoxyethylene decyl ether (C ₁₀ H ₂₁ O (C ₂ H ₄ O) ₁₀ H) was not blended in Example 1. Using this emulsion, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 4]
In Example 1, the amino-polyoxyalkylene group-containing organopolysiloxane (C) obtained in Production Example 1 was converted to an amino group-containing organopolysiloxane (viscosity: 1,200 mPa · s, amine equivalent: 1,600 g / mol). An emulsion was prepared in the same manner as in Example 1 except for changing to. Using this emulsion, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 1.

[Comparative Example 5]
Table 1 shows the evaluation of the untreated product of the tissue paper used in the examples.

[Comparative Example 6]
Table 1 shows the evaluation of the untreated non-woven fabric (industrial wiper) used in the examples.

にて算出した。 <Evaluation methods>
1. Amount of adhesion:

It calculated in.

2. Flexibility:
About the tissue paper and industrial wiper of an Example and a comparative example, three panelists evaluated by the following reference | standard by the touch.
◎: Very good ○: Good △: Somewhat bad ×: Bad

3. Slipperiness:
About the tissue paper and industrial wiper of an Example and a comparative example, three panelists evaluated by the following reference | standard by the touch.
◎: Very good ○: Good △: Somewhat bad ×: Bad

4). Water absorption:
With a dropper, water drops were dropped at three locations on the surface of the tissue paper and the industrial wiper in Examples and Comparative Examples, and the time until complete absorption was measured (two samples).

5). Emulsion storage stability:
The emulsions prepared in Examples and Comparative Examples were stored at 50 ° C. for 30 days, and the emulsion after 30 days was evaluated according to the following criteria.
○: Stable with no difference in density at upper and lower layers △: Separation of light and shade at upper and lower layers ×: Completely separated into two layers

Claims (4)

(A) an aminopolyoxyalkylene group-containing organopolysiloxane represented by the following general formula (1) :

{Wherein R is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and A is the following general formula (2)
-R ^1- (NR ² -R ³ ) _a -NR ⁴ R ⁵ (2)
[Wherein, R ¹ is a divalent hydrocarbon group having 1 to 8 carbon atoms, and R ² , R ⁴ and R ⁵ are hydrogen atoms or the following general formula (3)
—CH ₂ CH (OH) CH ₂ O (C ₂ H ₄ O) _b (C ₃ H ₆ O) _c R ⁶ (3)
(Wherein R ⁶ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 8 carbon atoms or an acyl group having 2 to 8 carbon atoms, b is an integer of 2 to 20, and c is an integer of 0 to 10). .)
Is a monovalent group represented by formula (3) and contains at least 30 mol% of R ² , R ⁴ and R ⁵ , and R ³ is a divalent carbon atom having 1 to 4 carbon atoms. A hydrogen group, a is an integer of 0-4. ]
It is a monovalent group shown by these. X is R, A or —OR ⁷ ( wherein R ⁷ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 8 carbon atoms), m is an integer of 5 to 500, and n is 0 to 100. An integer, but when n = 0, at least one of X is A. }
(B) a polyoxyalkylene group-containing organopolysiloxane,
(C) a surfactant,
(D) A sanitizer softener composition comprising water. Component (A), an aminopolyoxyalkylene group-containing organopolysiloxane, is obtained by reacting an organopolysiloxane represented by the following general formula (4) with a polyoxyalkylene glycidyl ether represented by the following general formula (5). The sanitizer softener composition according to claim 1.

[Wherein, R is the same as defined above, and B represents the following general formula (6)
  -R ¹ -(NH-R ^Three ) _a NH ₂                                       (6)
(Wherein R ¹ , R ^Three , A are the same as described above. And Z is R, B or -OR. ⁷ (However, R ⁷ Is the same as above. M and n are the same as above, but when n = 0, at least one of Z is B. ]

(Wherein R ⁶ , B and c are the same as described above. ) The sanitary softener composition according to claim 1 or 2, wherein the polyoxyalkylene group-containing organopolysiloxane (B) is an organopolysiloxane represented by the following general formula (7).
R ⁸ ₂ XSiO— (R ⁸ ₂ SiO) _r — (R ⁸ YSiO) _s —SiR ⁸ ₂ X (7)
[However, R ⁸ is a monovalent hydrocarbon group having 1 to 6 carbon atoms, and Y is the following formula (8)
_{^{-R 9 O- (C p H 2p}} O) q -R 10 (8)
(In the formula, R ⁹ is a divalent hydrocarbon group having 3 to 6 carbon atoms, R ¹⁰ is a hydrogen atom, a monovalent hydrocarbon group having 1 to 4 carbon atoms or an acyl group having 2 to 4 carbon atoms, p is an integer of 2 to 4, and q is an integer of 5 to 50.)
X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, R ⁸ or Y, r is an integer of 10 to 200, and s is an integer of 0 to 50, When s = 0, at least one of X is Y. ]   The sanitary softener composition according to claim 1, 2 or 3, wherein the substrate to be treated is paper or non-woven fabric.