JP4530255B2 - Water-dispersed water / oil repellent and water / oil repellent paper and sheet using the same - Google Patents

Description

  The present invention provides a treating agent composition capable of imparting water and oil repellency to various paper base materials without using a fluorine compound and a solvent.

  Paper materials used for food wrapping paper, packaging containers, cooking paper, etc. are deformed or damaged when taking out the oil and moisture of the food to prevent the surroundings from getting dirty, and when the food is sticky or adhered and taken out. Water and oil repellency and non-tackiness are imparted to prevent this.

  Conventionally, various compounds having a perfluoroalkyl group have been suitably used for this purpose, and various improvements have been made so far. As one of the methods, a method using a polymer having a polymerization unit of a polymerizable monomer having a perfluoroalkyl group is known. Many of them are dispersed in water, and have been widely used in an internal addition method in which these processing agents are added during papermaking or in an external addition method in which the papermaking paper is immersed in a treatment solution.

  For example, Reference 1 is a method for improving solubility, Reference 2 is a method for preventing a decrease in oil repellency by treatment, Reference 3 is for improving secondary processability, and Reference 4 is for improving adhesion. Proposals using can be seen.

  Another method is known that uses an amine salt of a phosphoric ester having a perfluoroalkyl group, and has been widely used in the same manner as that using the above-mentioned polymer. For example, Reference 5 and Reference 6 propose improvements in dispersion stability, and Reference 7 and Reference 8 propose improvements in storage stability for this method.

Japanese Patent Laid-Open No. 10-7738 JP 2000-169735 A JP 2001-98033 A JP 2002-220539 A JP-A 64-6196 JP-A-56-138197 JP 2000-87013 A JP 2000-144120 A

  However, as one of the causes of a serious environmental problem, fluoroaliphatic hydrocarbons have been regarded as ozone layer depleting substances or global warming substances and their use has been regulated. Therefore, even in the case of a fluorine compound having a similar structure, there is no denying the possibility that some kind of regulation will be made in the near future in relation to environmental problems. In addition, in food applications, it has been pointed out that there is a possibility that a harmful substance containing fluorine is generated even when cooking with a microwave oven or the like. A similar problem has been pointed out when incinerated for disposal, and it also releases harmful substances containing fluorine such as hydrofluoric acid to the environment.

  Under these circumstances, recently, a method for imparting water / oil repellency and non-tackiness to paper materials without using a compound having a perfluoroalkyl group has been demanded. PVA resin has long been used for paper substrate processing for sealing and the like, but its high hydrophilicity also has an effect of imparting oil repellency, and is expected as a substitute for a compound having a perfluoroalkyl group. However, due to its hydrophilicity, water repellency and non-adhesiveness are poor, and it is difficult to obtain a balanced performance in actual use.

  Silicone, on the other hand, is used for processing to impart water repellency and non-adhesiveness, but there are no substitutes that have sufficient performance in terms of oil repellency. Silicone is a hydrophobic material, and PVA resin is a hydrophilic material. Even if these are simply mixed, they are not mixed uniformly, and it is difficult to achieve both water and oil repellency.

  The present invention has been made in view of the above circumstances, and uses a processing agent comprising an emulsion type silicone release agent and a polyvinyl alcohol (hereinafter abbreviated as PVA) resin, to make a paper base such as kraft paper, fine paper, and cardboard. The object is to impart oil and water repellency to the material.

As a result of diligent efforts to achieve the above object,
(A) Functional group-containing organopolysiloxane 100 parts by mass (B) 0.1-30 parts by mass of cross-linking agent (C) PVA-based resin 50-1000 parts by mass (D) catalyst 0-5 parts by mass (E ) 100-100,000 parts by weight of water (F) Hydrolyzable group-containing silanes and / or their partially hydrolyzed condensates
1 to 250 parts by mass It has been found that excellent water and oil repellency can be imparted to a paper substrate by treatment with a water-dispersed water and oil repellent comprising these, and the present invention has been made.

  As a result of examining the combination of PVA resin with excellent oil repellency and silicone with good water repellency and non-adhesiveness to achieve the advantages of both materials, a material having a specific structure is combined under specific conditions. By blending a decomposable group-containing silane and a partially hydrolyzed condensate thereof, a treatment composition having both oil repellency, water repellency and non-tackiness was found and the present invention was reached. The composition is a combination of materials that are safe and harmless to the environment, and can be suitably used as a substitute for a compound having a perfluoroalkyl group. Since it can be used as a water-dispersed type that does not contain an organic solvent, disadvantages from environmental problems and dangers due to the use of the solvent can be avoided. The paper base treated with this composition is easy to recycle and becomes a product with low environmental impact. It can solve harmful and environmental problems derived from fluorine compounds. It does not contain a solvent and is unnecessary for use, so it is advantageous in terms of management and cost. Recycling is easy and environmental impact is reduced.

  Kraft paper, fine paper, liner, cardboard, etc., which are generally commercially available, can be used as the paper base material used in the present invention. For example, natural fibers such as Manila hemp, ridges, honey bees, etc., Tetron, vinylon, acrylic Those made from synthetic fibers such as these can be used.

The functional group-containing organopolysiloxane used as the component (A) for use in the present invention is composed of a straight chain which may contain a branched chain structure, mainly dimethylsiloxane, and has a viscosity at 25 ° C. Is 0.05 to 500 Pa · s. Those having a hydroxyl group or an alkenyl group as a functional group and capable of undergoing a curing reaction by combining a crosslinking agent of component (B) and a catalyst of component (D) described later are preferably used from the viewpoint of water repellency and non-adhesiveness. .
One preferred combination of component (A), component (B), and component (D) is that the functional group-containing organopolysiloxane of component (A2) below and the crosslinking agent of component (B2) depend on the catalyst of component (D2). It undergoes a condensation reaction. This component (A2) has a structure represented by the average composition formula (1) and has at least two hydroxyl groups in one molecule.

［式中、Ｒ^１は一価炭化水素基で、Ｒ^３は水酸基を示し、Ｘ^２は以下の式で示される基である。

[Wherein R ¹ represents a monovalent hydrocarbon group, R ³ represents a hydroxyl group, and X ² represents a group represented by the following formula:

（ａ２、ｂ２、ｃ２、ｄ２はオルガノポリシロキサンの２５℃での粘度が０．０５〜５００Ｐａ・ｓを満たす正数から選ばれ、ｂ２、ｃ２、ｄ２は０であってもよい。）］

(A2, b2, c2, d2 the viscosity at 25 ° C. of the organopolysiloxane is chosen from a positive number to fully plus the 0.05~500Pa · s, b2, c2, d2 may be zero.) ]

Wherein R ² in represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, for example, each a methyl group, an ethyl group, a propyl group, an alkyl group such as butyl group, cycloalkyl groups such as a cyclohexyl group, a vinyl group Chloromethyl in which some or all of the hydrogen atoms bonded to carbon atoms of alkenyl groups such as propenyl and butenyl groups, phenyl and tolyl groups, or carbon atoms of these groups are substituted with halogen atoms, cyano groups, etc. And a group selected from an unsubstituted or substituted monovalent hydrocarbon group such as a cyanoethyl group and the like. From the viewpoint of production and characteristics, it is preferable that at least 80% of R ² contained in the entire functional group-containing organopolysiloxane of the component (A2) is a methyl group.

  The hydroxyl group possessed by one molecule of the functional group-containing organopolysiloxane of component (A2) requires at least two functional groups for curing by a condensation reaction, and the crosslinking agent (B2) component described below and, if necessary, the catalyst Combined with the component (D2), it is used as a curing type. If there are less than two hydroxyl groups, there is a high possibility that uncrosslinked molecules remain even after curing, and the water repellency tends to decrease with time, which is not desirable.

Desirably, the content per 100 g of the functional group-containing organopolysiloxane is 0.0001 mol to 0.1 mol, and if it is less than 0.0001 mol, the water repellency decreases with time. Life is shortened and handling becomes difficult. The corresponding compound of formula (2) and the substituent ^{X 2 a2, b2, c2,} d2, the number of hydroxyl groups possessed by one molecule (b2 + c2 + 2) is selected to be in the range of 2 to 150.

  Component (B2) as a preferred crosslinking agent that undergoes a condensation reaction in combination with component (A2) is an organohydrogenpolysiloxane or organopolysiloxane having at least three SiH or hydrolyzable groups in one molecule. Available. The amount of SiH or hydrolyzable group contained is equivalent to 5 to 200 times the number of moles of the hydroxyl group contained in the component (A2). As, it is the range of 0.1-30 mass parts with respect to 100 mass parts of functional group containing organopolysiloxane of (A2) component.

  If the number of moles of SiH or hydrolyzable group contained in the blending amount of component (B2) is less than 5 times the number of moles of hydroxyl group contained in component (A2), it depends on the chemical reaction between the hydroxyl group and SiH or hydrolyzable group. While the bridging bond is not sufficient and the water repellency and non-adhesiveness are reduced, the effect does not increase remarkably even if it is added more than 200 times. Is also disadvantageous.

(B2) organohydrogenpolysiloxane used in component composition formula ^{_{R 2 f H g SiO (4}} -f-g) / 2 R 2 of (wherein, ^{R 2} is above average composition formula (1) F is 0 ≦ f ≦ 3, g is 0 <g ≦ 3, and f + g is a real number of 1 ≦ f + g <3), and has at least three SiH in one molecule The molecular structure may be linear, branched or cyclic. The viscosity may be in the range of several mPa · s to tens of thousands mPa · s.

  The following organopolysiloxanes can be mentioned as specific examples of the organohydropolysiloxane.

  However, in the above structural formula and composition formula, Y and Z are groups represented by the following structural formula, and h to w are integers in the following range. h, l and n are 3 to 500, m, p and s are 1 to 500, i, j, k, o, q, r, t, u, v and w are 0 to 500.

The organopolysiloxane used for the component (B2) has a composition formula R ² _f W _g SiO
In _{(4-f-g) /} 2 ( wherein, ^{R 2} is the same meaning as the ^{R 2} in the average composition formula described above (1), W represents a hydrolyzable group, f is 0 ≦ f ≦ 3, g is a real number of 0 <g ≦ 3 and f + g is 1 ≦ f + g <3), and it is necessary to have at least three hydrolyzable groups bonded to a silicon atom in one molecule. There is no particular limitation, and the molecular structure may be linear, branched or cyclic. The viscosity may be in the range of several mPa · s to tens of thousands mPa · s.

  Hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, methoxyethoxy, and isopropenoxy, which are directly bonded to silicon, acyloxy groups such as acetoxy, amino groups such as ethylamino, Examples thereof include those having an oxime group such as an amide group and an ethylmethylbutanoxime group, and a halogen atom such as chlorine and bromine.

  Specifically, the following polyorganosiloxane can be used.

ここでのＷはＣＨ_３ＣＯＯ−，ＣＨ_３（Ｃ_２Ｈ_５）Ｃ＝ＮＯ−，（Ｃ_２Ｈ_５）_２Ｎ−ＣＨ_３ＣＯ（Ｃ_２Ｈ_５）Ｎ−，ＣＨ_２＝（ＣＨ_３）ＣＯ−などの加水分解性基を示し、ｘ、ｙ、ｚは０〜５００の範囲の整数である。

Here, W is CH ₃ COO—, CH ₃ (C ₂ H ₅ ) C═NO—, (C ₂ H ₅ ) ₂ N—CH ₃ CO (C ₂ H ₅ ) N—, CH ₂ = (CH ₃ ) Represents a hydrolyzable group such as CO-, and x, y and z are integers in the range of 0 to 500.

  The (D2) component of the preferred catalyst for the combination of the (A2) and (B2) components is used to accelerate the condensation reaction to crosslink, impart water repellency and non-tackiness, and increase durability. Examples of the condensation catalyst include acids such as hydrochloric acid, phosphoric acid, methanesulfonic acid, paratoluenesulfonic acid, maleic acid, and trifluoroacetic acid, alkalis such as sodium hydroxide, potassium hydroxide, sodium ethoxide, and tetraethylammonium hydroxide, Examples include salts such as ammonium chloride, ammonium acetate, ammonium fluoride, and sodium carbonate, organic metal salts of metals such as magnesium, aluminum, zinc, iron, zirconium, cerium, and titanium, alkoxides, and chelate compounds. . For example, zinc dioctate, titanium tetraisopropoxide, aluminum tributoxide, zirconium tetraacetylacetonate and the like can be mentioned.

  Although the above condensation catalyst does not normally need to be added, it is added when it is difficult to obtain the original performance because sufficient heating and drying conditions for the reaction between the component (A2) and the component (B2) cannot be ensured. It is preferable to add 0.1 to 5% (mass ratio) as an active ingredient with respect to the total mass of the component (A2) and the component (B2) in order to impart and maintain performance, but the reactivity or desired of the components The amount can be appropriately increased or decreased depending on the curing rate.

  Another preferred combination of the component (A), the component (B), and the component (D) is a functional group-containing organopolysiloxane of the following component (A3) and a crosslinking agent of the component (B3) (D3) It is an addition reaction. The functional group-containing organopolysiloxane of component (A3) has a structure represented by the average composition formula (2) and has at least two alkenyl groups in one molecule.

［式中、Ｒ^１ は一価炭化水素基であり、Ｒ^２はアルケニル基を示し、Ｘ^３は以下の式で示される基である。

[In the formula, R ¹ is a monovalent hydrocarbon group, R ² represents an alkenyl group, X ³ is a group represented by the following formula.

（ａ３、ｂ３、ｃ３、ｄ３、ｅ３はオルガノポリシロキサンの２５℃での粘度が０．０５〜５００Ｐａ・ｓを満たす正数から選ばれ、２８≦ａ３＋ｂ３×（ｄ３＋ｅ３＋１）＋ｃ３≦２，０００、ｂ３、ｃ３、ｄ３、ｅ３は０であってもよい。α及びβは、０，１，２または３である。）］

(A3, b3, c3, d3 , e3 the viscosity at 25 ° C. of the organopolysiloxane is chosen from a positive number to fully plus the 0.05~500Pa · s, 28 ≦ a3 + b3 × (d3 + e3 + 1) + c3 ≦ 2,000 , B3, c3, d3, e3 may be 0. α and β are 0, 1, 2, or 3)]

R ¹ here is a group selected from the same monovalent hydrocarbon group having 1 to 20 carbon atoms as described above. From the viewpoint of production and characteristics, it is preferable that at least 80% of R ¹ contained in the entire functional group-containing organopolysiloxane of component (A3) is a methyl group, and R ² is a vinyl group.

  The alkenyl group of one molecule of the functional group-containing organopolysiloxane of the component (A3) requires two or more functional groups for curing by addition reaction, and the crosslinking agent (B3) component and catalyst (D3 described later) ) In combination with ingredients, it is used as a curable mold. If the number of alkenyl groups is less than 2, there is a high possibility that uncrosslinked molecules remain after curing, and the water repellency tends to decrease with time as in the case of (A2), which is not desirable.

Desirably, the content per 100 g of the functional group-containing organopolysiloxane is 0.001 mol to 0.1 mol, and if it is less than 0.001 mol, the water repellency decreases with time. Life is shortened and handling becomes difficult. The a3, b3, c3, d3, e3 of the corresponding formula (2) and substituents ^{X 3,} number {b3 × (e3 + α) + c3 + 2 × α} alkenyl group having 1 molecule is in the range of 2 to 150 So chosen.

  The component (B3) as a preferred crosslinking agent that undergoes addition reaction with the component (A3) is an organohydrogenpolysiloxane having at least three SiHs in one molecule, and the organohydrogenpolysiloxane among the components (B2) described above. The same as siloxane can be used. The amount of SiH contained is an amount corresponding to 1 to 5 times the number of moles of the alkenyl group contained in the component (A3), and as a blending mass part in a general organohydropolyenepolysiloxane, (A3) It is the range of 0.1-20 mass parts with respect to 100 mass parts of functional group containing organopolysiloxane of a component.

  When the number of moles of SiH contained in the blending amount of component (B3) is less than one times the number of moles of alkenyl groups contained in component (A3), the bridging bond due to the addition reaction between the alkenyl group and SiH is not sufficient. On the other hand, the aqueous and non-adhesive properties are reduced, but even if blended in excess of 5 times, a significant increase in the effect is not observed, which causes a change with time and is disadvantageous economically.

  A preferred catalyst (D3) component for the combination of the components (A3) and (B3) is used to promote the addition reaction to crosslink, impart water repellency and non-tackiness, and increase durability. Examples of such an addition reaction catalyst include platinum black, chloroplatinic acid, chloroplatinic acid-olefin complex, chloroplatinic acid-alcohol coordination compound, rhodium, rhodium-olefin complex, and the like. The addition reaction catalyst is preferably blended in an amount of 5 to 1000 ppm (mass ratio) as the amount of platinum or the amount of rhodium with respect to the total mass part of the component (A3) and the component (B3) in order to provide and maintain performance. However, it can be appropriately increased or decreased depending on the reactivity of the components or the desired curing rate.

The functional group-containing organopolysiloxanes (A2) and (A3) have a viscosity range of 0.05 to 500 Pa · s at 25 ° C., and non-adhesiveness is obtained when the viscosity is less than 0.05 Pa · s. It is difficult, and if it exceeds 500 Pa · s, the dispersibility with the component (C) decreases. Desirably, the viscosity is 0.1 to 100 Pa · s. As a, b, c, d, e of the corresponding formulas (2) to (3) and substituents X ^{2 to} X ³ , the polymerization degree {a + d + b × (c + e + 1) +2} is in the range of 30 to 2,000. Chosen to be.

  The main skeleton structure of the functional group-containing organopolysiloxane of the components (A2) and (A3) is a straight chain, but those containing a branched chain structure as shown in the case where b is not 0 can also be used. As these organopolysiloxanes, organopolysiloxanes modified with organic resins may be used. Examples of the organic resin include those having a polar group and a hydrophilic structure such as PVA resin, acrylic resin, polyester resin, and alkyd resin.

  Moreover, in the range which does not impair the characteristic with respect to the functional group containing organopolysiloxane of (A2) and (A3) component, the organopolysiloxane which does not contain the functional group shown by the following average composition formula (3) ( A1) can be used in combination.

式中、Ｒ^１は上記したと同様の一価炭化水素基を示す。Ｘ^１は以下の式で示される基である。

In the formula, R ¹ represents the same monovalent hydrocarbon group as described above. X ¹ is a group represented by the following formula.

ａ１、ｂ１、ｄ１はオルガノポリシロキサンの２５℃での粘度が０．０５〜５００Ｐａ・ｓを満を満たす正数から選ばれ、２８≦ａ１＋ｂ１×（ｄ１＋１）≦２，０００、ｂ１、ｄ１は０であってもよい。

a1, b1, and d1 are selected from positive numbers satisfying the viscosity of the organopolysiloxane at 25 ° C. of 0.05 to 500 Pa · s, and 28 ≦ a1 + b1 × (d1 + 1) ≦ 2,000, b1, and d1 are 0. It may be.

Here, R ¹ represents the same monovalent hydrocarbon group as described above, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, a cycloalkyl group such as a cyclohexyl group, a phenyl group, or a tolyl group. An unsubstituted or substituted monovalent hydrocarbon such as a chloromethyl group or a cyanoethyl group in which a part or all of the hydrogen atoms bonded to carbon atoms of these groups are substituted with a halogen atom, a cyano group, or the like A group selected from groups and the like. From the viewpoint of production and characteristics, it is preferable that at least 80% of R ¹ contained in the whole organopolysiloxane is a methyl group.

The organopolysiloxane (A1) is used as a silicone-based emulsion that is non-reactive with (B) and (D), unlike the components (A2) and (A3) described above. Since the component (A1) is not chemically bonded to the film, it is easily removed from the film, so that the water repellency tends to be lowered with time. As a method of suppressing this, a polar group or a hydrophilic group may be introduced as R ¹ to such an extent that the water repellency is not impaired, or it is modified with a resin having a large number of polar groups or structures as described later. May be selected or used together. The interaction with the PVA resin of the component (A) becomes larger, and an effect of suppressing the outflow from the film can be expected. Moreover, what combined the above-mentioned well-known polymerizable vinyl-type monomer can also be used for the PVA-type resin of (A) component to combine.

  The blending part by mass of the organopolysiloxane (A1) is in the range of 0 to 30 parts by mass with respect to 100 parts by mass of the functional group-containing organopolysiloxane of the component (A2). Moreover, it is the range of 0-30 mass parts with respect to 100 mass parts of functional group containing organopolysiloxane of (A3) component.

  By modifying the organopolysiloxane, the interaction with the PVA resin of the component (C) becomes stronger and the dispersibility is improved. Further, the organopolysiloxane is more strongly retained in the film and has a water repellency and non-adhesive property over time. Reduction is reduced. The amount of the organic resin used for modification is 5 mass% or less based on the organopolysiloxane to the extent that the water repellency and non-adhesiveness intended by the present invention are not impaired. Is adjusted as appropriate.

  As the PVA resin of the component (C) used in the present invention, a commercially available PVA resin can be used, but it is more advantageous to select a specific PVA resin as described below. The object of the present invention can be achieved.

  Rough characteristics of the PVA resin are defined by the degree of polymerization and the degree of saponification, but the degree of polymerization is 2 to 80 mPa · s as a viscosity of a 4% aqueous solution at 20 ° C., and the degree of saponification is 80 to 99.5 mol%. It is preferable to use one or more types of PVA-based resins that satisfy the requirements. When the viscosity at 20 ° C. of the 4% aqueous solution is less than 2 mPa · s, the film forming property is insufficient, and when it exceeds 80 mPa · s, the coating property is deteriorated. If the degree of saponification is less than 80 mol%, sufficient oil repellency may not be obtained, and if it exceeds 99.5 mol%, the water repellency may decrease.

  Particularly preferably, a PVA resin satisfying a viscosity of 10 to 50 mPa · s at 20 ° C. of a 4% aqueous solution and a saponification degree of 85 to 95 mol% is selected. Even if the viscosity at 20 ° C. of the 4% aqueous solution is less than 10 mPa · s or more than 50 mPa · s, it is difficult to obtain a good dispersion state with the silicone emulsion of the component (B), and the saponification degree is 85 to 95. If it is out of the mol% range, the level of oil repellency obtained tends to depend on the processing conditions. The corresponding approximate degree of polymerization is 200 to 3000, more preferably 500 to 2500.

  Although depending on the use of the water- and oil-repellent paper of the present invention, a PVA-based resin having a high temperature exhibiting thermoplasticity can be preferably used. Few.

  As the PVA resin used in the present invention, a copolymerized copolymer of a known polymerizable vinyl monomer within a range that does not impair the oil-repellent effect with 5 mol% or less as a guide. Examples of the polymerizable vinyl monomer include methacrylic acid esters such as methyl methacrylate, propyl methacrylate, and allyl methacrylate, acrylic acid esters such as methyl acrylate and butyl acrylate, butyl vinyl ether, styrene, butene, butadiene, acrylonitrile, Examples include acrylamide, maleic anhydride, vinyl chloride and the like.

  Similarly, a hydrocarbon group having 1 to 20 carbon atoms such as an alkyl group, an aryl group, and a hydrogen atom thereof substituted with a silicon-containing group can be used with 5 mol% or less of the side chain group as a guide. it can.

  Various additives may be added to the PVA resin used in the present invention as long as the effect is not impaired. For example, if a silane coupling agent is added in an amount of 0.5 to 10% by mass with respect to the PVA resin, an improvement in adhesion can be expected. Suitable silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane and the like. Results are obtained.

(C) The compounding quantity of the PVA-type resin of a component is 50-1000 mass parts with respect to 100 mass parts of the organopolysiloxane of (A) component, and if it is less than 50 mass parts, oil repellency falls and exceeds 1000 mass parts. And water repellency will be insufficient.

(E) Water of a component is used as a dispersion medium of hydrophobic components, such as a solvent of PVA-type resin, and functional group containing organopolysiloxane in the composition of this invention. An impurity concentration of about the same level as tap water is sufficient, but water mixed with strong acid, strong alkali, a large amount of alcohol, salt, etc. is not suitable for use because it lowers dispersibility.

  The amount of water is adjusted so that the composition of the present invention satisfies the viscosity suitable for the coating apparatus actually used and the coating amount on the target paper material, and is not particularly limited. In general, the concentration is 1 to 20%. As a compounding quantity of water, 100-100000 mass parts is preferable with respect to 100 mass parts of (A) component. When the amount is less than 100 parts by mass, dispersion becomes difficult, and when the amount exceeds 100000 parts by mass, the degradation of the dispersed state with time increases.

  The hydrolyzable group-containing silane as the component (F) used in the present invention has one or more hydrolyzable groups per molecule, preferably two or more, more preferably three or more. Choose from what you have. The more hydrolyzable groups per molecule, the more easily the effect of improving oil repellency.

  Hydrolyzable groups include alkoxy groups such as methoxy, ethoxy, propoxy, butoxy, methoxyethoxy, and isopropenoxy, which are directly bonded to silicon, acyloxy groups such as acetoxy, amino groups such as ethylamino, And oxime groups such as an amide group and an ethylmethylbutanoxime group.

  The group other than the hydrolyzable group is selected from monovalent hydrocarbon groups having 1 to 20 carbon atoms. For example, monovalent hydrocarbons such as alkyl groups such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl groups such as cyclohexyl group, aryl groups such as phenyl group and tolyl group, alkenyl groups such as vinyl group and propenyl group Groups. Alternatively, these groups may have the following substituents, for example, a chloromethyl group in which some or all of the hydrogen atoms are substituted with halogen atoms, a cyanoethyl group substituted with a cyano group, or a glycidide substituted with an epoxy group. Examples thereof include a substituted monovalent hydrocarbon group such as a xylpropyl group, an aminopropyl group substituted with an amino group, a methacryloxypropyl group substituted with an acryl and methacryl group, and a mercaptopropyl group substituted with a thiol group.

  Specifically, tetramethyl silicate, tetraethyl silicate, tetrapropyl silicate, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, vinyltrimethoxysilane, γ-glycidoxy Examples thereof include propyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

  These hydrolyzable group-containing silanes as the component (F) can also be used as partially hydrolyzed and condensed oligosiloxanes. The advantage of using a partially hydrolyzed condensate is that it reduces the amount of hydrolysis by-products and reduces the effect thereof. However, if the degree of polymerization of the oligosiloxane becomes too high, the dispersibility in the composition becomes poor and the repellent properties are reduced. There is a tendency that the effect of improving the oiliness itself decreases. Although the optimum degree of polymerization varies depending on the structure of the selected silane, favorable results can be expected in many cases by setting the average degree of polymerization of oligosiloxane to 50 or less, preferably 10 or less. Moreover, the combined use of the partially hydrolyzed and condensed oligosiloxane and the silane monomer is also possible.

The blending amount of the component (F) is 1 to 250 parts by mass with respect to 100 parts by mass of the functional group-containing organopolysiloxane of the component (A), and a marked improvement in water repellency is not seen at less than 1 part by mass. When the amount exceeds 250 parts by mass, a decrease in dispersibility may be observed over time.

  Preparation of the composition is 0.1 to 30 parts by mass of the crosslinking agent of component (B) and 50 to 50 of PVA-based resin for 100 parts by mass of the functional group-containing organopolysiloxane of component (A). 1000 parts by mass, 1 to 250 parts by mass of the hydrolyzable group-containing silane of component (F) and its partial hydrolysis condensate are blended, and the viscosity and concentration are adjusted in accordance with the coating method and coating amount described below. (E) 100-100000 mass parts of dilution water of a component is added suitably, and it disperse | distributes uniformly using a well-known method, and is set as a processing agent composition. (D) When using the catalyst of a component, it mix | blends a required amount just before coating and disperse | distributes it uniformly.

  Since the functional group-containing organopolysiloxane of component (A) and the cross-linking agent of component (B) are hydrophobic, they are pre-emulsified for the purpose of further improving dispersibility in water-containing compositions. May be. The emulsion may be produced by uniformly dispersing the above components using a known method. For example, the component (A), a part of the component (E), and the component (B) are mixed with a high amount such as a planetary mixer or a combination mixer. Examples of the method include mixing using a shearable stirrer, emulsifying by a phase inversion method, and adding the residue of component (E) to dilute to form an emulsion. Each component may be used alone or in combination of two or more.

  Surfactants can also be utilized to make the emulsion easier to manufacture and improve its stability. Preferred surfactants are nonionic, for example, alkyl ether types such as polyoxyethylene lauryl ether and polyoxyethylene tridecyl ether, and alkyl ester types such as polyoxyethylene oleate and polyoxyethylene laurate. Can be mentioned. These nonionic emulsifiers can be used singly or in combination of two or more. In order to obtain a stable silicone emulsion, it is desirable that these nonionic emulsifiers have an HLB of 10 to 15 either alone or after mixing.

  Anionic surfactants and cationic surfactants can also be used, but it is desirable to use them together with nonionic surfactants from the viewpoint of dispersibility.

  The blending amount of the surfactant is desirably a minimum amount that can sufficiently obtain a good dispersion state and its sustainability. Specifically, it is 0.1 to 10 parts by mass, preferably 0.2 to 6 parts by mass with respect to 100 parts by mass of the functional group-containing organosiloxane of component (A). When the amount is less than 0.1 parts by mass, the effect of promoting emulsification cannot be obtained, and when the amount exceeds 10 parts by mass, the addition reaction between the component (A3) and the component (B3) is inhibited, resulting in a decrease in water repellency and non-adhesiveness. There is.

  As for the water (E) component at the time of emulsification, 100-400 mass parts is preferable with respect to 100 mass parts of (A) component. If the amount is less than 100 parts by mass, the dispersion becomes difficult, and if the amount exceeds 400 parts by mass, the deterioration of the dispersed state over time increases.

  As an alternative to emulsification, use a commercially available silicone emulsion that is water-dispersed and that can be mixed with a PVA resin to form a good dispersion. You can also. A silicone-based emulsion mainly composed of dimethylsiloxane and having a skeleton structure mainly composed of silicone is preferable from the viewpoint of water repellency and non-adhesiveness. For example, silicone for water repellent treatment, release treatment, release paper, etc. A curable emulsion is suitable for use.

  It is desirable that the condensation catalyst (D2) and the addition reaction catalyst (D3) component are not emulsified at the same time as the components (A) and (B) and are added immediately before use. More preferably, the catalyst is preferably water-dispersible prior to addition. For example, a method in which the catalyst is mixed in advance with a surfactant or a method in which an emulsion is formed by the above-described method is effective.

  As for the component (F), the dispersibility in the composition depends on the structure of the hydrolyzable group-containing silane to be selected and the partially hydrolyzed condensate thereof. When it cannot be obtained, it is preferable to adopt a treatment for improving the dispersibility of the component (F). For this purpose, a known method can be used. For example, the following method can be adopted. One of the methods is a method of adding a self-emulsifying type by adding the component (F), an emulsifier and water, or a solution or emulsion. As the emulsifier and the emulsification method used, known ones and methods can be adopted. However, the emulsifier and method used for emulsifying the components (A) and (B) described above may be used, and in some cases (A ) When the component (B) is emulsified, the component (F) can also be blended and emulsified together. As another method, the (F) component and water are mixed and stirred in advance, and part or all of the hydrolyzable functional groups are hydrolyzed to change to silanol groups, thereby increasing dispersibility and obtaining a uniform aqueous solution. It is a method of blending the food. If it is difficult to homogenize, hydrolysis can be promoted by raising the temperature or adjusting the pH of the aqueous phase to 2 to 4 using a small amount of acid. However, if the pH is lowered too much, condensation proceeds and the reverse effect is obtained.

  Water that can be used is sufficient if the impurity concentration is about the same as tap water, but water mixed with strong acid, strong alkali, a large amount of alcohol, salts, etc. is not suitable for use because it lowers dispersibility.

  In addition to these components, catalyst activity inhibitors such as various organic nitrogen compounds, organic phosphorus compounds, acetylene derivatives, oxime compounds, and organic halides are used for the purpose of suppressing the catalytic activity of other optional components such as platinum group metal catalysts. For the purpose of controlling non-stickiness, silicone resin, silica, organopolysiloxane having no hydrogen atom or alkenyl group bonded to silicon atom, leveling agent such as surfactant, water-soluble polymer such as methyl cellulose Thickeners such as cellulose derivatives and starch derivatives, and known improvers such as styrene / maleic anhydride copolymers may be added as necessary for the purpose of improving film-forming properties. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  A coating method which contains 20 to 300 parts by mass of the silicone emulsion and preferably 5 to 100 parts by mass as a silicone component in the emulsion with respect to 100 parts by mass of the PVA resin, and which will be described later. In order to adjust the viscosity and concentration according to the coating amount, the (C) component dilution water is added as appropriate, and uniformly dispersed using a known method to obtain a treating agent composition. The water of component (C) that can be used is sufficient if it has an impurity concentration equivalent to tap water, but water mixed with strong acid, strong alkali, a large amount of alcohol, salts, etc. is suitable for use because it reduces dispersibility. Absent.

  The amount of water is not particularly limited as it is adjusted so as to satisfy the viscosity suitable for the coating apparatus actually used and the coating amount to the target paper material. The concentration is 1 to 20%. As a compounding quantity of water, 100 to 10000 mass parts is preferable with respect to 100 mass parts of (A) component. If the amount is less than 100 parts by mass, the dispersion is difficult, and if it exceeds 10,000 parts by mass, the deterioration of the dispersed state over time increases.

  In addition to these components, other optional components such as silicone resin, silica, or organopolysiloxane having no hydrogen atom or alkenyl group bonded to a silicon atom for the purpose of controlling non-stickiness, a surfactant, etc. Agents, water-soluble polymers, for example, cellulose derivatives such as methylcellulose, thickeners such as starch derivatives, and known improving agents such as styrene / maleic anhydride copolymer for the purpose of improving film-forming properties. Can be added. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

The method of coating the treating agent composition on the paper substrate is usually performed in consideration of the viscosity of the coating liquid, coating speed, etc., calendar coating, gravure coater, air knife coater, roll Coating and spray coating using various coaters such as a coater and a wire bar can be used. The coating amount of the treatment composition is 0.1 g / ^{m 2} or more as a solid content, allyl preferably in the range of 1 to 5 g / ^{m 2.} It is less than 0.1 g / m ² it is difficult to maintain good oil repellency, even performance improvement beyond 5 g / m ² is cost-disadvantageous small.

  After coating, a water- and oil-repellent paper is obtained by passing through a dryer and drying by heating. The heat drying conditions are typically, for example, a temperature of 140 ° C. or higher and a time of 10 seconds or longer.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

A. Preparation of raw materials
Preparation Example 1
To a 5 liter composite emulsifying device having a vertical stirring device capable of stirring the entire interior of the container and a rotatable disc having small tooth-shaped projections alternately provided on the periphery, the following as component (A2) 100 parts by mass of the polyorganosiloxane represented by the formula

（式中のＭｅはメチル基を示し、２５℃での粘度が２Ｐａ・ｓ、シラノール基含有量＝０．０１モル／１００ｇ）、
（Ｂ２）成分として以下の式で示されるメチルハイドロジエンポリシロキサンを３質量部

(Me in the formula represents a methyl group, the viscosity at 25 ° C. is 2 Pa · s, the silanol group content = 0.01 mol / 100 g),
(B2) 3 parts by mass of methylhydrogenpolysiloxane represented by the following formula as a component

（式中のＭｅはメチル基を示し、粘度が２５ｍＰａ・ｓ、Ｈ含有量＝１．５モル／１００ｇ）、界面活性剤としてポリオキシエチレンラウリルエーテルのＨＬＢが１３．６のもの１質量部、４％水溶液の２０℃での粘度３０ｍＰａ・ｓ、ケン化度９０モル％のＰＶＡ樹脂５質量部（予め１０％水溶液に調整したもの５０質量部として使用）を仕込み、均一に撹拌混合した。

(Me in the formula represents a methyl group, viscosity is 25 mPa · s, H content = 1.5 mol / 100 g), 1 part by mass of polyoxyethylene lauryl ether having an HLB of 13.6 as a surfactant, 5 parts by mass of a PVA resin having a viscosity of 30 mPa · s at 20 ° C. and a saponification degree of 90 mol% (used as 50 parts by mass in advance of a 10% aqueous solution) was charged and mixed uniformly.

  To this mixture, 10 parts by mass of water was added for phase inversion, followed by stirring for 30 minutes. An additional 836 parts by mass of water was added, diluted and stirred to obtain an O / W emulsion having a solid content of 10%. This was used as a silicone emulsion of components (A2) and (B2).

Preparation Example 2
In a 5 liter composite emulsifying device having a vertical stirring device capable of stirring the entire inside of the container and a rotatable disk in which small tooth-shaped projections are alternately provided on the periphery on the periphery,
(A3) 100 parts by mass of a polyorganosiloxane represented by the following formula as a component

（式中のＭｅはメチル基を示し、Ｖｉはビニル基を示し、２５℃での粘度が０．４Ｐａ・ｓ、ビニル基含有量は０．０３モル／１００ｇ）、（Ｂ３）成分として以下の式で示されるメチルハイドロジエンポリシロキサンを６質量部

(Me in the formula represents a methyl group, Vi represents a vinyl group, the viscosity at 25 ° C. is 0.4 Pa · s, and the vinyl group content is 0.03 mol / 100 g). 6 parts by mass of methylhydrogenpolysiloxane represented by the formula

（式中のＭｅはメチル基を示し、粘度が２５ｍＰａ・ｓ、Ｈ含有量＝１．５モル／１００ｇ）、界面活性剤としてポリオキシエチレンラウリルエーテルのＨＬＢが１３．６のもの１質量部、４％水溶液の２０℃での粘度３０ｍＰａ・ｓ、ケン化度９０モル％のＰＶＡ樹脂５質量部（予め１０％水溶液に調整したもの５０質量部として使用）、触媒活性抑制剤としてエチニルシクロヘキサノール０．４質量部を仕込み、均一に撹拌混合した。

(Me in the formula represents a methyl group, viscosity is 25 mPa · s, H content = 1.5 mol / 100 g), 1 part by mass of polyoxyethylene lauryl ether having an HLB of 13.6 as a surfactant, 5 parts by mass of a PVA resin having a viscosity of 30 mPa · s at 20 ° C. in a 4% aqueous solution and a saponification degree of 90 mol% (used as 50 parts by mass previously adjusted to a 10% aqueous solution), ethynylcyclohexanol 0 as a catalyst activity inhibitor .4 parts by mass were charged and stirred and mixed uniformly.

  To this mixture, 10 parts by mass of water was added for phase inversion, followed by stirring for 30 minutes. An additional 833 parts by weight of water was added, diluted and stirred to obtain an O / W emulsion having a solid content of 10%. This was used as a silicone emulsion of components (A3) and (B3).

Preparation Example 3
A 10% aqueous solution was prepared by mixing 100 parts by mass of a PVA resin having a viscosity of 30 mPa · s at 20 ° C. and a saponification degree of 90 mol% with 900 parts by mass of water and stirring until a uniform solution was obtained. . This was used as a PVA-based resin as component (C).

Preparation Example 4
A 10% aqueous solution was prepared by mixing 100 parts by mass of a 4% aqueous solution with a viscosity of 5 mPa · s at 20 ° C. and 100 parts by mass of PVA resin having a saponification degree of 80 mol% and 900 parts by mass of water and stirring until a uniform solution was obtained. . This was used as a PVA-based resin as component (C).

Preparation Example 5
A 4% aqueous solution was mixed with 100 parts by mass of PVA resin having a viscosity of 60 mPa · s at 20 ° C. and a saponification degree of 98 mol% and 900 parts by mass of water, and stirred until a uniform solution was obtained to prepare a 10% aqueous solution. . This was used as a PVA-based resin as component (C).

B. Preparation of treatment composition
Example 1
100 parts by mass of the silicone emulsion of Preparation Example 1, 200 parts by mass of the PVA-based resin aqueous solution of Preparation Example 3 and 3 parts by mass of tetraethoxysilane were mixed well and used as a treating agent composition.

Example 2
100 parts by mass of the silicone emulsion of Preparation Example 2, 200 parts by mass of the PVA resin aqueous solution of Preparation Example 3, 3 parts by mass of methyltriethoxysilane, and platinum catalyst emulsion CAT-PM-10A manufactured by Shin-Etsu Chemical Co., Ltd. A treatment composition was prepared by mixing 1 part by mass (platinum mass 100 ppm with respect to silicone) and mixing well.

Example 3
100 parts by mass of the silicone emulsion of Preparation Example 2, 200 parts by mass of the PVA resin aqueous solution of Preparation Example 3, 3 parts by mass of an average dimerized tetraethoxysilane, and 1 part by mass of CAT-PM-10A are mixed well. This was used as a treating agent composition.

Example 4
A treating agent prepared by mixing 100 parts by mass of the silicone emulsion of Preparation Example 2, 1000 parts by mass of the PVA resin aqueous solution of Preparation Example 3, 25 parts by mass of tetraethoxysilane, and 1 part by mass of CAT-PM-10A and mixing them well. It was set as the composition.

Example 5
100 parts by mass of the silicone emulsion of Preparation Example 2, 50 parts by mass of the PVA resin aqueous solution of Preparation Example 3, 0.1 part by mass of tetraethoxysilane, and 1 part by mass of CAT-PM-10A were mixed well. A treating agent composition was obtained.

Example 6
Treatment agent prepared by mixing 100 parts by mass of the silicone emulsion of Preparation Example 2, 200 parts by mass of the PVA resin aqueous solution of Preparation Example 4, 3 parts by mass of tetraethoxysilane, and 1 part by mass of CAT-PM-10A. It was set as the composition.

Example 7
100 parts by mass of the silicone emulsion of Preparation Example 2, 200 parts by mass of the PVA resin aqueous solution of Preparation Example 5, 3 parts by mass of tetraethoxysilane, and 1 part by mass of CAT-PM-10A were mixed well and treated. It was set as the composition.

Comparative Example 1
100 parts by mass of the silicone emulsion of Preparation Example 2, 200 parts by mass of the PVA-based resin aqueous solution of Preparation Example 3, and 1 part by mass of CAT-PM-10A were mixed well to obtain a treating agent composition.

Comparative Example 2
100 parts by mass of the silicone emulsion of Preparation Example 2, 200 parts by mass of the PVA resin aqueous solution of Preparation Example 3, 0.05 parts by mass of tetraethoxysilane, and 1 part by mass of CAT-PM-10A were mixed well. A treating agent composition was obtained.

Comparative Example 3
100 parts by weight of the silicone emulsion of Preparation Example 2, 200 parts by weight of the aqueous PVA resin solution of Preparation Example 3, 27 parts by weight of tetraethoxysilane, and 1 part by weight of CAT-PM-10A are mixed well and treated. It was set as the composition.

Comparative Example 4
100 parts by weight of the silicone emulsion of Preparation Example 2, 1200 parts by weight of the PVA aqueous resin solution of Preparation Example 3, 3 parts by weight of tetraethoxysilane, and 1 part by weight of CAT-PM-10A were mixed well and treated. It was set as the composition.

Comparative Example 5
100 parts by mass of the silicone emulsion of Preparation Example 2, 30 parts by mass of the PVA resin aqueous solution of Preparation Example 3, 3 parts by mass of tetraethoxysilane, and 1 part by mass of CAT-PM-10A were mixed well and treated. As a composition

C. Preparation of water- and oil-repellent paper Apply the treatment composition prepared in the Preparation Example to a commercial kraft paper having a basis weight of 50 g / m ² using a bar coater so that the coating amount as a solid content is 2 g / m ^2. And heated with a drier at 140 ° C. for 30 seconds to prepare a water / oil repellent paper.

D. Evaluation methods
The appearance after standing at room temperature for 1 week in a dispersed state was visually observed. The case where separation was not observed was unsatisfactory.

It was measured by an oil repellency 3M kit test (TAPPI-RC-338). The 3M kit test method is a test in which a test oil containing castor oil, toluene, and heptane is placed on the surface of a water- and oil-repellent paper to determine whether or not it is permeated. The kit number of the largest test oil that did not permeate was taken as the evaluation result, and the larger the value, the better the oil repellency. A kit number of 12 or more was shown as ◯, a kit number of 8 to 11 as Δ, and a kit number of 7 or less as x.

The water- repellent water-repellent and oil-repellent paper surface was measured by the contact angle with water. A larger contact angle indicates better water repellency. Those having a contact angle exceeding 100 ° were shown as ◯, those having a contact angle of less than 100 ° and 90 ° or more were shown as Δ, and those having a contact angle of less than 90 ° were shown as ×.

A Nitto 31B tape (width 50 mm) was applied to the surface of non-adhesive water and oil repellent paper, and after aging for 20 hours under the condition of 70 ° C. under a load of 20 g, the force required to peel the tape in the 180 ° direction was measured with an autograph. . Those having a peeling force of 1 N or less are indicated by ◯, and those having a peeling force exceeding 1 N are indicated by ×.

Elution test A water- and oil-repellent paper having a coating surface of 10 cm 2 was immersed in 20 ml of distilled water, allowed to stand at 60 ° C. for 30 minutes, and then filtered to obtain an eluate. In an Erlenmeyer flask, 10 ml of eluate, 0.5 ml of sulfuric acid, and 1 ml of 0.002 mol / l potassium permanganate solution were taken and boiled for 5 minutes. After heating, 1 ml of a 0.01 mol / l sodium oxalate solution was added and titrated with a 0.002 mol / l potassium permanganate solution until the color turned slightly red. Separately, the eluate was titrated with distilled water to obtain a blank, and the amount of eluate from the water- and oil-repellent paper coated surface was calculated as the potassium permanganate consumption amount using the following formula.
Potassium permanganate consumption (ppm) = {eluent titration (ml) -blank titration (ml)} × 31.6
A smaller value indicates better water repellency and water resistance.

E. Evaluation results The results are summarized in Table 1 below.

Claims (8)

Ing from the following ingredients water dispersion type water and oil repellent composition.
(A) Functional group-containing organopolysiloxane 100 parts by mass (B) Cross-linking agent 0.1-30 parts by mass (C) Polyvinyl alcohol (hereinafter abbreviated as PVA) resin 50-1000 parts by mass (D) Catalyst As an active ingredient 0 to 5 parts by mass (E) Water 100 to 100000 parts by mass (F) Hydrolyzable group-containing silane and / or its partial hydrolysis condensate
1 to 250 parts by mass The water-dispersed water / oil repellent according to claim 1 , wherein the components ( A) , (B) and (D) are the following components (A2) , (B2) and (D2), respectively.
(A2) Organopolysiloxane having a structure represented by the following average composition formula (1) and having at least two hydroxyl groups in one molecule

[Wherein, R ¹ represents a monovalent hydrocarbon group, R ³ represents a hydroxyl group, and X ² represents a group represented by the following formula:

(A2, b2, c2, d2 the viscosity at 25 ° C. of the organopolysiloxane is chosen from a positive number to fully plus the 0.05~500Pa · s, b2, c2, d2 may be zero.) ]
(B2) Organohydrogenpolysiloxane or organopolysiloxane having at least three hydrogen atoms bonded to silicon atoms (hereinafter abbreviated as SiH) or hydrolyzable groups in one molecule, and contained SiH or hydrolysis moles sex groups, (A2) weight portion corresponding to 5 to 200 times the number of moles of hydroxyl groups contained in the component (D2) catalytic amount of a condensation catalyst The water-dispersed water / oil repellent according to claim 1 , wherein the components ( A) , (B) and (D) are the following components (A3) , (B3) and (D3), respectively.
(A3) Organopolysiloxane having a structure represented by the following average composition formula (2) and having at least two alkenyl groups in one molecule

[In the formula, R ¹ is a monovalent hydrocarbon group, R ² represents an alkenyl group, X ³ is a group represented by the following formula.

(A3, b3, c3, d3 , e3 the viscosity at 25 ° C. of the organopolysiloxane is chosen from a positive number to meet the 0.05~500Pa · s, b3, c3, d3, e3 is 0 Α and β are 0, 1, 2 or 3.)]
(B3) An organohydrogenpolysiloxane having at least three SiHs in one molecule, wherein the number of moles of SiH contained corresponds to 1 to 5 times the number of moles of alkenyl groups contained in component (A3) Part (D3) catalyst amount of a platinum group metal catalyst The component (C) PVA-based resin is one or two selected from the range in which the viscosity at 20 ° C. of the 4% aqueous solution satisfies the saponification degree of 80 to 99.5 mol% at 2 to 80 mPa · s. The water-dispersed water / oil repellent according to any one of claims 1 to 3, wherein the above is used. Component (C) is a PVA-based resin, or a polymerizable vinyl monomer in the range of 5 mol% or less are those obtained by copolymerizing, or 1 to 20 carbons in the hydrocarbon group and their the groups in which some or all are substituted with a silicon-containing group of the hydrogen atom, any one of claims 1 to 3, 5 mol% of side groups following is characterized in that substituted Water-dispersed water and oil repellent. (F) silane component, an alkoxy group as a hydrolyzable functional group, an acyloxy group, a group selected from an oxime group, according to any one of claims 1 to 5 are those with 2 or more per molecule Water-dispersed water and oil repellent. Repellent oiled paper and sheets treated with water dispersion type water and oil repellent of any one of claims 1 to 6. Either a water dispersion type water and oil repellent of any preceding claim, water- oil paper and sheet produced by the addition method among to be added upon papermaking of claims 1 to 6.