CN101195726B - Coating emulsion composition, and water/oil-repellent paper and making method - Google Patents
Coating emulsion composition, and water/oil-repellent paper and making method Download PDFInfo
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- CN101195726B CN101195726B CN2007101807592A CN200710180759A CN101195726B CN 101195726 B CN101195726 B CN 101195726B CN 2007101807592 A CN2007101807592 A CN 2007101807592A CN 200710180759 A CN200710180759 A CN 200710180759A CN 101195726 B CN101195726 B CN 101195726B
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- 230000033228 biological regulation Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010073 coating (rubber) Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001354 dialkyl silanes Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HTSRFYSEWIPFNI-UHFFFAOYSA-N ethyl-dimethoxy-methylsilane Chemical compound CC[Si](C)(OC)OC HTSRFYSEWIPFNI-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 235000021393 food security Nutrition 0.000 description 1
- 238000009432 framing Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000010733 inhibited oil Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- OTIVLGJBKUFOEX-UHFFFAOYSA-N n-tetradecoxyaniline Chemical compound CCCCCCCCCCCCCCONC1=CC=CC=C1 OTIVLGJBKUFOEX-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000004028 organic sulfates Chemical class 0.000 description 1
- PFPYHYZFFJJQFD-UHFFFAOYSA-N oxalic anhydride Chemical compound O=C1OC1=O PFPYHYZFFJJQFD-UHFFFAOYSA-N 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical group [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- WQQPDTLGLVLNOH-UHFFFAOYSA-M sodium;4-hydroxy-4-oxo-3-sulfobutanoate Chemical class [Na+].OC(=O)CC(C([O-])=O)S(O)(=O)=O WQQPDTLGLVLNOH-UHFFFAOYSA-M 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical class [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
- Paper (AREA)
Abstract
The invention provides a paint latex composition, a water-resistance/oil-resistance paper sheet and a production method thereof. An organic polysiloxane comprising at least two silicon-bonded hydroxyl groups, the reaction product of an amino-containing organoalkoxysilanea dicarboxylic anhydride and an dicarboxylic acid ahhydride, an organic polysiloxane containing long-chain alkyl and alkoxy groups, but free of hydroxyl groups are emulsified and dispersed in water in the presence of a surfactant to form a coating emulsion composition.
Description
Technical field
The present invention relates to have the coating emulsion compsn of coating uniform characteristics.The invention still further relates to and refuse water, refuse oilpaper material and method of manufacture thereof; This paper wood can be used for packaging material for food; Be used to comprise the housing material of paper substrate; Can be used for packing the housing material of chocolate and dessert, or can be used for packing the carton and the paper bag of fried potato, fried chicken, fried face volume, biscuit and cake, and can be used for packing the housing material of hamburger and fried food product.
Background technology
Like Japanese patent application JP-A-5-98579 corresponding to USP 5254621; Japanese patent application JP-A-8-85760; Japanese patent application JP-A-9-208826 corresponding to USP 5827921; Corresponding to disclosed among the Japanese patent application JP-A-2000-34410 of USP 6140414 and the Japanese patent application JP-A-2001-55510, the cross linking polysiloxane emulsion compositions of many curable one-tenth rubber coatings is known in this area.This based composition is coated on and applies effectively when fabric, building slab and other have the matrix of irregular surface that to handle be feasible.Yet, when with this type applying coating at film, paper wood has with other can produce some problems when forming shallow layer on the base material of smooth surface.Because the weight at applying step process floating coat can change, thereby can not form the uniform coating of thickness.
Have refusing water, refusing packaging material for food and housing material that the oilpaper material is used as packing rich food such as fried food product and oil-containing, lipid food etc. usually of inhibited oil infiltration function.This type refuse water, refuse that the oilpaper material not only requires is to refuse water fully and refuse oil, but also must be safe.The many suggestions that proposed are well known in the art.Recently, those wherein blending the refusing water, refuse the oilpaper material and caused the concern of people of organic fluorine to its security.As substitute, Japanese patent application JP-A8-209590 and JP-A-9-87994 disclose and on paper substrate, have been formed with the paper wood of refusing water, refusing oil reservoir.
Have the prior art of organic fluorine to refuse water with blending, refuse the oilpaper material and compare, in order to guarantee safety, those are formed with the paper wood of refusing water, refusing oil reservoir on paper substrate be to be difficult to provide enough water and oil repellents refused.It must be noted that, particularly at paper wood through being bent into carton or when the ground, the refusing water and can understand impaired significantly of its bending part with oil repellent.
Summary of the invention
First purpose of the present invention provides the coating emulsion compsn with coating uniform characteristics.Second purpose provide improved water repellency and oil repellent refuse water and the method for refusing the oilpaper material and preparing this paper wood, wherein this paper wood after bending, the bending place refuse water and oil repellent loses hardly, and have separability and security feature.
Through in the presence of tensio-active agent, will be improved the coating emulsion compsn of coating uniformity with disperseing like component (A)-(F) emulsification in water of giving a definition, thereby realize this first purpose.
In first aspect, coating emulsion compsn provided by the invention comprises:
(A) comprise at least two organopolysiloxanes with the oh group of silicon bonding in the 100 weight part molecules,
(B) the 0.5-20 weight part contains the amino organoalkoxysilane and the reaction product of dicarboxylic anhydride,
(C) the 0-20 weight part contains organoalkoxysilane and/or its partial hydrolysate of epoxy,
(D) 0-50 weight part colloidal silica and/or polysilsesquioxane,
(E) 0-10 weight part curing catalysts, and
(F) the 0.5-20 weight part contains chain alkyl and alkoxy base but the organopolysiloxane of non-hydroxyl group,
In the presence of tensio-active agent, emulsification and dispersed component (A)-(F) in water.
The coating that is formed by the coating emulsion compsn can stick on any matrix evenly, fully.When handling fiber, paper, film, leather and material of construction with said composition, the coating of formation has water repellency, water-repellancy and barrier property.If the surface of coated base material is more regular, then can obtain best result.Said composition also can be used as the tackiness agent of adhesive function property inorganic filler such as photocatalyst.
Applying processing with the present composition can form uniform coating and difference in thickness can not occur.
The embodiment that reaches second purpose of the present invention be folding resistance improved, have refuse water, oil repellent can paper wood, this paper wood comprise scribble on paper substrate and at least one surface thereof refuse water, refuse oil, strippable polyorganosiloxane resin layer.Bending part when if paper wood comprises common planar section with bending; Then planar section has the Kit value and is at least 9 oil-proofness; Bending part has the Kit value and (presses J.TAPPI paper/pulp test No41-83 at least 8 oil-proofness; Under 20 ℃ and 50% humidity condition, measure), planar section has the water repellency of R8 at least, and bending part has the water repellency of R7 (press J.TAPPI paper/pulp test No.68:2000 mensuration) at least.
Because paper wood of the present invention scribbles and has the polyorganosiloxane resin layer of refusing water, refusing oil and stripping performance, therefore, this paper wood has good water, the oil repellent ability of refusing usually.Even paper wood is bent, refuse water, the oil repellent of bending part also lose hardly.Therefore this paper wood can be used for packaging material for food; Be used to comprise the housing material of paper substrate and the housing material of packing chocolate and dessert; Also can be used for packing the carton and the paper bag of fried potato, fried chicken, Deep-fried doughnut, biscuit and cake, and can be used for packing the housing material of hamburger and fried food product.
The present invention also provides a kind of method of refusing water, refusing the oilpaper material that is used to make; This method comprises mainly comprising refusing water, refusing oil compsns and be coated at least one surface of paper substrate of water-based polyorganosiloxane resin emulsion; So that the weight of dry coating reach at least 1.0 grams/square metre, thereby formed refuse water, refuse oil, strippable polyorganosiloxane resin layer.Paper substrate is selected from NBSK paper, non-wood pulp paper, cardboard, lining facial tissue, glassine and vellum paper.
Through will mainly comprise water-based polyorganosiloxane resin emulsion refuse water, refuse surface that oil compsns is coated in paper substrate just can make very easily have improved refuse water, oil repellent can paper wood.
Paper wood of the present invention because of applied have refuse water, refuse oil and the polyorganosiloxane resin layer of peelable performance have improvedly refuse water, oil repellent can; Even through bending; It refuses water, also almost free of losses of oil repellent, perhaps at bending part within actual allowed band.Therefore, this is refused water, refuses that the oilpaper material is applicable to commercial food product packing and as the various rich foods of packing such as fried food product and oil-containing, lipid outer package of food material.
Embodiment
In the present disclosure of the invention, symbol (Cn-Cm) is meant that every group contains the group of n carbon atom-m carbon atom.All umbers all are meant weight part, except as otherwise noted.
First embodiment
Coating emulsion compsn according to the first embodiment of the present invention comprises following component.
Component (A) is to comprise at least two organopolysiloxanes with the oh group of silicon bonding in each molecule, generally is the organopolysiloxane with an average group accepted way of doing sth (1):
R is C independently of one another in the formula
1-C
20Alkyl group or C
6-C
20Aromatic yl group.X is C independently of one another
1-C
20Alkoxy base or oh group, condition are that at least two X are oh groups.Subscript " a " is 0 or is the positive number of 0＜a≤1000 that " b " is the positive number of 100≤b≤10000, and " c " is 0 or is the positive number of 0＜c≤1000,100≤a * c+b≤100000, and r is 1,2 or 3.
Particularly, R is selected from C independently of one another
1-C
20Alkyl group and C
6-C
20Aromatic yl group, for example: the chain-like alkyl group, like methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl; Group of naphthene base is like cyclopentyl, cyclohexyl and suberyl; And aromatic yl group, like phenyl, tolyl and naphthyl, and methyl is preferred.X is selected from C independently of one another
1-C
20, (preferred C
1-C
6) alkoxy base and oh group, the instance of suitable alkoxy base comprises methoxyl group, oxyethyl group, propoxy-, butoxy and pentyloxy group.
If " a " surpasses 1000, the undercapacity of the coating that obtains.Therefore, a is-1000 a positive number more than 0 or 0, is preferably more than 0-200 positive number.If the coating that " b " less than 100, obtains is flexible not enough.If " b " surpasses 10000, the tear strength that obtains coating is lower.Therefore " b " is the positive number of 100-10000, is preferably the positive number of 1000-5000.Preferably " c " is the positive number of 1-1000.Be pointed out that,, should comprise at least two oh groups with the silicon bonding in the molecule of organopolysiloxane (A) from crosslinked.
The instance of organopolysiloxane (A) comprise following formula (i)-(polymkeric substance vi):
Me represent methylidene, Ph represent phenyl in the formula.Subscript m is 0 or the positive number of 0＜m≤1000, preferred 0＜m≤200; N is the positive number of 100≤n≤10000, preferred 1000≤n≤5000; D is 0 or the positive number of 0＜p≤1000, preferred 1≤p≤1000.
Organopolysiloxane can prepare through well-known technology.For example, can pass through annular siloxane (like octamethylcyclotetrasiloxane) and α, the alpha, omega-dihydroxy siloxane oligomer carries out balanced reaction and prepares in the presence of catalyzer such as metal hydroxides.Because component (A) is preferably used with emulsion form, so it can obtain with emulsion form through well-known emulsion polymerization technology.Specifically; Can be by negatively charged ion or cats product; The optional catalyzer (like acidity or basic material) that adds makes annular siloxane and α, alpha, omega-dihydroxy siloxane oligomer, α in advance; ω-dialkoxy siloxane oligomer or organoalkoxysilane carry out emulsification and dispersion in water, and carry out polyreaction and easily make.
This emulsion is preferably through at least a organic sulfonic acid that is selected from; Under the existence of the AS of organic sulfate and organic sulfonate; Make above-mentioned organopolysiloxane emulsification and be dispersed in to form initial latex in the aqueous medium, initial latex polymerization and neutralization are prepared.Be preferably formed this emulsion to mean particle size and be 500 nanometers at the most, more preferably 400 nanometers at the most.If granularity surpasses 500 nanometers, then emulsion will be unstable, and the polymerization rate that can slow down needs to prolong the running time.
For the polymerization of emulsion, polymerization temperature is preferably 0 ℃-90 ℃, more preferably 5 ℃-80 ℃.Temperature is lower than 0 ℃ of polyreaction that can slow down, and is higher than 90 ℃, and emulsion can loss of stability during carrying out polyreaction.The preferred 1-200 of polyreaction required time hour, more preferably 5-100 hour.Polyreaction is preferably in stable state, or under moderate agitation, carries out.
After polyreaction was accomplished, the interpolation alkaline matter was neutralized to preferred pH value with this system and is 4-9.If the pH value is lower than 4 or be higher than 9, the permanent stability of the organic polysiloxane emulsion that obtains can descend.Preferred pH value should be 5-8.The instance of addible alkaline matter comprises inorganic alkaline compound such as alkali metal hydroxide, alkaline earth metal hydroxides, alkaline carbonate and alkaline earth metal carbonate, and organic basic compound such as ammonia and organic amine.
In order to improve the stability that obtains by letex polymerization as the organic polysiloxane emulsion of component (A); Can carry out before or after the letex polymerization; Perhaps behind N-process, add any other AS; Nonionogenic tenside and amphoterics, only otherwise infringement the object of the invention.The AS that is suitable for comprises the salt of high alkyl sulfate, salt, sulfonated alkylbenzene, the salt of senior alkyl SULPHOSUCCINIC ACID ESTER, the salt of ethoxylation high alkyl sulfate, the salt of ethoxylated alkyl phenyl ether sulfuric ester and the salt of ethoxylation senior alkyl SULPHOSUCCINIC ACID ESTER of alkyl phenyl ether sulfuric ester.The ionic surfactant pack that is suitable for is drawn together ethoxylation higher alcohols, ethoxylated alkylphenol, polyhydric alcohol fatty acid ester, ethoxylation polyhydric alcohol fatty acid ester, ethoxylated fatty acid, ethoxylated fatty acid acid amides, Sorbitol Powder, sorbitan fatty(acid)ester, ethoxylation sorbitan fatty(acid)ester and sucrose fatty ester.The amphoterics that is suitable for comprises amino acid and beet alkali surface activator.
Component (B) is to contain the amino organoalkoxysilane and the reaction product of dicarboxylic anhydride.It has useful effect to improving polysiloxane coating to the adhesivity of base material.Component (B) can be reacted and makes through containing amino organoalkoxysilane and dicarboxylic anhydride.A kind of organoalkoxysilane reagent that contains amino is the organoalkoxysilane with formula:
A(R)gSi(OR)
3-g
The regulation of R is the same in the formula, and A is amido-containing group-R
3(NHR
3)
hNHR
4(R wherein
3Be C independently of one another
1-C
6Divalent hydrocarbyl mission, R
4Be R or hydrogen, h is the 0-6 integer), g is 0,1 or 2, promptly contain non-substituted amino group (promptly-NH
2) or substituted amino group (promptly-NHR
4) organoalkoxysilane.The illustrative example of organoalkoxysilane is following:
(C
2H
5O)
3SiC
3H
6NH
2
(C
2H
3O)
2(CH
3)SiC
3H
6NH
2
(CH
3O)
3SiC
3H
6NH
2
(CH
3O)
2(CH
3)SiC
3H
6NH
2
(CH
3O)
3SiC
3H
6NHC
2H
4NH
2
(CH
3O)
2(CH
3)Sic
3H
6NHC
2H
4NH
2
Comprise maleic anhydride, Tetra hydro Phthalic anhydride, succinyl oxide, methylsuccinic acid acid anhydride, Pyroglutaric acid and itaconic anhydride with the instance of the dicarboxylic anhydride that contains amino organoalkoxysilane reaction.Wherein maleic anhydride is preferred; Is 0.5 in amino group with the mol ratio of acid anhydrides: 1-2: 1 ratio makes the organoalkoxysilane that contains amino combine with dicarboxylic anhydride; And under room temperature or elevated temperature, choose wantonly in hydrophilic organic solvent, to mix and easily to carry out this reaction.The suitable hydrophilic organic solvent comprises: alcohol, like methyl alcohol, ethanol, Virahol and butanols, ketone is like acetone and methylethylketone, acetonitrile, THF etc.
The consumption of component (B) is that per 100 parts by weight of component (A) are the 0.5-20 weight part.Component (B) consumption is lower than 0.5 weight part improving not too effective aspect the adhering effect of base material, if be higher than 20 weight parts, then can make the coating hardening, become fragile.Preferable amount is the 1-10 weight part.
Component (C) is organoalkoxysilane and/or its partial hydrolysate that contains epoxy group(ing).It is effective aspect raising polysiloxane coating and the adhering effect of base material.The example comprises:
γ-glycidoxypropyltrime,hoxysilane
γ-glycidoxy propyl group dimethoxy-methyl silane,
β-(3，4-Huan Yanghuanjiji)Yi Jisanjiayangjiguiwan and
β-(3, the 4-epoxycyclohexyl) ethyl dimethoxy-methyl silane.
The consumption of component (C) is that per 100 parts by weight of component (A) are the 0-20 weight part.Component (C) consumption is higher than 20 parts of meetings to be made the coating hardening, becomes fragile.Preferable amount is the 1-10 weight part.
Component (D) is colloidal silica and/or polysilsesquioxane, and adds as the form of film toughener.The instance of component (D) comprises colloidal silica and as the poly methyl silsesquioxane of the hydrolytic condensate of trimethoxymethylsila,e.The type of colloidal silica is unrestricted.Its common granularity is the 5-50 nanometer and carries out stabilization through sodium, ammonia or aluminium.It is commercially available can be used for colloidal silica of the present invention; Their commodity are called Snowtex (Nissan Chemical Industries Ltd.); Ludox (W.R.Grace & Co.); Silicadol (Nippon Chemical Industrial Co.Ltd.), Adelite AT (AsahiDenka Kogyo K.K) and Cataloids (Catalysts & Chemicals Industries Co.Ltd.).
Obtain poly methyl silsesquioxane and be through: add the condensation catalyst that is selected from acid (like sulfuric acid) and basic cpd (like Pottasium Hydroxide) to water phase surfactant mixture; Drip trimethoxymethylsila,e; Stirred solution makes emulsifying soln, thereby obtains to contain the emulsion of poly methyl silsesquioxane.In order to adjust the degree of crosslinking of polysilsesquioxane, in reaction process, can add alkoxyl group trialkyl silane, dialkoxy dialkyl silane or tetraalkoxysilane.In order to improve the reactive behavior of polysilsesquioxane, also can add vinyl silanes, epoxy silane, acrylic silane or methylacrylic acid silane.The consumption of component (D) is that per 100 parts by weight of component (A) are the 0-50 weight part.Component (D) consumption then can make the polysiloxane coating hardening, become fragile if be higher than 50 weight parts.Preferable amount is the 1-30 weight part, more preferably the 2-25 weight part.Component (D) preferred size is the 2-200 nanometer.
Component (E) is to promote the condensation reaction between each component in the compsn, to cause the curing catalysts of crosslinked and solidification.The catalyzer that is suitable for comprises: organic acid metal-salt such as dibutyl tin laurate, two sad dibutyl tins, two LAURIC ACID 99 MIN dioctyl tins, two alkanecarboxylic acid dioctyl tins, oxalic acid dioctyl tin, two oil base oxysuccinic acid dibutyl tins, stannous octoate, Zinic stearas, zinc octoate, zinc acetate and iron octoate; Amine compound such as normal hexyl Amine and guanidine.Except those water-soluble catalysts, curing catalysts is hoped also can be by tensio-active agent emulsification in water, dispersion and formerly be transformed into emulsion.The consumption of component (E) is that per 100 parts by weight of component (A) are the 0-10 weight part, is preferably the 0-5 weight part.Be higher than 10 weight parts like fruit component (E) consumption, this catalyst component of then staying in the coating with the non-volatile substance form can possibly have a negative impact to the performance of coating.Even the content of component (E) is zero, crosslinking reaction also can be carried out, and this is can play promotor because contain amino organoalkoxysilane with reaction product as the dicarboxylic anhydride of component (B).The addition of component (E) is 10 weight parts at the most, is preferably at the most 5 weight parts can reach desired solidification rate and coating characteristic.
Component (F) is to contain long-chain (preferred C
4-C
20) alkyl and alkoxy grp, but the organopolysiloxane of hydroxyl group not adds component (F) to improve the homogeneity of coat operations process floating coat.Preferably, component (F) is for having the organopolysiloxane of an average group accepted way of doing sth (2):
R in the formula
1Be C independently of one another
1-C
3Alkyl or phenyl, Q are C independently of one another
4-C
20Alkyl, Z are respectively done for oneself independently-OR
2,-C
2H
4-Si (OR
2)
3Or-C
3H
6-Si (OR
2)
3Group, wherein R
2Be C
1-C
6Alkyl, subscript d are the positive numbers of 1-100, and e is the positive number of 1-100, and f is that positive number and the q of 0.1-30 is 0,1,2 or 3.
Specifically, R
1Be phenyl or C independently of one another
1-C
3Alkyl group, the example comprise methyl, ethyl and propyl group, and methyl is preferred.Q is C independently of one another
4-C
20Alkyl group, for example butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl.Wherein hexyl, octyl group, decyl and dodecyl are preferred.Z is-OR independently of one another
2,-C
2H
4-Si (OR
2)
3Or-C
3H
6-Si (OR
2)
3Group, wherein R
2Be C
1-C
6Alkyl group.The instance of Z comprise methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy ,-C
2H
4-Si (OCH
3)
3,-C
2H
4-Si (OC
2H
5)
3,-C
3H
6-Si (OCH
3)
3,-C
3H
6-Si (OC
2H
5)
3Deng.Wherein methoxyl group, oxyethyl group and--C
2H
5-Si (OCH
3)
3Be preferred.
Have in the organopolysiloxane of an average group accepted way of doing sth (2), the organopolysiloxane with average group accepted way of doing sth (3) is preferred.
Q is selected from hexyl, octyl group, decyl and dodecyl separately in the formula, Z be selected from independently of one another methoxyl group, oxyethyl group and-C
2H
4-Si (OCH
3)
3, subscript d is the positive number of 1-100, e is the positive number of 1-100, f is the positive number of 0.1-30.
With regard to coating uniformity, d is the positive number of 1-100, and e is the positive number of 1-100, and f is the positive number of 0.1-30; Preferably, d is the positive number of 2-90, and e is the positive number of 2-90, and f is the positive number of 0.1-20.
The consumption of component (F) is that per 100 parts by weight of component (A) are the 0.5-20 weight part.Component (F) consumption then can lose the effect of giving coating uniformity if be lower than 0.5 weight part, if be higher than 20 weight parts, then can hinder the curing of coating, thereby can have a negative impact to coating performance.The preferable amount of component (F) is that per 100 parts by weight of component (A) are 1-15 weight part, more preferably 1-10 weight part.
Use tensio-active agent (G) so that above-mentioned each component keeps emulsion form.Tensio-active agent is had no particular limits.The tensio-active agent that is suitable for comprises: AS, for example alkyl-sulphate, sulfonated alkylbenzene and alkyl phosphate (being salt); Nonionogenic tenside, for example Voranol EP 2001, polyoxyethylene alkyl phenyl ether and polyoxyethylene fatty acid ester; Cation surface activating, for example quaternary ammonium salt and alkylamine acetate and amphoterics, for example alkyl betaine and alkyl imidazoline compound.Water-soluble polymers such as Z 150PH also are suitable for.
Coating emulsion compsn of the present invention can get said components (A)-(F) emulsification, decentralized system through in the presence of tensio-active agent (G).Emulsification, the dispersion steps of preparation emulsion compositions hope it is in high-pressure emulsification machine (normally homogenizer), under the shear pressure of at least 10 MPas, implement.If pressure is lower than 10 MPas, then be difficult to form the mean particle size emulsion of 500 nanometers at the most.Shear pressure surpasses 200 MPas can not be effective, because and may not be certain just to have the effect of further reduction mean particle size.Preferred shear pressure is the 15-150 MPa, more preferably the 20-100 MPa.Before high pressure emulsification, can adopt homomixer such as Agi-Homo-Mixer (Primix Corp.) as required, Combi-Mix (PrimixCorp.), Supraton (trade(brand)name), Clear-Mix (M Technique), colloidal mills etc. carry out elementary emulsification.Similarly emulsification, dispersion technology also can be applicable in the embodiment, wherein earlier prepare the independent emulsion of component (A)-(F) respectively, and then they are mixed.
Method for coating emulsion compsn of the present invention is coated on the base material has no particular limits.Can compsn be coated on the base material through well-known any coating technology, this type coating technology comprises brushing, roller coat, groove roller coat, wind the line excellent coating, spraying, blade coating, dip-coating, boils off moisture then, so obtain polysiloxane coating.In order to improve the efficient of coat operations, can add the viscosity that the material of thickening material and so on is regulated compsn to said composition.The thickening material that is suitable for comprises CMC 99.5, ZX-I, starch, casein, FM, Natvosol and Z 150PH.
Coating emulsion compsn of the present invention is coated in and can be used as water repllents, anti-water absorbent, release agent or stain control agent above film, the paper wood etc., but the purposes of said composition is not limited thereto.
Second embodiment
Below will refusing water, refuse the oilpaper material and describe to second embodiment according to the present invention.
Refuse water, refuse the oilpaper material and be included in that at least one of paper substrate lip-deeply refused water, refused oil, strippable polyorganosiloxane resin layer.
Have no particular limits for paper substrate used herein.Can select paper wood according to concrete purposes, as long as can on its at least one surface, form the polyorganosiloxane resin layer.The paper substrate that is suitable for comprises NBSK paper, non-wood pulp paper, cardboard, lining facial tissue, glassine and vellum paper.The fibrous material of making paper substrate is not limited to Mierocrystalline cellulose and derivatived cellulose.Remove Mierocrystalline cellulose and cellulose-derived beyond the region of objective existence, the Woven fabric and the supatex fabric that comprise the fiber that is obtained by other starting material also can be used as base material to replace paper substrate.
Polyorganosiloxane resin layer or coating not only have the good water repellency and the peel property of ZGK 5, but also have good film strength and oil repellent because of the three-dimensional crosslinking structure characteristic of resin.Because this characteristic, thereby can have oil repellent, water repellency and separability simultaneously.Because polyorganosiloxane resin is more pliable and tougher than other organic resin, thereby the coating that forms has good anti-bending property.So even stand bending, this paper wood also keeps good oil and the water repellency refused.
For the purpose of the convenience of explaining, this paper wood comprises normal planar section and bending part (if the words through bending).Owing to of the present inventionly refuses water, refuses the oilpaper material and comprise having snappiness, refuse oil, refuse the polyorganosiloxane resin layer of water and separability characteristic, thereby this paper wood has improved oil-proofness and water repellency as mentioned below.The oil-proofness of planar section is 9Kit value at least, and the oil-proofness of bending part is 8Kit value at least, and this two value all is according to J.TAPPI paper/pulptest No.41-83, under 20 ℃ and 50% humidity, measures.This mensuration is the result show, the oil-proofness after bending descends few.Equally, the water repellency of planar section is R8 at least, and the water repellency of bending part is R7 at least, and this two value is all measured according to J.TAPPIpaper/pulp test No.68:2000.This result shows that the water repellency after bending descends few.
Refuse water, refusing the oilpaper material can be through will mainly comprising refusing water, refusing at least one surface that oil compsns is coated in paper substrate and go up and to make of water-based polyorganosiloxane resin emulsion; Coating amount to make dry coating weight reach at least 1.0 the gram/square metre; Preferred 1.0-4.0 gram/square metre, guaranteeing to have enough water, oil repellents refused, and keep the snappiness of paper; From industrial production, preferred dry coating weight be 1.0-2.0 gram/square metre.It must be noted that suitable coating weight can change with concrete purposes with the type of paper substrate.
Can adopt any satisfactory coating machine such as stack, applying glue pressure roller, roller coating machine, blade coating device, air knife spreading machine, the excellent coating machine of coiling and groove roller coating machine to carry out coat operations.The applying step number can come suitably decision with final coating wt according to the coating wt that applies once.Make then be coated on the paper substrate refuse water, refuse oil compsns for example 80-160 ℃ dry 20 seconds-2 minutes down, thereby make compsn solidify, form the polyorganosiloxane resin layer simultaneously.The thickness of this polyorganosiloxane resin layer is generally about 1 micron-Yue 4 microns.
Below will be to being used on paper substrate forming refusing water, refusing oil compsns and describe of polyorganosiloxane resin layer.From security consideration, said composition is preferably the polysiloxane group that mainly comprises water-based polyorganosiloxane resin emulsion and refuses water, oil repellent compsn, and specifically, water-based polyorganosiloxane resin emulsion comprises component (a)-(e):
(a) contain at least two organopolysiloxanes with the oh group of silicon bonding in the 100 weight part per molecules,
(b) 0.5-20 weight part dicarboxyl acidic group solidifying agent,
(c) 1-50 weight part silicon-dioxide,
(d) the 2-4 weight part contains chain alkyl and alkoxy base but the organopolysiloxane of non-hydroxyl group, and
(e) tensio-active agent of the significant quantity of formation emulsion,
Because the coating that is obtained has improved oil repellent, water repellency, separability and snappiness.
Component (a) is to contain at least two in the per molecule, preferred 2-200 the organopolysiloxane with the oh group of silicon bonding.The ZGK 5 main framing of this organopolysiloxane is generally linear structure, and its polymerization degree is 100-10000, but and branching reach the flexible degree that can not damage the coating that forms.If the polymerization degree is lower than 100, then the oil repellent of coating when bending can be very poor, if the polymerization degree is higher than 10000, the oil repellent of coating can variation.The preferred polymerization degree is 1000-5000.
Also be connected with on the two ends of organopolysiloxane and the Siliciumatom of side chain and comprise C
1-C
20Alkyl group and C
6-C
20Aromatic yl group is C with part
1-C
20The organic group of alkyl group.Consider that from crosslinked action each intramolecularly must comprise at least two oh groups with the silicon bonding.The illustrative example that is suitable for organic group comprises methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, cyclopentyl, cyclohexyl, suberyl, phenyl, tolyl and naphthyl, and methyl is preferred.The alkoxy base that is suitable for comprises methoxyl group, oxyethyl group, propoxy-, butoxy, hexyloxy, heptan oxygen base, octyloxy, dodecyloxy and tetradecyloxyaniline.
The instance of organopolysiloxane (a) can be identical with component (A), comprises formula (i)-(polymkeric substance vi).
Component (b) is the linking agent that solidifies polysiloxane coating as forming, and also can be used for improving coating and the adhering dicarboxylicacid solidifying agent of base material.This dicarboxylicacid solidifying agent is selected from dicarboxylic anhydride and reaction product thereof usually.
The instance of dicarboxylic anhydride comprises oxalic anhydride, maleic anhydride, Tetra hydro Phthalic anhydride, succinyl oxide and methylsuccinic acid acid anhydride.
Adopt the reaction product of dicarboxylic anhydride and basic cpd, with its solubleness of further raising, or the reaction product of employing and silane coupling agent, with the adhesivity of further raising to base material.The instance that is used for the silane coupling agent of this paper comprise alkyl silicate (like tetraethyl orthosilicate) and organoalkoxysilane for example alkylalkoxy silane (like Union carbide A-162), contain the organoalkoxysilane (like vinyltriethoxysilane) of alkenyl; Contain amino organoalkoxysilane (like the 3-aminopropyltriethoxywerene werene); The organoalkoxysilane (like the methacryloxypropyl triethoxyl silane) that contains methacryloxy, and the condenses of above-claimed cpd.
The instance that can adopt said components (B) is as component (b).
The consumption of component (b) is that per 100 parts by weight of component (a) are the 0.5-20 weight part.Component (b) content is if be lower than 0.5 weight part, and is then not good with the adhesivity effect of base material to improving coating, if be higher than 20 weight parts, the coating hardening become fragile, and when bending, refuses oil, water repellency variation.The preferable amount of component (b) is the 1-10 weight part.
Component (c) is a silicon-dioxide, adds as the film toughener.Can adopt the silicon-dioxide of wet method or dried preparation, commercially available silicon-dioxide is aqueous silica dispersion.Though the type to silicon-dioxide does not limit, wetting ability silicon-dioxide is preferred.The specific surface area of preferred silicon-dioxide is 10-1000 meters squared per gram (pressing the BET method measures), and the mean particle size of former grain is the 2-200 nanometer.Used silicon-dioxide instance comprise AEROSIL (NipponAerosil Co., Ltd.), TOKUSIL (Tokuyama Co., Ltd.), NIPSIL (TosohSilica Co., Ltd.), and SYLYSIA (Fuji Sylysia Co., Ltd.).Component (D) colloidal silica also can be used as component (c); The example comprises Snowtex (NissanChemical Industries Ltd.), Ludox (W.R.Grace&Co.), Silicadol (Nippon Chemical Industrial Co.; Ltd.); Adelite AT (Asahi DenkaKogyo K.K.) and Cataloid S (Calatyst&Chemicals Industries Co., Ltd.).
The consumption of component (c) is that per 100 parts by weight of component (a) are the 1-50 weight part.Be lower than 1 part like fruit component (c) consumption, then can make strength of coating low, and oil repellent be very poor.If consumption is higher than 50 parts, then can makes the coating hardening, become fragile, the oil repellent variation through bending the time.The preferable amount of component (c) is 5-30 part.
Component (d) is to contain chain alkyl and alkoxy base but the organopolysiloxane of non-hydroxyl group, and the coating of polysiloxane group being refused oil compsns has promoter action.Component (d) can improve the leveling characteristics of coating when applying and have improved flatness, inhomogeneity coating to guarantee to form, and the final performance of processing paper wood that improves.
This type organopolysiloxane has the general linear structure that the polymerization degree is 5-260, and on two end groups and side chain, comprises the organic group that is connected with Siliciumatom.These organic groups mainly are C
1-C
3Alkyl group.For the effect that improves coating performance, each molecule of organopolysiloxane should comprise 1-100, more preferably 1-80 long chain alkyl group that contains 4-20 carbon atom, 0.1-30, more preferably 1-30 C
1-C
6Alkoxy base, perhaps have replacement on it contain C
1-C
6The C of the alkoxysilyl group of alkoxyl group
2-C
3Alkyl group.
C
1-C
3The instance of alkyl group comprises methyl, ethyl and propyl group, and methyl is preferred.The instance that contains the long chain alkyl group of 4-20 carbon atom comprises butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl, and hexyl, octyl group, decyl and dodecyl are preferred.C
1-C
6The instance of alkoxy base comprises methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy and hexyloxy.Have replacement on it contain C
1-C
6The C of the alkoxysilyl group of alkoxyl group
2-C
3The instance of alkyl group comprises ,-C
2H
4-Si (OCH
3)
3,-C
2H
4-Si (OC
2H
5)
3,-C
3H
6-Si (OCH
3)
3,-C
3H
6-Si (OC
2H
5)
3Deng.Wherein methoxyl group, oxyethyl group and--C
2H
4-Si (OCH
3)
3Be preferred.
The instance that can adopt above-mentioned component (F) is as component (d).
The consumption of component (d) is that per 100 parts by weight of component (a) are the 2-4 weight part.The consumption of component (d) is lower than 2 weight parts, then to promoting the coat operations nearly unavailable, may the oil repellent of coating be had a negative impact and be higher than 4 weight parts.
Component (e) is to be used to make above-mentioned each component to keep the tensio-active agent of emulsion state.Type to tensio-active agent has no particular limits.The tensio-active agent that is suitable for comprises: AS, for example alkyl-sulphate, sulfonated alkylbenzene and alkyl phosphate (that is salt); Nonionogenic tenside, for example Voranol EP 2001, polyoxyethylene alkyl phenyl ether and polyoxyethylene fatty acid ester; And cats product, for example quaternary ammonium salt and alkylamine acetate.The instance of those components (G) also can adopt.
Consumption to component (e) has no particular limits, as long as can effectively form emulsion.Normally per 100 parts by weight of component of the consumption of component (e) (a) are the 1-20 weight part.
Refusing water, refusing in the oil compsns, can add and be used to promote condensation reaction between above-mentioned each component and the solidified catalyzer, as required, to be per 100 parts by weight of component (a) be 10 weight parts at the most to its consumption, more specifically says to be 5 weight parts at the most.Catalyzer does not always need to add, because component (b) has this type catalytic performance.
Refusing water, refusing in the oil compsns, can sneak into the polyorganosiloxane resin emulsion that meets food security standard on any be coated in paper substrate that is purchased, only otherwise can influence the object of the invention.Polysiloxane group refuses water, refuse also can be mixed with in the oil compsns skimmer etc. to improve the smoothness of polyorganosiloxane resin layer etc.
Embodiment
To be further described the present invention through embodiment and control Example below, but the present invention is not limited.All shares and per-cent are all by weight in an embodiment.
Synthetic embodiment 1
In 2 liters of Vilaterm beakers, pack into 498 the gram octamethylcyclotetrasiloxanes, 2 the gram triethoxyphenylsilan, 50 the gram 10% lauryl sulfate sodium water solutions and 50 the gram the 10% Witco 1298 Soft Acid aqueous solution.Adopt homomixer to make the emulsification equably of each component, after the emulsification, add 400 gram water lentamente and dilute.Under 30 MPa pressure, carry out twice emulsification through high-pressure homogenizer then, obtain uniform white emulsion.Then this emulsion is transferred in 2 liters of glass flask that whisking appliance, TM, reflux exchanger are housed, implemented polyreaction 24 hours down at 50 ℃.10 ℃ of following slakings 24 hours, using 12 grams, 10% aqueous sodium carbonate to be neutralized to the pH value then was 6.2.This emulsion is 45.4% through the non-volatile substance content of 105 ℃ of dryings after 3 hours, and comprises the soft gel organopolysiloxane of illiquidity, and its average group accepted way of doing sth is following and with hydroxy-end capped.Make the emulsion (A-1) that contains 44.4% component (A) in this way.
Me represent methylidene in the formula, Ph represents phenyl, m=1, n+p=1000.
Synthetic embodiment 2
In 2 liters of Vilaterm beakers, pack into 500 the gram octamethylcyclotetrasiloxanes, 50 the gram 10% lauryl sulfate sodium water solutions and 50 the gram 10% dodecyl-Phenylsulfonic acid aqueous solution.Adopt homomixer to make the emulsification equably of each component, after the emulsification, add 400 gram water lentamente and dilute.Under 30 MPa pressure, carry out twice emulsification through high-pressure homogenizer then, obtain uniform white emulsion.Then emulsion is transferred in 2 liters of glass flask that whisking appliance, TM, reflux exchanger are housed, implemented polyreaction 24 hours down at 50 ℃.10 ℃ of following slakings 24 hours, using 12 grams, 10% aqueous sodium carbonate to be neutralized to the pH value then was 6.2.This emulsion through 105 ℃ of dryings after 3 hours non-volatile substance content be 45.5%, and comprise the gumminess organopolysiloxane, chemical formula is HO-[(CH
3)
2SiO]
n-H, viscosity was higher than for 1000 handkerchief seconds.Made the emulsion (A-2) that contains 44.5% component (A) in this way.
Synthetic embodiment 3
Dissolving 154 gram maleic anhydrides in 500 gram ethanol.At room temperature, introversive this solution dripped 346 gram 3-aminopropyltriethoxywerene werene in 1 hour, reacted 24 hours with alcohol reflux at 80 ℃ then.Obtain containing the light yellow clear solution (B-1) of 50% component (B) thus.This solution through 105 ℃ of dryings after 3 hours non-volatile substance content be 45.1%.Analyze through IR, GC, NMR and GCMS, the reaction product in the solution is the mixture of about 60% following formula: compound and the oligopolymer therefrom of surplus (about 40%):
(C
2H
3O)
3SiC
3H
6-NHCO-CH＝CHCOOH and
(C
2H
3O)
3SiC
3H
6-NH
3 +C
2H
3OCOCH＝CHCOO
-
Synthetic embodiment 4
In 2 liters of Vilaterm beakers, add 300 gram two LAURIC ACID 99 MIN dioctyl tins and 50 gram T 46155 nonylplenyl ethers (adduct of EO10 mole), mix equably with homomixer.Add 650 gram water lentamente to mixture, thereby make these components emulsification and dispersion in water.Under 30 MPa pressure, carry out twice emulsification through high-pressure homogenizer, obtain containing the emulsion (E-1) of 30% component (E).
Synthetic embodiment 5
500 grams of in 2 liters of Vilaterm beakers, packing into contain organopolysiloxane chain alkyl and alkoxy base, that an average group accepted way of doing sth is as follows (dynamic viscosity is 37 a square millimeters/gram); 20 gram T 46155 decyl ethers (adduct of EO4 mole) and 5 gram sodium sulfosuccinates mix with homomixer equably.Add 475 gram water lentamente to this mixture, thereby make these components emulsification and dispersion in water.Under 30 MPa pressure, carry out twice emulsification through high pressure homogenisers, obtain containing the emulsion (F-1) of 50% component (F).
Embodiment 1-4 and control Example 1-3
The component (C) that adopts is γ-glycidoxypropyltrime,hoxysilane (C-1).The component (D) that adopts is colloidal silica (Snowtex C, Nissan Chemical IndustriesLtd., an active principle content 20%).Prescription (institute's number of columns is purified component) according to table 1 is mixed and made into a series of silicone emulsion compositions with component (A)-(F).Adopt wire-wound rod blade coating device that silicone emulsion composition is coated on the white board, clean coating amount be 2 grams/square metre, coatingsurface state (being coated with the back state) is with visual observation.With coating 80 ℃ dry 1 minute down, carry out surface viscosity then and to the adhesiveness test of base material.This coating is also carried out stripping test, the pressure sensing adhesive band is sticked on the coatingsurface for this reason, peel off adhesive tape then.Test-results is listed in the table 1.
Table 1
*1 zero: level and smooth, *: unsmooth
*2 zero: not sticking, *: be clamminess
*3 zero: the finger friction coatings is not peeled off, *: the finger friction coatings is peeled off
*4 zero: be prone to peel off, *: anti-peeling off, because of the part sticks on the base material
Embodiment 5
Following component is mixed:
Component (a): linear methyl polysiloxane (polymerization degree is 1000, and hydroxy radical content is 0.004 mole/100 grams) 100 grams,
Component (b): reaction product 1 gram of maleic anhydride and 3-aminopropyltriethoxywerene werene (mol ratio=1/1),
Component (c): untreated dried silica (the BET surface-area is the former grain of 200 meters squared per gram mean particle size 10 nanometers) 15 grams,
Component (d): linear polysiloxane (polymerization degree is 30, and the organic group that links to each other with Siliciumatom is 10% octyl group group, 2% propoxy-group, all the other are methyl group) 3 grams,
Sodium Lauryl Sulphate BP/USP 10 grams
Water 129 grams,
And carry out uniformly emulsify with homomixer, to form uniform white water-based polyorganosiloxane resin emulsion.This emulsion is to contain refusing water, refusing oily ZGK 5 based composition and use thereof in packaging of 50% active principle.
The paper substrate that adopts be basic weight be 350 grams/square metre, the white board (basic paper) of uncoated functional reagent.Adopt #5 wire-wound rod blade coating device that polysiloxane group is refused water, refused oil compsns and be coated on the surface of basic paper, make dry coating weight be the 1.5-2.0 gram/square metre.Make the coating drying and solidified for 30 seconds to form the polyorganosiloxane resin layer at 120 ℃.Process and refuse water, refuse the oilpaper material in this way.
This is refused water, refuses oil-proofness, water tolerance and the separability of oilpaper material through following test determination.Measuring the result lists in the table 2.
The oil-proofness of planar section:
Measure coated surfaces according to J.TAPPI paper/pulp test No.41-83 (Kit method).This mensuration is with visual observation.
The oil-proofness of bending part:
The paper sample is bent secondary so that coated surfaces is outside.Bending part is exerted pressure from last by following condition: wide 1.0 millimeters, dark 0.7 millimeter with pressure 2.5 kgfs/square centimeter second, analyse to confirm to bend fully.Then the paper sample is opened again, measured the curved oil-proofness of analysing part according to J.TAPPI paper/pulp test No.41-83 (Kit method).This mensuration is with visual observation.
The planar section water repellency
No.68:2000 measures coated surfaces according to J.TAPPI paper/pulp test.This mensuration is with visual observation.
The water repellency of bending part
The paper sample is bent twice so that coated surfaces is outside.In order to confirm bending fully, from last the curved part of analysing is exerted pressure by following condition: wide 1.0 millimeters, dark 0.7 millimeter with pressure 2.5 kgfs/square centimeter seconds.Then the paper sample is opened again, measured the water repellency of bending part according to J.TAPPI paper/pulp test No.68:2000.This mensuration is with visual observation.
Separability
With 18 millimeters * 35 millimeters Pressuresensitive Tapes (Cellotape
; Nichiban Co.; Ltd.) stick on the coated surfaces, and to use one stroke pressure be that 2 kilograms adhesive tape roller carries out roll-in to it.This compound sample is incubated 1 hour down in 25 ℃; Then to adherent adhesive tape peel manually from and the stripping performance of this coating pattern evaluated; When the adherent adhesive tape is left by peel manually easily and does not have noise; Then, need bigger peeling force when when the adherent tape stripping, having noise or peel manually to leave, then with " * " expression (separability is poor) with " O " expression (smooth peeling off).
Control Example 4
This instance is with reference to embodiment.To uncoated refuse water, the basic weight of refusing oily ZGK 5 based composition and use thereof in packaging is 350 grams/square metre white board (basic paper) make an experiment according to embodiment 5 steps.
Control Example 5
Except that the water-based polyorganosiloxane resin emulsion of preparation does not contain the component (d), all the other adopt active principle by embodiment 5 steps is 50% refuse water, refuse the coated paper sample of oily polysiloxane group preparation of compositions.Sample is similarly tested.
Table 2
Visible from table 2, of the present inventionly refuse water, refuse the oilpaper material and have good oil resistant, refuse water and stripping performance.The performance number of bending part is suitable with the planar section performance number.When bending, have only minimum oil-proofness and water repellency loss.
Claims (5)
1. coating emulsion compsn, said composition comprises:
(A) comprise at least two organopolysiloxanes with the oh group of silicon bonding in the 100 weight part per molecules,
(B) the 0.5-20 weight part contains the amino organoalkoxysilane and the reaction product of dicarboxylic anhydride,
(C) the 0-20 weight part contains organoalkoxysilane and/or its partial hydrolysate of epoxy,
(D) 0-50 weight part colloidal silica and/or polysilsesquioxane,
(E) 0-10 weight part curing catalysts, and
(F) the 0.5-20 weight part contains chain alkyl and alkoxy base but the organopolysiloxane of non-hydroxyl group,
Emulsification in water in the presence of tensio-active agent, dispersed component (A)-(F).
2. the emulsion compositions of claim 1, wherein component (F) has an average group accepted way of doing sth (2) and is:
R in the formula
1C respectively does for oneself
1-C
3Alkyl or phenyl, Q are C independently of one another
4-C
20Alkyl, Z are-OR independently of one another
2,-C
2H
4-Si (OR
2)
3Or-C
3H
6-Si (OR
2)
3Group, wherein R
2Be C
1-C
6Alkyl, subscript d are the positive numbers of 1-100, and e is the positive number of 1-100, and f is that positive number and the q of 0.1-30 is 0,1,2 or 3.
3. the emulsion compositions of claim 1, wherein component (F) has an average group accepted way of doing sth (3) and is:
Q is selected from hexyl, octyl group, decyl and dodecyl independently of one another in the formula, Z be selected from independently of one another methoxyl group, oxyethyl group and-C
2H
4-Si (OCH
3)
3, subscript d is the positive number of 1-100, e is the 1-100 positive number, f is the positive number of 0.1-30.
4. one kind has refusing water, refusing the oilpaper material of improved anti-bending property, said paper wood comprise paper substrate and lip-deeply refuse water at least one of paper substrate, refuse oil, strippable polyorganosiloxane resin layer,
Bending part when said paper wood comprises common planar section with bending,
The Kit value of the oil-proofness of planar section is at least 9, and the Kit value of the oil-proofness of bending part is at least 8, the Kit value of oil-proofness measure under 20 ℃ and 50% humidity according to J.TAPPI paper/pulp test No.41-83 and
The water repellency of planar section is at least R8; And the water repellency of bending part is R7 at least; Water repellency is measured according to J.TAPPI paper/pulp test No.68:2000; Said polyorganosiloxane resin layer is through will refusing water, refuse oil compsns and be coated on the surface of paper substrate and form, and said compsn mainly comprises water-based polyorganosiloxane resin emulsion, and this polyorganosiloxane resin emulsion comprises:
(a) contain at least two organopolysiloxanes with the oh group of silicon bonding in the 100 weight part per molecules,
(b) 0.5-20 weight part dicarboxyl acidic group solidifying agent,
(c) 1-50 weight part silicon-dioxide,
(d) the 2-4 weight part contains chain alkyl and alkoxy base but the organopolysiloxane of non-hydroxyl group, and
(e) tensio-active agent of formation emulsion significant quantity.
5. one kind prepares the method for refusing water, refusing the oilpaper material; This method comprises refusing water, refuse oil compsns and be coated at least one surface of paper substrate main aquosity polyorganosiloxane resin emulsion; So that the weight of dry coating reach at least 1.0 the gram/square metre; Thereby form and to refuse water, refuse oil, strippable polyorganosiloxane resin layer and
Paper substrate is selected from NBSK paper, non-wood pulp paper, cardboard, lining panel, glassine and vellum paper, saidly refuses water, the oil repellent compsn mainly comprises water-based polyorganosiloxane resin emulsion, and this polyorganosiloxane resin emulsion comprises:
(a) contain at least two organopolysiloxanes with the oh group of silicon bonding in the 100 weight part per molecules,
(b) 0.5-20 weight part dicarboxyl acidic group solidifying agent,
(c) 1-50 weight part silicon-dioxide,
(d) the 2-4 weight part contains chain alkyl and alkoxy base, but the organopolysiloxane of hydroxyl group not, and
(e) tensio-active agent of formation emulsion significant quantity.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006-279815 | 2006-10-13 | ||
| JP2006279815A JP2008095251A (en) | 2006-10-13 | 2006-10-13 | Water and oil repellent paper and method for producing the same |
| JP2006279800 | 2006-10-13 | ||
| JP2006279815 | 2006-10-13 | ||
| JP2006-279800 | 2006-10-13 | ||
| JP2006279800A JP5057022B2 (en) | 2006-10-13 | 2006-10-13 | Emulsion composition for coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101195726A CN101195726A (en) | 2008-06-11 |
| CN101195726B true CN101195726B (en) | 2012-11-21 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101807592A Expired - Fee Related CN101195726B (en) | 2006-10-13 | 2007-10-12 | Coating emulsion composition, and water/oil-repellent paper and making method |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5057022B2 (en) |
| CN (1) | CN101195726B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101367942B (en) * | 2008-07-11 | 2011-06-15 | 黄山市强力化工有限公司 | Preparation method for branched chain type amino-long chain alkyl co-modified silicone oil and its microemulsion, and uses thereof |
| CN101768896B (en) * | 2009-12-25 | 2011-10-05 | 中冶美利纸业股份有限公司 | Preparation method of Stefan parchment paper |
| JP5620167B2 (en) * | 2010-06-30 | 2014-11-05 | サンスター技研株式会社 | Floor coating composition |
| CN102561106A (en) * | 2012-03-04 | 2012-07-11 | 山东大易化工有限公司 | Organosilicon paper waterproof treatment agent and use method thereof |
| JP6079033B2 (en) * | 2012-08-07 | 2017-02-15 | Jnc株式会社 | Photo / thermosetting composition |
| JP5954255B2 (en) * | 2013-05-15 | 2016-07-20 | 信越化学工業株式会社 | Curable silicone emulsion composition |
| CN105778505B (en) * | 2014-12-25 | 2019-04-30 | 广东生益科技股份有限公司 | A silicone resin composition and white prepregs and white laminates using the same |
| CN105778506B (en) | 2014-12-25 | 2019-04-30 | 广东生益科技股份有限公司 | A kind of organosilicon resin composition and prepreg, laminate, copper-clad plate and aluminum substrate using it |
| DE102015222139A1 (en) * | 2015-11-10 | 2017-05-11 | Wacker Chemie Ag | Process for the impregnation of textiles with compositions containing alkoxypolysiloxanes |
| KR102617690B1 (en) * | 2016-11-03 | 2023-12-26 | 삼성에스디아이 주식회사 | Battery pack |
| CA3060548A1 (en) * | 2017-04-17 | 2018-10-25 | Cornell University | Fluorine-free oil repellent coating, methods of making same, and uses of same |
| US20200199404A1 (en) * | 2017-06-13 | 2020-06-25 | 3M Innovative Properties Company | Amino-functional silsesquioxane copolymer coatings |
| CN108102115B (en) * | 2017-12-26 | 2019-04-19 | 南京瑞思化学技术有限公司 | A kind of preparation method of polysiloxane emulsion |
| JP6812607B1 (en) * | 2019-06-19 | 2021-01-13 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Water-based coating composition |
| CN110205821B (en) * | 2019-06-20 | 2021-12-14 | 广州百思创科技有限公司 | Green fluorine-free waterproof finishing agent and application thereof in fiber products |
| CN111206457A (en) * | 2020-01-15 | 2020-05-29 | 黄细英 | Waterproof stain-resistant corrugated carton and preparation process thereof |
| JP7446215B2 (en) * | 2020-12-17 | 2024-03-08 | 信越化学工業株式会社 | Curable coating composition and article |
| KR102553392B1 (en) * | 2021-07-21 | 2023-07-11 | 다우 글로벌 테크놀로지스 엘엘씨 | Aqueous Dispersions of Silicone Pressure Sensitive Adhesive Bases and Methods of Making and Using Dispersions |
| CN114656642B (en) * | 2022-04-26 | 2023-06-20 | 宁波辉宏新材料有限公司 | Organic fluorine-silicon emulsion release agent and preparation method thereof |
| IT202200013786A1 (en) * | 2022-06-29 | 2022-09-29 | Biakko Srl In Liquidazione | PROCESS FOR MANUFACTURING ARTICLES MADE OF VITRIFIED CELLULOSE MATERIAL AND VITRIFIED CELLULOSE MATERIAL OBTAINED THUS |
| CN117487395A (en) * | 2022-07-21 | 2024-02-02 | 佛山市顺德区美的电热电器制造有限公司 | Polysiloxane non-stick aids, coating compositions, coatings, and articles having non-stick coatings and methods of forming coatings |
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| DE2449085A1 (en) * | 1974-10-15 | 1976-04-29 | Wacker Chemie Gmbh | Release paper coating compsns - contg polysiloxanes, crosslinking agent, accelerator and polyvinyl alcohol |
| US5140061A (en) * | 1989-02-03 | 1992-08-18 | Rhone-Poulenc Chimie | Aqueous silicone dispersions comprised of aminosilanes/amidosilanes and crosslinkable into elastomeric state |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5057022B2 (en) | 2012-10-24 |
| JP2008095002A (en) | 2008-04-24 |
| CN101195726A (en) | 2008-06-11 |
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