CN107789214A - A kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue and preparation method thereof - Google Patents

A kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue and preparation method thereof Download PDF

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CN107789214A
CN107789214A CN201711094248.9A CN201711094248A CN107789214A CN 107789214 A CN107789214 A CN 107789214A CN 201711094248 A CN201711094248 A CN 201711094248A CN 107789214 A CN107789214 A CN 107789214A
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wet tissue
quaternary ammonium
ammonium salt
acrylic acid
nonwoven fabric
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葛宏伟
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SUZHOU BORAGE DAILY CHEMICAL CO Ltd
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SUZHOU BORAGE DAILY CHEMICAL CO Ltd
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60Sugars; Derivatives thereof
    • A61K8/604Alkylpolyglycosides; Derivatives thereof, e.g. esters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0208Tissues; Wipes; Patches
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/34Alcohols
    • A61K8/345Alcohols containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/55Phosphorus compounds
    • A61K8/553Phospholipids, e.g. lecithin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005Antimicrobial preparations
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/005Preparations for sensitive skin
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • A61Q19/10Washing or bathing preparations
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
    • D06M14/20Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
    • D06M14/22Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic

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Abstract

A kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue, it includes wet tissue body and wet tissue liquid, wherein, wet tissue body be have selected with antimicrobial membranes or the non-woven fabrics of nano particle with positive charge, and the antimicrobial membranes or nano particle are formed by chemical bonds;Wet tissue liquid selective RO purified waters, 12 18 alkyl glucosides, lecithin or hydrolecithin, 1,2 pentanediols, skin conditioning agent, other additives, then 0.1 1.0mg/L ozone concentration is passed through in wet tissue liquid, finally, wet tissue liquid is added to wet tissue body by certain weight ratio, pack, that is, form a kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue.The product belongs to the wet tissue of zero precipitation preservative, soft to skin, non-stimulated, without allergy, especially suitable for allergy skin, the tender skin of children etc..

Description

A kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue and preparation method thereof
Technical field
The present invention relates to a kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue, more particularly to a kind of infant's hip pad are wet Towel.
Background technology
In recent years, because the application of wet tissue brings convenience to the life of people, it is increasingly becoming in people's life Necessity, therefore annual production and the consumption rapid growth of wet tissue, along with the application field of wet tissue constantly expands, accordingly The exploitation of product requires also more and more higher.At present, wet tissue species is relatively more, there is hand mouth wet tissue, wet sanitary napkins, makeup-removing wet tissue, clean Skin wet tissue etc., with the lasting expansion of market scale, national industrial policies encourage wet tissue industry to high-tech, high added value The line of production develops, and improves product competitiveness and the market share, therefore the exploitation of wet tissue formula technique will play important work With.
Wet tissue preservative is the topic that consumer especially pays close attention to, and most preservative is all by being connect with cell membrane After touch, with some components of cell membrane, mainly with albumen qualitative response, protection structure or the interference for destroying microbial cell are thin The metabolism of born of the same parents, the normal growth order of cell is influenceed, so as to reach corrosion-resistant purpose, cation then mainly passes through shadow Its osmotic pressure is rung, makes membranolysis, contraction and dehydration, so as to be sterilized.Mainly there are 3 kinds of modes:1) microorganism egg is made Leucismus or solidification, there is substantial amounts of protein in microbial body, all factors that can destroy protein spatial configuration, can make egg White matter is denatured or solidification.2) enzyme system of microorganism is disturbed, the effect of microorganism endocellular enzyme is relevant with its active group, all energy Change or destroy the material of intracellular enzyme activities group function, can suppress the activity of microbial enzyme.3) the logical of cell membrane is changed After permeability, cationic surfactant and phenols act on microorganism, membrane structure can be changed, its normal function is disturbed, enter It is and dead.
Preservative species used in China's wet tissue industry is various at present, wherein the overwhelming majority is chemical preservative, chemistry Preservative is because its is simple in construction, the mechanism of action is apparent, property is stable, has a broad antifungal spectrum, cheap and deep liked by wet tissue producer Love.In fact, some people have found mysterious phenomenon, the addition of same preservative in the user of preservative It has been several times several years ago, the putrid and deteriorated phenomenon of product has still occurred, most of is because certain a kind of (kind) sterilization and anticorrosion Agent is used continuously and causes flora to reduce the sensitiveness of the bactericide for a long time, and so as to cause antisepsis and sterilization effect to decline, this is just It is the resistance to the action of a drug of the so-called microorganism to sterilization antiseptic, also easily causes allergy to consumer skin in this case, stimulates Situations such as.But with the reach of science, the continuous improvement of consumer safety consciousness and the growing interest to health, people Gradually find that the chemical preservative in wet tissue can produce ill-effect to human body, therefore the requirement that wet tissue preservative uses also is got over Come higher, promote wet tissue industry to begin look for the alternative route of chemical preservative, to reduce the injury to consumer skin.And Traditional chemical preservative can not meet " green ", " health " idea that people pursue, and natural antiseptic agent and preservative free Appearance compensate for this part vacancy just, therefore study and use non-stimulated, safe chemical preservative substitute Have become a kind of trend in current daily use chemicals industry.
CN103566371A discloses a kind of antimicrobial method, and it is by the bi-quaternary ammonium salt of lower formula (I):(R1R2R3N+ X-) wherein, each R1 independently is C8-18 alkyl, C8-18 alkenyls or C8-18 alkynyls to-R5- (R1R2R3N+X-) (I);Each R2 and R3 independently is methyl or ethyl;R5 is C3-10 alkylidenes, and it is in β-position or more distant positions by three (C1-3 alkoxies) Siloxy or the substitution of three (C1-3 alkoxies) silicyl-C1-6 alkoxies;It independently is pharmaceutically acceptable with each X- to contend with Anion, being applied to needs to form antimicrobial membranes on antimicrobial body surface.The physics antimicrobial membranes, can be extensive For the mould proof of every profession and trade, antibacterial, deodorization, new combination articles, such as paper can be also combined to form with the product of these industries Industry, face tissue, hygenic towelette, dixie cup etc..But the wet tissue obtained with this method still has the problem of separating out preservative, antibacterial Performance need to be improved, and comfortableness also has much room for improvement.
CN101716359A discloses a kind of bactericidal disinfectant material, and it is will to carry capture bacterium, disease by graft process The compound of the functional group of poison is fixed on nonwoven fabric surface with chemical bond, and the compound includes quaternary ammonium salt, sulfur-bearing chemical combination Thing, containing the one or more in sulfoacid compound.The bactericidal disinfectant material can be widely used in sterilizing product, Such as wet towel, cotton balls, sterilization infantees.
CN 106726636A disclose a kind of physical antibacterial wet tissue, and it grafts on bi-quaternary ammonium salt by x ray irradiation x wet On towel body, antibiotic property, soft and smooth property and the less antibacterial wet tissue of excitant have been obtained.But above-mentioned graft reaction connects Branch rate, and the wet tissue need further to be lifted in antibiotic property, flexibility and excitant.
In order to solve wet tissue antibiotic property, flexibility difference in the prior art and have irritating problem, the present invention provides A kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue, its act on be by positively charged antimicrobial membranes or particle with Negatively charged microbial cell film produces electrostatic force and causes the rupture of microbial cell film or morphologic change and cause micro- life Thing is dead, and so as to be provided with anti-corrosive antibacterial ability, the product strong antibacterial, flexibility is good, soft to skin, non-stimulated, Without allergy, especially suitable for allergy skin, the tender skin of children etc..
The content of the invention
The invention provides a kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue.The wet tissue includes wet tissue body and wet Towel liquid, wet tissue body have selected with antimicrobial membranes or the non-woven fabrics of nano particle with positive charge, and this is antimicrobial Film or nano particle are formed by chemical bonds;Wet tissue liquid selective RO purified waters, surfactant, emollient, guarantor Humectant, skin conditioning agent, other additives, 0.1-1.0mg/L ozone concentration is then passed through in wet tissue liquid, finally, Wet tissue liquid is added to wet tissue body by certain weight ratio, packed, that is, forms a kind of acrylic acid bi-quaternary ammonium salt grafting Wet nonwoven towel.
Specifically, the invention provides a kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue, it is by wet tissue body and wet Towel liquid forms, and the wet tissue body is the non-woven fabrics for being bonded high molecular quaternary;The wet tissue liquid is with weight by following Measure each component composition of percentage:
RO purified waters 65-70%
12-18 alkyl glucosides 0.2-0.8%
Lecithin or hydrolecithin 0.3-0.8%
1,2- pentanediol 25-30%
Skin conditioning agent 0.2-2%
Other additives 1-6%,
Each component content sum is 100%;
Wherein, the preparation method of wet tissue body is:
(1) length is used as 40-50mm, and a diameter of 0.04-0.1mm bamboo pulp fiber is as raw material, through cross lapping water Bamboo pulp non-woven fabrics is made after piercing technique, the nonwoven carrier that thickness is 3-5mm is obtained after clipped, high-temperature sterilization;
(2) nonwoven carrier made from step (1) is placed in the monomer solution of isopropanol/water mixed solvent preparation, room Temperature lower lucifuge immersion 12-24 hours;
(3) under nitrogen protection, CeCl is added in monomer solution3/ HCl/water solution, with x ray irradiation x above-mentioned steps (2) in it is soaking after obtained non-woven fabrics, irradiation intensity 80-200KGy;
(4) after irradiation terminates, unreacted monomer and homopolymer are fallen in extracting, and wet tissue body is obtained after drying;
Wherein, the acrylic acid that monomer is bi-quaternary ammonium salt and degree of neutralization is 60-70%, bi-quaternary ammonium salt in monomer solution Mass fraction is 0.1-0.2%, and the mol ratio of bi-quaternary ammonium salt and (acrylic acid+acrylates) is (20-30): 1;CeCl3 Initial concentration in reaction system is (1-2) × 10-4The initial concentration of mol/L, HCl in reaction system is (1-2) × 10- 3mol/L;
Wherein, the bi-quaternary ammonium salt is the compound shown in formula 1 or formula 2:
The skin conditioning agent is one in ceramide, Co-Q10, tocopherol acetate, resveratrol, astaxanthin Kind is a variety of;
Other described additives are one or more kinds of mixing in antioxidant, chelating agent, pH adjusting agent Thing, the one kind being chosen in particular from Butylated Hydroxytoluene, EDTA-2Na, EDTA-4Na, arginine, citric acid, sodium citrate or it is a kind of with On mixture.
The 12-18 alkyl glucosides are lauryl glucoside or octadecyl glucoside.
Present invention also offers a kind of preparation method of wet tissue liquid, it is characterised in that wet tissue liquid is transparent and stable Facial treatment milk, this method comprise the following steps:
(1) 12-18 alkyl glucosides 0.2-0.8%, lecithin or hydrolecithin 0.3-0.8% are mixed and heated To 50-80 DEG C, at this temperature, 5-20min is quickly stirred, to obtaining clear solution A;
(2) RO purified waters 65-70%, 1,2- pentanediols 25-30%, other additives 1-6% are mixed and heated to 60-90 DEG C, it is evenly stirred until clear solution B;
(3) under high-speed stirred, B solution is slowly added in solution A, until obtaining clear solution C;
(4) C solution that cools addition skin conditioning agent 0.2-2%, stirs to less than 45 DEG C and is made clear solution D;
(5) ozone is passed through in solution D, ozone concentration is maintained in the range of 0.1-1.0mg/L, produces wet tissue liquid E.
Further, present invention also offers a kind of preparation method of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue, its It is characterised by adding the ratio of wet tissue liquid E and the wet tissue body by weight 1.5: 1-4: 1 for being cut into suitable dimension, then Pack, produce acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue.
Compared with traditional wet tissue, the wet tissue has the following advantages that:
1st, traditional wet tissue is that antiseptic is fixed in non-woven fabrics using adhesive, and the wet tissue is by stable change Bond is learned together in non-woven fabrics, thus is the product of zero precipitation preservative;
2nd, traditional wet tissue anti-corrosion function is the new old generation of protection structure by destroying microbial cell or interference cell Thank, influence the normal growth order of cell, so as to reach corrosion-resistant purpose.And the wet tissue anti-corrosion function is by positively charged Antimicrobial membranes or nano particle and negatively charged microbial film make the rupture of microbial cell film dead by electrostatic force Die, so as to reach anti-corrosive antibacterial function.
4th, chemical preservation antiseptic wet tissue imposes on human body surface for a long time may cause the symptoms such as human allergy, make as excessive With may result in dermatitis, spot, or even DNA damage can be caused.In addition, during production, variation bacterium or tolerance are also easily grown Bacterium, the security risk problem that can not be estimated is added for company, and the application of the wet tissue completely avoid above-mentioned unfavorable factor.
5th, by making specific bi-quaternary ammonium salt under CeCl3/HCl initiation systems and acrylic acid-grafted on wet tissue body, The grafting rate of bi-quaternary ammonium salt is improved, only excellent antibacterial effect is can reach with seldom amount of monomer, makes the antibacterial of the wet tissue Effect has exceeded common antibacterial wet tissue of the prior art, and wet tissue has splendid flexibility, uses extremely gentle And it is nonirritant, drug resistance will not be produced, available for infant's hip pad wet tissue, infant's hand mouth wet tissue, clean skin wet tissue and is defended Raw wet tissue etc., the wet tissue can be acted rapidly to skin problems such as dermatitis, eczema, bedsore, the red hip of baby, have suppression Bacterium is antipruritic, the positive effect of skin care, is particularly suitable for using during the red hip of baby.
Brief description of the drawings
Fig. 1 is the nuclear magnetic spectrogram of bi-quaternary ammonium salt A described in preparation example 1.
Fig. 2 is the nuclear magnetic spectrogram of bi-quaternary ammonium salt B described in preparation example 2.
Embodiment
Preparation example 1:
1) dry hydrogen chloride gas is imported in the anhydrous ether solution of octadecyldimethyl tertiary amine, produces white Precipitation.Then using water as solvent, epoxychloropropane is placed in dropping funel, starts to be slowly added dropwise, 35min is dripped off, at room temperature After stirring, 12h is reacted in 80 DEG C, determines reaction end by titrating epoxychloropropane quaternary ammonium salt content, reaction finishes Afterwards, rotary evaporation removes solvent at room temperature, obtains faint yellow paste residue, with acetone recrystallization paste residue, waits to analyse Go out to depressurize after crystal and filter, be so repeated several times, finally white powder mono-quaternaries product --- (3- is chloro- by intermediate product N- 2- hydroxypropyls)-N, N- dimethyl stearyl ammonium chlorides.Wherein, octadecyldimethyl tertiary amine: hydrogen chloride: epoxychloropropane Mol ratio be 1.5: 1.2: 1.
2) N, N- dimethyl -1,2- are sequentially added in the four-hole boiling flask equipped with electric mixer, thermometer and still Ethylenediamine, methyl oleate, dibutyl tin dilaurate, hydroquinones, 110 DEG C are warming up to, back flow reaction 4 hours.Then will be anti- Answer device to be changed to distilling apparatus, continue to stir, be distilled off at the reaction temperatures unreacted methyl oleate and its with methanol Azeotropic mixture.Stop reaction, be evaporated under reduced pressure, vacuum drying obtains oleoyl ethyldimethyl amine.Wherein, N, N- dimethyl -1,2- The mol ratio of ethylenediamine and methyl oleate is 1: 4, and dibutyl tin dilaurate, the dosage of hydroquinones are respectively that reaction solution is total The 2% of quality and 0.1%.
3) gained in step 1) is sequentially added in the four-hole boiling flask equipped with electric mixer, thermometer and still to produce Thing I, acetone and hydroquinones.Heating water bath adds step 2) products therefrom II to 60 DEG C, reacts 4 hours.It is molten to filter removing Agent, unreacted raw material and hydroquinones, crystallisation by cooling, filter to obtain product III.With acetone recrystallization 3-4 times, vacuum drying. Wherein, product I and II mol ratio is 1: 4, and the dosage of hydroquinones is the 0.15% of reaction solution gross mass
4) gained in step 3) is sequentially added in the four-hole boiling flask equipped with electric mixer, thermometer and still to produce Thing III, 3- chloropropyl alcohol, is warming up to 160 DEG C, reacts 12h under the conditions of being stirred at reflux, and is evaporated under reduced pressure and removes residue, and then 40 DEG C vacuum drying 10h, produce product IV.
5) products therefrom IV in step 4) is placed in flask, addition dichloromethane is solvent, and triethylamine is used as and ties up acid Agent, acryloyl chloride is added dropwise under the conditions of ice-water bath, 30min is dripped off, and recession fall ice water-bath is added dropwise, temperature is warmed to room temperature Lucifuge is reacted 12 hours afterwards, and gained mixture is filtered, and filtrate rotary evaporation removes solvent, and 40 DEG C of vacuum drying 24h are produced down Bi-quaternary ammonium salt A described in formula.Wherein the mol ratio of product IV, acryloyl chloride and triethylamine is 1: 3: 4.
Preparation example 2:
It is identical with preparation example 1, differ only in:The anhydrous second of Dodecyl Dimethyl Amine is used in the 1) step Ethereal solution, finally give bi-quaternary ammonium salt B described in following formula.
Embodiment 1
The preparation method of wet tissue body is:
(1) length is used as 50mm, and a diameter of 0.08mm bamboo pulp fiber is as raw material, through cross lapping water jet process Bamboo pulp non-woven fabrics is made afterwards, the nonwoven carrier that thickness is 4mm is obtained after clipped, high-temperature sterilization;
(2) nonwoven carrier made from step (1) is placed in the monomer solution of 1L isopropanol/waters mixed solvent preparation, Lucifuge is soaked 24 hours at room temperature;The propylene that monomer is bi-quaternary ammonium salt A and the degree of neutralization neutralized with potassium hydroxide is 65% Acid, bi-quaternary ammonium salt A mass fraction is 0.1% in monomer solution, and bi-quaternary ammonium salt A and (acrylic acid+acrylates) mole Than for 25: 1, the volume ratio of isopropanol and water is 3: 1;
(3) under nitrogen protection, CeCl is added in monomer solution3/ HCl/water solution, with gamma-ray irradiation above-mentioned steps (2) in it is soaking after obtained non-woven fabrics, irradiation intensity 80KGy;CeCl3Initial concentration in reaction system is 2 × 10-4The initial concentration of mol/L, HCl in reaction system is 1 × 10-3mol/L;
(4) after irradiation terminates, unreacted monomer and homopolymer are fallen in extracting, and wet tissue body is obtained after drying;
In wet tissue liquid E preparation technology, solution A selects lauryl glucoside 0.2g, lecithin 0.3g.Solution B is selected 1,2- pentanediol 25g, EDTA-2Na 6g, RO purified water 66.5g.Skin conditioning agent selects water-soluble Cer NS g.
Specially:
1) Dodecyl Polyglucosides 0.2g, lecithin 0.3g are mixed and heated to 60 DEG C, at this temperature, quickly stirred 15min is mixed, to obtaining clear solution A.
2) 1,2- pentanediols 25g, EDTA-2Na 6g, RO purified water 66.5g is mixed and heated to 70 DEG C, stirred To clear solution B.
3) under high-speed stirred, B solution is slowly added in solution A, until clear solution C is obtained,
4) C solution that cools adds water-soluble Cer NS g to 40 DEG C, stirs and is made clear solution D.
5) ozone is passed through in solution D, ozone concentration is maintained at 0.3mg/L, produces wet tissue liquid E.
The ratio of above-mentioned wet tissue liquid E and wet tissue body by weight 4: 1 is added, then packs, produces acrylic acid Bi-quaternary ammonium salt grafted nonwoven fabric wet tissue.
Embodiment 2
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A is replaced with into obtained bi-quaternary ammonium salt B in preparation example 2.
Embodiment 3
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A mass fraction is replaced with into 0.2%.
Embodiment 4
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A mass fraction is replaced with into 0.15%.
Embodiment 5
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except the mol ratio of bi-quaternary ammonium salt A and (acrylic acid+acrylates) is replaced with into 20: 1.
Embodiment 6
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except the mol ratio of bi-quaternary ammonium salt A and (acrylic acid+acrylates) is replaced with into 30: 1.
Embodiment 7
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except gamma-rays is replaced with into ultraviolet.
Embodiment 8
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue Identical, except soak time is replaced with 12 hours, irradiation intensity replaces with 200KGy.
Embodiment 9
The preparation method and embodiment 2 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue Identical, except lauryl glucoside is replaced with into octadecyl glucoside, lecithin replaces with hydrolecithin.
Embodiment 10
The preparation method and embodiment 2 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except ozone concentration is maintained at into 1.0mg/L.
Embodiment 11
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except the ratio of wet tissue liquid E and wet tissue body by weight 1.5: 1 is added.
Embodiment 12
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue Identical, except the dosage of lauryl glucoside is replaced with into 0.8g, the dosage of lecithin replaces with 0.8g, 1,2- pentanediol Dosage replaces with 30g, and EDTA-2Na dosage replaces with 1g, RO purified waters 67.2g, and the dosage of water-soluble ceramide is replaced For 0.2g.
Embodiment 13
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue Identical, except the dosage of lauryl glucoside is replaced with into 0.5g, the dosage of lecithin replaces with 0.6g, 1,2- pentanediol Dosage replaces with 28g, and EDTA-2Na dosage replaces with 3g, RO purified waters 66.9g, and the dosage of water-soluble ceramide is replaced For 1g.
Comparative example 1
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A mass fraction is replaced with into 0.05%.
Comparative example 2
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except monomer is only bi-quaternary ammonium salt A.
Comparative example 3
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except being added without CeCl3/ HCl/water solution.
Comparative example 4
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A is replaced with into dimethyldiallylammonium salt.
Comparative example 5
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A is replaced with into N- methylacryoyloxyethyls-N, N- dimethylammonium-α-N- methyl carboxybetaines.
Comparative example 6
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A is replaced with into oleamide Ethyldimethylaminopropyl methyl dimethoxysilane quaternary ammonium salt.
Comparative example 7
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A is replaced with into 2- triethoxysilicanes propane Oxy-1-octadecylene base-3- octadecyldimethyl ammoniums Propane dichloride.
Comparative example 8
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A is replaced with into 2- triethoxysilicanes propane Oxy-1-octenyl-3- octadecyldimethyls ammonium third Alkane dichloride.
Comparative example 9
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A is replaced with into 2- triethoxysilicanes propane Oxy-1-laurylene base-3- octadecyldimethyl ammoniums Propane dichloride.
Comparative example 10
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A is replaced with into 2- triethoxysilicane propane Oxy-1-N, N- Dimethylacryloyl-3- octadecanes Base dimethylammonium propane dichloride.
Comparative example 11
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except bi-quaternary ammonium salt A is replaced with into 2- triethoxysilicane propane Oxy-1-N, N- Dimethylacryloyl-3- dodecanes Base dimethylammonium propane dichloride.
Comparative example 12
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except monomer solution is replaced with into 2- triethoxysilicane propane Oxy-1-N, the N- dimethyl that mass fraction is 0.1% The solution of acryloyl group -3- octadecyldimethyl ammonium propane dichloride.
Comparative example 13
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except monomer solution is replaced with into 2- triethoxysilicane propane Oxy-1-N, the N- dimethyl that mass fraction is 0.1% The solution of acryloyl group -3- dodecyl dimethyl ammonium propane dichloride.
Comparative example 14
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except 1,2- pentanediols are replaced with into 1,5-PD.
Comparative example 15
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except 1,2- pentanediols are replaced with into 1,2-PD.
Comparative example 16
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue Identical, except the dosage of 1,2- pentanediols is replaced with into 22g, the dosage of RO purified waters replaces with 69.5g.
Comparative example 17
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue Identical, except the dosage of 1,2- pentanediols is replaced with into 33g, the dosage of RO purified waters replaces with 65g, EDTA-2Na dosage 1g is replaced with, the dosage of water-soluble ceramide replaces with 0.5g.
Comparative example 18
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except lecithin is replaced with into lanolin.
Comparative example 19
The preparation method and embodiment 1 of wet tissue body, wet tissue liquid E and acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue It is identical, except lauryl glucoside is replaced with into sodium cocoyl glutamate.
Technique effect:
1. fungistatic effect
By the evaluation criterion testing example in Disposable Sanitary Accessory sanitary standard GB15979-2002 appendix Cs It is as shown in table 1 with the bacteriostasis rate of wet tissue in comparative example, test result:
The fungistatic effect of the wet tissue of table 1
It can be seen from the data in table 1 compared with the wet tissue in comparative example, wet tissue product of the invention has more excellent Different anti-microbial property.
2. soft and smooth property
Group is evaluated using 5 people to evaluate the flexibility of wet tissue in embodiment and comparative example by ten point system, test knot Fruit is as shown in table 2:
The soft and smooth property of the wet tissue of table 2
It can be seen from the data in table 2 compared with the wet tissue in comparative example, wet tissue product of the invention has more excellent Different softness and smoothness.
3. excitant
Foundation《Disinfection technology standard》In an intact skin stimulation test to wet tissue carry out skin irritation detection, survey Test result is as shown in table 3:
The excitant of the wet tissue of table 3
Standards of grading:
Erythema is formed:0 is nothing, and 1 is visible reluctantly, and 2 be obvious, and 3 be serious, and 4 be aubergine erythema, and has eschar;
Oedema is formed:0 is nothing, and 1 is visible reluctantly, and 2 be cutaneous protuberance, and profile understands, 3 be that oedema swells about 1mm, and 4 are Oedema is swelled more than 1mm.
It can be seen from the data in table 3 compared with the wet tissue in comparative example 4-19, wet tissue product of the invention has Smaller excitant.
4. comfort level
Wet tissue in above-described embodiment and comparative example is used 10 days to red hip baby, the effect such as institute of table 4 after use Show:
The red hip baby of table 4 uses wet tissue effect
It can be seen from the data in table 4 compared with the wet tissue in comparative example, use the present invention's to red hip baby After physical antibacterial pasteurization towelette, sufferer improves significantly, suitable for popularization and application.

Claims (10)

1. a kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue, it is made up of wet tissue body and wet tissue liquid, the wet tissue sheet Body is the non-woven fabrics for being bonded high molecular quaternary;The wet tissue liquid is made up of following with each component of percentage by weight:
RO purified waters 65-70%
12-18 alkyl glucosides 0.2-0.8%
Lecithin or hydrolecithin 0.3-0.8%
1,2- pentanediol 25-30%
Skin conditioning agent 0.2-2%
Other additives 1-6%,
Each component content sum is 100%;
Wherein, the preparation method of wet tissue body is:
(1) length is used as 40-50mm, and a diameter of 0.04-0.1mm bamboo pulp fiber is as raw material, through cross lapping spun lacing work Bamboo pulp non-woven fabrics is made after skill, the nonwoven carrier that thickness is 3-5mm is obtained after clipped, high-temperature sterilization;
(2) nonwoven carrier made from step (1) is placed in the monomer solution of isopropanol/water mixed solvent preparation, at room temperature Lucifuge soaks 12-24 hours;
(3) under nitrogen protection, CeCl is added in monomer solution3/ HCl/water solution, passed through with x ray irradiation x above-mentioned steps (2) The non-woven fabrics obtained after immersion, irradiation intensity 80-200KGy;
(4) after irradiation terminates, unreacted monomer and homopolymer are fallen in extracting, and wet tissue body is obtained after drying;
Wherein, the acrylic acid that monomer is bi-quaternary ammonium salt and degree of neutralization is 60-70%, the quality point of bi-quaternary ammonium salt in monomer solution Number is 0.1-0.2%, and the mol ratio of bi-quaternary ammonium salt and (acrylic acid+acrylates) is (20-30): 1;CeCl3In reactant Initial concentration in system is (1-2) × 10-4The initial concentration of mol/L, HCl in reaction system is (1-2) × 10-3mol/L;
The bi-quaternary ammonium salt is the compound shown in formula 1 or formula 2:
2. acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue as claimed in claim 1, wherein, the skin conditioning agent is nerve One or more in acid amides, Co-Q10, tocopherol acetate, resveratrol, astaxanthin.
3. acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue as claimed in claim 1, wherein, other described additives are antioxygen One or more kinds of mixtures in agent, chelating agent, pH adjusting agent.
4. the acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue as described in claim 1 or 3, wherein, other additives choosing From one or more kinds of mixing in Butylated Hydroxytoluene, EDTA-2Na, EDTA-4Na, arginine, citric acid, sodium citrate Thing.
5. acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue as claimed in claim 1, wherein, the 12-18 alkyl glucosides For lauryl glucoside.
6. acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue as claimed in claim 1, wherein, the 12-18 alkyl glucosides For octadecyl glucoside.
7. acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue as claimed in claim 1, wherein, the ray be selected from ultraviolet, Electron beam, X ray, alpha ray, β rays or gamma-rays.
8. the preparation method of the acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue as described in claim 1-7 any one, it is special Sign is:
The preparation method of wet tissue body is:
(1) length is used as 40-50mm, and a diameter of 0.04-0.1mm bamboo pulp fiber is as raw material, through cross lapping spun lacing work Bamboo pulp non-woven fabrics is made after skill, the nonwoven carrier that thickness is 3-5mm is obtained after clipped, high-temperature sterilization;
(2) nonwoven carrier made from step (1) is placed in the monomer solution of isopropanol/water mixed solvent preparation, at room temperature Lucifuge soaks 12-24 hours;
(3) under nitrogen protection, CeCl is added in monomer solution3/ HCl/water solution, passed through with x ray irradiation x above-mentioned steps (2) The non-woven fabrics obtained after immersion, irradiation intensity 80-200KGy;
(4) after irradiation terminates, unreacted monomer and homopolymer are fallen in extracting, and wet tissue body is obtained after drying;
Wherein, the acrylic acid that monomer is bi-quaternary ammonium salt and degree of neutralization is 60-70%, the quality point of bi-quaternary ammonium salt in monomer solution Number is 0.1-0.2%, and the mol ratio of bi-quaternary ammonium salt and (acrylic acid+acrylates) is (20-30): 1;CeCl3In reactant Initial concentration in system is (1-2) × 10-4The initial concentration of mol/L, HCl in reaction system is (1-2) × 10-3mol/L;
The bi-quaternary ammonium salt is compound shown in formula 1 or formula 2:
Wet tissue liquid is the facial treatment milk of transparent and stable, and its preparation method is:
(1) 12-18 alkyl glucosides 0.2-0.8%, lecithin or hydrolecithin 0.3-0.8% are mixed and heated to 50- 80 DEG C, at this temperature, 5-20min is quickly stirred, to obtaining clear solution A;
(2) RO purified waters 65-70%, 1,2- pentanediols 25-30%, other additives 1-6% are mixed and heated to 60-90 DEG C, it is evenly stirred until clear solution B;
(3) under high-speed stirred, B solution is slowly added in solution A, until obtaining clear solution C;
(4) C solution that cools addition skin conditioning agent 0.2-2%, stirs to less than 45 DEG C and is made clear solution D;
(5) ozone is passed through in solution D, ozone concentration is maintained in the range of 0.1-1.0mg/L, produces wet tissue liquid E;
Finally, the ratio of wet tissue liquid E and the wet tissue body by weight 1.5: 1-4: 1 for being cut into suitable dimension is added, then Pack, produce acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue.
9. preparation method as claimed in claim 8, wherein ozone concentration are in 0.1-0.5mg/L scopes.
10. preparation method as claimed in claim 8, wherein wet tissue liquid E are with being cut into the wet tissue body of suitable dimension by weight The ratio addition of amount 2: 1-3: 1.
CN201711094248.9A 2017-11-09 2017-11-09 A kind of acrylic acid bi-quaternary ammonium salt grafted nonwoven fabric wet tissue and preparation method thereof Pending CN107789214A (en)

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Application publication date: 20180313