Summary of the invention
The present invention is directed to current domestic manufacture cleansing tissue cellulose fluff nonwoven fabric (viscose, wood pulp fibre, cotton fiber and copper ammonia fibre used, component content is more than 70%) exist dust amount cannot, for the defect of toilet, provide a kind of nonwoven fabric that dust amount is little, ion concentration is low, nonvolatile organic compound content is low and manufacture method thereof that is applicable to toilet greatly.
The present invention solves the problems of the technologies described above by the following technical solutions.
For the manufacture of a nonwoven fabric for dust-free cleaning paper, comprise the nonwoven fabric that contains cellulose fibre, the Treatment Solution of described nonwoven fabric through containing polyvinyl alcohol, water polyacrylic acid, water-based isocyanate crosslinking agent processed and formed.
The degree of polymerization of described polyvinyl alcohol is 1700 ~ 1750, and alcoholysis degree is 96% ~ 98%.
Described water polyacrylic acid is water miscible polyacrylate.
Described polyacrylate refers to the polymer of acrylate.
Described polyacrylate is that butyl acrylate, hydroxy-ethyl acrylate, allyl polyethenoxy ether, methyl methacrylate, methacrylic acid are polymerized.
Described polyacrylate be first by methyl methacrylate, methacrylic acid, initator in 80 ~ 85 ℃ of polymerizations, and then add butyl acrylate, hydroxy-ethyl acrylate, allyl polyethenoxy ether, initator in 80 ~ 85 ℃ of polymerizations.
Described polyacrylate is first by methyl methacrylate, methacrylic acid emulsification, obtains pre-emulsion A; Butyl acrylate, hydroxy-ethyl acrylate, allyl polyethenoxy ether emulsification are obtained to pre-emulsion B; Then in pre-emulsion A, introduce initator, in 80 ~ 85 ℃ of polymerizations, then add pre-emulsion B and initator to continue at 80 ~ 85 ℃ of polymerizations.
Polyvinyl alcohol in described Treatment Solution (PVA) accounts for 0.2% ~ 2% of Treatment Solution gross mass, is preferably 0.4% ~ 1%.
Water polyacrylic acid in described Treatment Solution (PA) accounts for 0.3% ~ 3% of Treatment Solution gross mass, is preferably 0.6% ~ 2%.In described Treatment Solution, water-based isocyanate crosslinking agent quality is 1% ~ 10% of polyvinyl alcohol and water polyacrylic acid gross mass, is preferably 3%.
The present invention is also provided for manufacturing the manufacture method of the nonwoven fabric of dust-free cleaning paper, comprises the following steps: (1) configuration process solution: polyvinyl alcohol, water polyacrylic acid and water-based isocyanate crosslinking agent are added to the water and are re-dubbed Treatment Solution; (2) process: adopt above-mentioned Treatment Solution to pad processing to the nonwoven fabric of containing cellulose fiber, pick-up is 180%; (3) dry: the nonwoven fabric of step (2) is trained at 120~180 ℃ and dried 30~300s.
Polyvinyl alcohol in described step (1) accounts for 0.2% ~ 2% of Treatment Solution gross mass, is preferably 0.4% ~ 1%.
Water polyacrylic acid in described step (1) accounts for 0.3% ~ 3% of Treatment Solution gross mass, is preferably 0.6% ~ 2%.
Water-based isocyanate crosslinking agent quality in described step (1) is 1 ~ 10% of polyvinyl alcohol and water polyacrylic acid total amount, is preferably 3%.
The polyvinyl alcohol degree of polymerization in described step (1) is 1700 ~ 1750, and alcoholysis degree is 96% ~ 98%.
Water polyacrylic acid in described step (1) is water miscible polyacrylate.
The polymer that polyacrylate in described step (1) is acrylate.
Polyacrylate in described step (1) is that butyl acrylate, hydroxy-ethyl acrylate, allyl polyethenoxy ether, methyl methacrylate and methacrylic acid are polymerized.
The polyacrylate of described step (1) be first by methyl methacrylate, methacrylic acid, initator in 80 ~ 85 ℃ of polymerizations, and then add butyl acrylate, hydroxy-ethyl acrylate, allyl polyethenoxy ether, initator in 80 ~ 85 ℃ of polymerizations.
Water polyacrylic acid in described step (1) is first by methyl methacrylate, methacrylic acid emulsification, obtains pre-emulsion A; Butyl acrylate, hydroxy-ethyl acrylate, allyl polyethenoxy ether emulsification are obtained to pre-emulsion B; Then in pre-emulsion A, add initator, in 80 ~ 85 ℃ of polymerizations, then add pre-emulsion B and initator to continue at 80 ~ 85 ℃ of polymerizations.
Water polyacrylic acid in described step (1) synthesizes by following steps: (1) adds certain volume deionized water for stirring by 0.05% ~ 1%OP-10, and be added dropwise to 2 ~ 30% methyl methacrylates, 1% ~ 5% methacrylic acid, vigorous stirring also slowly adds deionized water, obtains pre-emulsion A; (2) 0.05% ~ 1%OP-10 is added to certain volume deionized water for stirring, then drip 10% ~ 30% butyl acrylate, 1% ~ 5% hydroxy-ethyl acrylate, 10% ~ 50% allyl polyethenoxy ether, vigorous stirring also slowly adds deionized water, obtains pre-emulsion B; (3) pre-emulsion A is added in four-hole bottle and is stirred, and be 6.5 ~ 7.5 with ammoniacal liquor adjusting pH, be directly warming up to 80-85 ℃, and add ammonium persulfate 0.3%, and remain on this temperature, drip pre-emulsion B, be added dropwise to complete rear dropping ammonium persulfate 0.7%, insulation reaction 2 ~ 3h; (4) the every 20min test reaction of course of reaction liquid pH, regulates pH to 6.5 ~ 7.5 with ammoniacal liquor, after having reacted, obtains white emulsion; (5) with ammoniacal liquor, regulate pH to 8 ~ 9, the expanded 1h of high-speed stirred, then under agitation, adds PEG400 and glycerol (PEG400: glycerol=1:1) by 40g alcohol/100g emulsion droplets, be stirred to the transparency liquid that solution is blue light, obtain water polyacrylic acid.
The gross mass that adds water in step (1) and step (2): the gross mass=7:3 of methyl methacrylate, methacrylic acid, butyl acrylate, hydroxy-ethyl acrylate and allyl polyethenoxy ether.
First, the Treatment Solution that the present invention adopts polyvinyl alcohol, water polyacrylic acid and water-based isocyanate crosslinker compounding to become is processed the nonwoven fabric of containing cellulose fiber.On the one hand, because polyvinyl alcohol and water-based multi isocyanate crosslinking form cross-linked polymer I, water polyacrylic acid and water-based multi isocyanate crosslinking form cross-linked polymer II, the network of polymer I and polymer II is the interspersed interpenetrating net polymer that forms mutually, because interpenetrating net polymer is mutually to be interted and form continuously by the network of gained after each self-crosslinking of at least two kinds of cross-linked polymers, form the network of crosslinked IPN, so adopt more merely polyacrylate or polyvinyl alcohol, its cleanliness factor better effects if after nonwoven fabric is processed.On the other hand, part of hydroxyl reaction due to the part water-based isocyanate in interpenetrating net polymer and cellulose fibre, thereby interpenetrating net polymer is combined on nonwoven fabric securely, can effectively increase the fastness between nonwoven fabric short fiber, reduce its powder amount (LPC), ion concentration and do not increase non-VOC (NVR) content.Therefore, the cellulose fibre on the polyvinyl alcohol in treatment fluid, water polyacrylic acid, water-based isocyanate crosslinking agent, nonwoven fabric reacts to each other between two and acts on, and gives nonwoven fabric good clean performance.Moreover water polyacrylic acid of the present invention has adopted allyl polyethenoxy ether monomer when synthetic, has greatly improved the flexibility of nonwoven fabric.
In a word, nonwoven fabric of the present invention is soft, and cleanliness factor is high, and manufacture method industry is fairly simple, is easy to realize industrialization.
The specific embodiment
Test index and method of testing thereof.
LPC (Liquid particle counts) method of testing is with reference to the single shaft shaking table test method(s) of IEST-RP-CC004.3 the 6th chapter, difference is that pre-treatment part changes pallet into 1000ml beaker, add 600ml deionized water, add a slice cleansing tissue and be placed on single shaft oscillator with the velocity fluctuation 5min of 150rpm, then with liquid-borne particle counter, testing.
The method of testing of ion concentration is as follows: folder a slice cleansing tissue is placed in the beaker that contains 200ml deionized water, soaks one hour, intermittently shakes beaker.Use clean tweezers to take out specimen, and detect with chromatography of ions instrument.
NVR method of testing is as follows: get a slice cleansing tissue and be placed in the beaker that contains 100ml isopropyl alcohol, soak 24 hours, intermittently shake beaker.With graduated cylinder, 50ml sample liquid is transferred on aluminium dish several times, each time in aluminium dish sample liquid be evaporated to residue a little time supplement, during evaporation, note not boiling, use totally 10 milliliters, identical solvent washing graduated cylinder 3 times, three times flushing liquor is all poured into aluminium dish.Continue heating, until all solvents are evaporated completely, and aluminium dish is placed in to drier is at least 1 hour and again weighs aluminium dish, precision is 0.0001g.Record weight as the final weight of sample, and aluminium circles or whirl in the air white.
Pliability method of testing is as follows: choose 10 all ages and classes, property others, with hand, twist with the fingers dust-free cleaning paper, and according to sense of touch, the softness of all samples sorted.
Water polyacrylic acid of the present invention refers to water miscible polyacrylate, the synthetic method of water polyacrylic acid is as follows: (1) adds 10ml deionized water for stirring by 0.5%OP-10, and be added dropwise to 30% methyl methacrylate, 2% methacrylic acid, vigorous stirring also slowly adds 60ml deionized water, obtains pre-emulsion A.(2) by 1%OP-10, add 10ml deionized water for stirring, then drip 18.3% butyl acrylate, 3% hydroxy-ethyl acrylate, 46.7% allyl polyethenoxy ether, vigorous stirring also slowly adds 60ml deionized water, obtains pre-emulsion B.(3) pre-emulsion A is added in four-hole bottle and is stirred, and be 7 with ammoniacal liquor adjusting pH, be warming up to 85 ℃, and add ammonium persulfate 0.3%, remain on this temperature, drip pre-emulsion B, be added dropwise to complete rear dropping ammonium persulfate 0.7%, insulation reaction 3h.(4) the every 20min test reaction of course of reaction liquid pH, regulates pH to 7 with ammoniacal liquor, after having reacted, obtains white emulsion.(5) with ammoniacal liquor, regulate pH to 8, the expanded 1h of high-speed stirred, then under agitation, adds PEG400 and glycerol (1:1) by 40g alcohol/100g emulsion droplets, is stirred to the translucent liquid that solution is blue light, obtains water polyacrylic acid WPEA-1.
The gross mass that adds deionized water in step (1) and step (2): the gross mass of methyl methacrylate, methacrylic acid, butyl acrylate, hydroxy-ethyl acrylate and allyl polyethenoxy ether is 7:3.
In step, the percentage composition of all substances is all that to take the gross mass of methyl methacrylate, methacrylic acid, butyl acrylate, hydroxy-ethyl acrylate and allyl polyethenoxy ether be benchmark, and for example 0.05%OP-10 is that the addition of OP-10 is not 0.05% of the gross mass of methyl methacrylate, methacrylic acid, butyl acrylate, hydroxy-ethyl acrylate and allyl polyethenoxy ether.
OP-10 in step (1) can be 0.05% ~ 1%, and methyl methacrylate can be 2 ~ 30%, and methacrylic acid can be 1% ~ 3%; OP-10 in step (2) can be 0.05% ~ 1%, and butyl acrylate can be 10% ~ 30%, and hydroxy-ethyl acrylate can be 1% ~ 5%, and allyl polyethenoxy ether can be 10% ~ 50%; The reaction temperature of step (3) can be 80-85 ℃, and the reaction time can be 2-3h; The pH value of step (4) can be 6.5-7.5; The pH value of step (5) can be 8-9.
The contrast synthetic method of polyacrylate is as follows: (1) adds 10ml deionized water for stirring by 0.5%OP-10, and is added dropwise to 20% methyl methacrylate, 3% methacrylic acid, and vigorous stirring also slowly adds 60ml deionized water, obtains pre-emulsion A.(2) 1%OP-10 is added to 10ml deionized water for stirring, then drip 15% butyl acrylate, 2% hydroxy-ethyl acrylate, vigorous stirring also slowly adds 60ml deionized water, obtains pre-emulsion B.(3) pre-emulsion A is added in four-hole bottle and is stirred, and be 7 with ammoniacal liquor adjusting pH, be warming up to 85 ℃, and add ammonium persulfate 0.3%, remain on this temperature, drip pre-emulsion B, be added dropwise to complete rear dropping ammonium persulfate 0.7%, insulation reaction 3h.(4) the every 20min test reaction of course of reaction liquid pH, regulates pH to 7 with ammoniacal liquor, after having reacted, obtains white emulsion.(5) with ammoniacal liquor, regulate pH to 8, the expanded 1h of high-speed stirred, then under agitation, adds PEG400 and glycerol (1:1) by 40g alcohol/100g emulsion droplets, is stirred to the translucent liquid that solution is blue light, obtains water polyacrylic acid WPEA-2.
In step, the percentage composition of all substances is all that to take the gross mass of methyl methacrylate, methacrylic acid, butyl acrylate, hydroxy-ethyl acrylate and allyl polyethenoxy ether be benchmark, and for example 0.05%OP-10 is that the addition of OP-10 is not 0.05% of the gross mass of methyl methacrylate, methacrylic acid, butyl acrylate, hydroxy-ethyl acrylate and allyl polyethenoxy ether.
Embodiment 1: the treatment step of nonwoven fabric is as follows: (1) configuration process solution: the polyvinyl alcohol that the degree of polymerization is 1700, alcoholysis degree is 97% is dissolved to 1h in boiling water, then add respectively above-mentioned synthetic water polyacrylic acid WPEA-1, water-based polyisocyanate crosslinker, vigorous stirring is to mixing; Wherein polyvinyl alcohol (PVA) accounts for 0.4% of solution gross mass, and polyacrylate (PA) accounts for 0.6% of solution gross mass, and water-based polyisocyanate crosslinker accounts for 0.03% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; Adopt the Treatment Solution of step (1) to pad processing once to nonwoven fabric, pick-up is 180%.(3) dry: by the nonwoven fabric of step (2), in training baking machine, at 180 ℃, 1min is dried in training, obtains sample 1.
The nonwoven fabric of comparative example 1:70% viscose and 30% polyster fibre combination, grammes per square metre is 30g/m
2, be designated as sample 1A.
Comparative example 2: the treatment step of nonwoven fabric is as follows: (1) configuration process solution: enclosed type water-based polyisocyanate crosslinker polymer is added to dissolved dilution in the aqueous solution, and vigorous stirring is to mixing; Isocyanate crosslinking accounts for 1% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; Adopt the Treatment Solution of step (1) to pad processing once to nonwoven fabric, pick-up is 180%.(3) dry: the nonwoven fabric of step (2) is trained and dried 1min in training baking machine at 180 ℃, obtain sample 1B.
Comparative example 3: with 1% polyvinyl alcohol, process separately nonwoven fabric, the treatment step of nonwoven fabric is as follows: (1) configuration process solution: the polyvinyl alcohol that the degree of polymerization is 1700, alcoholysis degree is 98% is added to 1h in the boiling water aqueous solution, and vigorous stirring is to all dissolving; Polyvinyl alcohol (PVA) accounts for 1% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; The treatment fluid of nonwoven fabric being put into step (1) pads processing once, and pick-up is 180%.(3) dry: the nonwoven fabric of step (2) is trained and dried 1min in training baking machine at 180 ℃, obtain sample 1C.
Comparative example 4: with 1% water polyacrylic acid, process separately nonwoven fabric, the treatment step of nonwoven fabric is as follows: (1) configuration process liquid: water polyacrylic acid A is added in the aqueous solution, and vigorous stirring 1h is to all dissolving; Water polyacrylic acid accounts for 1% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; The treatment fluid of nonwoven fabric being put into step (1) pads processing, and pick-up is 180%.(3) dry: the nonwoven fabric of step (2) is trained and dried 1min in training baking machine at 180 ℃, obtain sample 1D.
Comparative example 5: the treatment step of nonwoven fabric is as follows: (1) configuration process liquid: the polyvinyl alcohol that the degree of polymerization is 1700, alcoholysis degree is 98% is dissolved to 1h in boiling water, then add and add respectively above-mentioned synthetic water polyacrylic acid A, vigorous stirring to mixing; Wherein polyvinyl alcohol (PVA) accounts for 0.4% of solution gross mass, and polyacrylate (PA) accounts for 0.6% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; The treatment fluid of nonwoven fabric being put into step (1) pads processing once, and pick-up is 180%.(3) dry: by the nonwoven fabric of step (2), in training baking machine, at 180 ℃, 1min is dried in training, obtains sample 1E.
Comparative example 6: the treatment step of nonwoven fabric is as follows: (1) configuration process liquid: the polyvinyl alcohol that the degree of polymerization is 1700, alcoholysis degree is 98% is dissolved to 1h in boiling water, then add and add respectively above-mentioned synthetic water polyacrylic acid WPEA-2, water-based polyisocyanate crosslinker, vigorous stirring is to mixing; Wherein polyvinyl alcohol (PVA) accounts for 0.4% of solution gross mass, and polyacrylate (PA) accounts for 0.6% of solution gross mass, and water-based polyisocyanate crosslinker accounts for 0.03% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; The treatment fluid of nonwoven fabric being put into step (1) pads processing once, and pick-up is 180%.(3) dry: by the nonwoven fabric of step (2), in training baking machine, at 180 ℃, 1min is dried in training, obtains sample 1F.
Embodiment 2: the treatment step of nonwoven fabric is as follows: (1) configuration process liquid: the polyvinyl alcohol that the degree of polymerization is 1750, alcoholysis degree is 98% is dissolved to 1h in boiling water, then add water polyacrylic acid WPEA-1, water-based polyisocyanate crosslinker, vigorous stirring is to mixing; Wherein polyvinyl alcohol (PVA) accounts for 0.2% of solution gross mass, and water polyacrylic acid (PA) accounts for 2% of solution gross mass, and water-based polyisocyanate crosslinker accounts for 0.022% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; The treatment fluid of nonwoven fabric being put into step (1) pads processing once, and pick-up is 180%.(3) dry: the nonwoven fabric of step (2) is trained and dried 5min at 120 ℃ in training baking machine, obtain sample 2.
Embodiment 3: the treatment step of nonwoven fabric is as follows: (1) configuration process liquid: the polyvinyl alcohol that the degree of polymerization is 1750, alcoholysis degree is 98% is added and in boiling water, dissolves 1h, then add water polyacrylic acid WPEA-1, water-based polyisocyanate crosslinker, vigorous stirring is to mixing; Wherein polyvinyl alcohol (PVA) accounts for 1% of solution gross mass, and polyacrylate (PA) accounts for 3% of solution gross mass, and water-based polyisocyanate crosslinker accounts for 0.4% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; The treatment fluid of nonwoven fabric being put into step (1) pads processing once, and pick-up is 180%.(3) dry: the nonwoven fabric of step (2) is trained and dried 3min in training baking machine at 140 ℃, obtain sample 3.
Embodiment 4: the treatment step of nonwoven fabric is as follows: (1) configuration process liquid: the polyvinyl alcohol that the degree of polymerization is 1750, alcoholysis degree is 98% is added and in boiling water, dissolves 1h, then add water polyacrylic acid WPEA-1, water-based polyisocyanate crosslinker, vigorous stirring is to mixing; Wherein polyvinyl alcohol (PVA) accounts for 2% of solution gross mass, and polyacrylate (PA) accounts for 0.3% of solution gross mass, and water-based polyisocyanate crosslinker accounts for 0.115% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; The treatment fluid of nonwoven fabric being put into step (1) pads processing once, and pick-up is 180%.(3) dry: the nonwoven fabric of step (2) is trained and dried 30s in training baking machine at 160 ℃, obtain sample 4.
Embodiment 5: the treatment step of nonwoven fabric is as follows: (1) configuration process liquid: the polyvinyl alcohol that the degree of polymerization is 1750, alcoholysis degree is 98% is added and in boiling water, dissolves 1h, then add water polyacrylic acid WPEA-1, water-based polyisocyanate crosslinker, vigorous stirring is to mixing; Wherein polyvinyl alcohol (PVA) accounts for 1% of solution gross mass, and polyacrylate (PA) accounts for 0.6% of solution gross mass, and water-based polyisocyanate crosslinker accounts for 0.048% of solution gross mass.(2) process: the present embodiment is selected the nonwoven fabric of 70% viscose and 30% polyster fibre combination, and nonwoven fabric grammes per square metre is 30g/m
2; The treatment fluid of nonwoven fabric being put into step (1) pads processing once, and pick-up is 180%.(3) dry: the nonwoven fabric of step (2) is trained and dried 1min in training baking machine at 180 ℃, obtain sample 5.
Prepared sample is cut into the cleansing tissue of 9cm * 9cm, and tests, test result is as shown in table 1.
The cleanliness factor table with test results of table 1 sample.
Pliability sequence: 1A > 1D > 2 > 1 > 1E > 3 > 5 > 1F > 4 > 1C > 1B.
Data from table can be found out, adopt the nonwoven fabric of polyvinyl alcohol, water polyacrylic acid and the processing of water-based isocyanate crosslinking agent, have higher cleanliness factor.This may be to form a kind of inierpeneirating network structure because polyvinyl alcohol and water-based multi isocyanate crosslinking form cross-linked polymer with water polyacrylic acid and water-based multi isocyanate crosslinking formation cross-linked polymer, thereby compared with the polymer of non-inierpeneirating network structure, it more can effectively reduce powder amount, the reduction total ion concentration of cleansing tissue, do not increase NVR content simultaneously, and interpenetrating net polymer can with cellulose fibre on active group react, viscosity is strong, difficult drop-off.In addition, the addition increase along with polyvinyl alcohol in treatment fluid, can obviously reduce and inhale isopropyl alcohol amount, thereby can save dust-free cleaning paper solvent use amount in use.
Moreover, to be not difficult to find out, water polyacrylic acid of the present invention is owing to having introduced after allyl polyethenoxy ether, and flexibility improves.