CN103911902B - Hygienic Paper additive, toilet paper manufacture method and toilet paper using the additive - Google Patents
Hygienic Paper additive, toilet paper manufacture method and toilet paper using the additive Download PDFInfo
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Abstract
Necessary dry paper intensity can be assigned when manufacturing toilet paper, while the hygienic Paper additive and the manufacture method for the paper for using the additive that are had no adverse effects to productivity and quality the invention provides a kind of.The hygienic Paper additive contains both sexes (methyl) acrylamide polymer A and water soluble aluminum compound B, it is A: B=95: 5 ~ 40: 60 that the content ratio of the two, which is converted into solids by weight ratio, wherein, both sexes (methyl) acrylamide polymer A is that the monomer component copolymerization containing (methyl) acrylamide a162 ~ 98.95 mole %, cationic vinyl monomer a20.55 ~ 20 mole % and anionic vinyl monomer a30.5 ~ 18 mole % is obtained, cationic vinyl monomer a2 and anionic vinyl monomer a3 ionic equivalent ratio（A2 cation equivalent/a3 anion equivalents）For 1.1 ~ 40.
Description
Technical field
The present invention relates to the additive used during a kind of manufacture of toilet paper, use the additive toilet paper manufacture method and
Toilet paper.
Background technology
Toilet paper may be generally classified as paper handkerchief, toilet paper, tissue etc..The feature of above-mentioned toilet paper can be enumerated as thin, softness,
General paper handkerchief, toilet paper weight it is very light, quantification of 10 ~ 30g/m2.In addition, the density of toilet paper is 0.2 ~ 0.3g/cm3, with one
As the density of good quality paper be about 0.8g/cm3, newsprint density be about 0.6g/cm3Compare, its volume is big, very soft.Make
For toilet paper, water imbibition is necessary, compared with other paper, and reduction density, increase paper void can improve water imbibition.But,
The intensity of paper can be reduced while reduction paper density, and toilet paper requirement has the dry paper intensity of resistance to use level.
, can using the high softwood kraft pulp of fiber length, intensity as main material generally, as the raw material of toilet paper
In the case where reducing paper density, the dry paper intensity of resistance to use level is assigned.For example enumerate quality of the toilet paper in JIS commercial sizes
The rupture strength of dry paper intensity is used as in regulation（JIS P4501）.In addition, being higher than a certain tensile strength generally for toilet paper
It is necessary.
However, in recent years, because the softwood kraft pulp as main material is different because region difference obtains complexity
And factor in terms of price, the increase of the adding rate and waste paper utilization rate of broad leaf tree paper pulp is caused, accordingly, there exist raw material paper
Pulp fibres intensity decreases, it is difficult to the problem of obtaining with the toilet paper for providing dry paper intensity.
It is used as the countermeasure of above mentioned problem, it is known that when toilet paper is manufactured paper with pulp, cationic starch, second is added into pulp
The additives such as dialdehyde polyacrylamide based polymer and the method for assigning dry paper intensity, but its effect is insufficient.In addition, being
Improve dry paper intensity and excessively increase additive, the problem of there is the flexibility and quality for damaging made toilet paper.
The content of the invention
It is an object of the invention to provide one kind when manufacturing toilet paper, the toilet paper institutes such as flexibility, water imbibition can maintained
It is required that quality while, assign the necessary dry paper intensity of toilet paper hygienic Paper additive.And there is provided a kind of toilet paper
Manufacture method, methods described when using the pulp for the paper pulp fiber for largely having coordinated intensity difference as raw material,
Can efficiently it manufacture with the dry sufficiently high toilet paper of paper intensity.
The present patent application contains both sexes (methyl) acrylamide polymer and water-soluble aluminum by using with special ratios
The additive of compound, so as to solve above-mentioned problem.
Usually, as dry paper power reinforcing agent, it is known to polyacrylamide based polymer, wherein branched both sexes polypropylene
Acid amides is functional, but in the toilet paper of light basis weight, branched both sexes polypropylene amine compendency is high, causes to strengthen paper strength
Effect reduction.In the technology of the present invention, find both sexes (methyl) acrylamide polymer and water soluble aluminum compound with specific
Ratio is mixed, it is possible to decrease compendency, improves the effect of enhancing paper strength, and then, can further it be dropped containing water-soluble electrolytes
Low aggegation effect, while the viscosity stability of the polyacrylamide solution containing water soluble aluminum compound can be improved.
That is, the present invention relates to a kind of hygienic Paper additive, the hygienic Paper additive contains both sexes (methyl) acrylamide
Based polymer A and water soluble aluminum compound B, it is A: B=95: 5 ~ 40 that the content ratio of the two, which is converted into solids by weight ratio:
60, wherein, both sexes (methyl) acrylamide polymer A is containing (methyl) acrylamide a162 ~ 98.95 mole %, cation
What vinyl monomer a20.55 ~ 20 mole % and anionic vinyl monomer a30.5 ~ 18 mole % monomer component copolymerization were obtained,
Cationic vinyl monomer a2 and anionic vinyl monomer a3 ionic equivalent ratio（A2 cation equivalent/a3 anion
Equivalent）For 1.1 ~ 40；The invention further relates to further containing the water-soluble inorganic electrolyte in addition to above-mentioned water soluble aluminum compound B
C and/or water-soluble organic bath D hygienic Paper additive.The invention further relates to above-mentioned hygienic Paper additive addition exists
The toilet paper manufacture method that copy paper is characterized is carried out in pulp；Utilize toilet paper made from above-mentioned toilet paper manufacture method.
When manufacturing toilet paper, the hygienic Paper additive of the present invention is added into pulp can improve the strong of made toilet paper
Degree, particularly dry paper intensity.According to the manufacture method of the present invention, in general toilet paper manufacturing environment, when only using raw material
Paper pulp be unable to reach as defined in intensity or a large amount of when coordinating the poor starting pulps of intensity, can assign excellent dry paper intensity.
Therefore, the selection of starting pulps species can be expanded, coordinate scope, the toilet paper of high-quality can be stably manufactured.
Embodiment
The hygienic Paper additive of the present invention is a kind of aqueous solution or aqueous dispersions, and the aqueous solution or aqueous dispersions contain two
Property (methyl) acrylamide polymer A and water soluble aluminum compound B, the content ratio of the two is converted into solids by weight ratio
For A: B=95: 5 ~ 40: 60, wherein, both sexes (methyl) acrylamide polymer A is containing (methyl) acrylamide, cation
What the polymeric composition copolymerization of vinyl monomer and anionic vinyl monomer was obtained.
Both sexes (methyl) the acrylamide polymer A of the present invention（Hereinafter referred to as polymer A）Middle (methyl) third used
Acrylamide a1（Hereinafter referred to as a1 compositions）Refer to acrylamide or Methacrylamide（Hereinafter, (methyl) represents same meaning
Think）, mentioned component can be used alone or be applied in combination, from the economic viewpoint, acrylamide be used alone preferable.A1 compositions
Ratio be not particularly limited, generally from the viewpoint of sufficient paper strength effect is ensured, relative to (methyl) acryloyl
The molal quantity summation of the polymeric composition of amine system copolymer, a1 ratio is 62 ~ 98.95 weight %, preferably 70 ~ 97 weight %.
It is used as the cationic vinyl monomer a2 used in polymer A（Hereinafter referred to as a2 compositions）, for example, (first can be enumerated
Base) dimethylaminoethyl acrylate, (methyl) diethylaminoethyl acrylate, dimethylamino-propyl (methyl) acrylamide, two
The inorganic acid salt or acylate of ethylaminopropyl (methyl) acrylamide etc., or the vinyl monomer containing the tertiary amino with
Vinyl monomer, the alkene for the quaternary ammonium salt that the reaction of the quaternizing agents such as chloromethanes, benzyl chloride, dimethyl suflfate, epoxychloropropane is obtained
The inorganic acid salt or acylate of propylamine, diallylamine, N- methyl diallylamines etc., dimethyldiallylammonium salt etc..Relatively
In the molal quantity summation of the polymeric composition of (methyl) acrylamide based copolymer, the ratio of a2 compositions is chosen as 0.55 ~ 20 and rubbed
You are %, preferably 2 ~ 10 moles %.During less than 0.55 mole of %, it cannot get sufficient paper strength effect.During more than 20 moles of %, because
Compendency strengthens, and causes paper messy texture, cannot get sufficient paper strength effect.
It is used as the anionic vinyl monomer a3 used in polymer A（Hereinafter referred to as a3 compositions）, for example, (first can be enumerated
Base) monocarboxylic acid such as acrylic acid, crotonic acid, the dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, viscous furancarboxylic acid, vinyl sulfonic acid,
The organic sulfonic acids such as styrene sulfonic acid, 2- acrylamide-2-methyl propane sulfonics, in addition, sodium salt, sylvite of above-mentioned various organic acids etc.
Ammonium salt of alkali metal salt and above-mentioned various organic acids etc.（Note, except (methyl) allyl sulphonic acid and/or its salt）.Relative to polymer
The molal quantity summation of A polymeric composition, the ratio of a3 compositions can be 0.5 ~ 18 mole of %, preferably 1 ~ 10 mole %.Rubbed less than 0.5
During your %, it cannot get sufficient paper strength effect.During more than 18 moles of %, because of compendency enhancing, cause paper messy texture, do not have
It is improved the effect of paper strength.
And then, in polymer A, the ratio of the cation equivalent of a2 compositions and the anion equivalents of a3 compositions（A2 cation
Equivalent/a3 anion equivalents）Must be between 1.1 ~ 40.When ionic equivalent ratio（A2 cation equivalent/a3 anion is worked as
Amount）During less than 1.1, compendency enhancing causes paper messy texture, it is difficult to strengthen paper strength；When above-mentioned mol ratio is more than 40
When, it cannot get sufficient paper strength effect.From the same viewpoint, ionic equivalent ratio（A2 cation equivalent/a3 the moon
Ionic equivalent）Preferably 1.1 ~ 10.In addition, the anion equivalents of the present invention refer to the anionic property functional group that polymer A contains
Number, cation equivalent refers to the number for the cationic functional group that polymer A contains.When contained a3 compositions in polymer A
During for 1 valency, anion equivalents are its molal quantity；When contained a3 compositions are multivalence in polymer A, anion equivalents are rubbed by it
The product of that number and valence mumber is calculated（Many kinds of substance is as a3 compositions in use, anion equivalents are the total after calculating respectively
Value）, cation equivalent can be by calculating acquisition with the same method of above-mentioned anion equivalents.
Polymer A can be the EVA only by above-mentioned monomer component copolymerization, if necessary, if meeting above-mentioned monomer group
Into with ionic equivalent ratio（A2 cation equivalent/a3 anion equivalents）, also can be combined and use other monomers composition.For example,
From the viewpoint of sufficient paper strength effect is ensured, preferred compositions use cross-linkable monomer, and crosslinking is imported into polymer A
Structure（Branched structure）.And then, for control reaction speed, regulation molecular weight, chain transfer monomer can be used, in addition it is also possible to
Nonionic vinyl monomer is applied in combination.
As cross-linkable monomer, for example, di-2-ethylhexylphosphine oxide (methyl) acrylamide, ethylenebis (methyl) acryloyl can be enumerated
Amine, N, polyfunctional group (methyl) acrylic amide, Triallyl isocyanurate, season such as N- diallyls (methyl) acrylamide
Penta tetra-acrylate, tetraallyl epoxide ethane, N hydroxymethyl acrylamide, pi-allyl (methyl) acrylate, second two
The polyfunctional monomers such as alcohol two (methyl) ethyl acrylate, the allyl ester of pyromellitic acid four, diglycol monotertiary (methyl) acrylate, N,
N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide etc. by oxygen radical dehydrogenation free radical type crosslinking
Sex ethylene base monomer etc..Above-mentioned monomer be can be used alone a kind, or two or more is used in mixed way.Wherein, preferred di-2-ethylhexylphosphine oxide (first
Base) acrylamide, DMAA.It is poly- relative to (methyl) acrylamide based copolymer during using cross-linkable monomer
The molal quantity summation of synthesis point, its usage amount is typically about 5 moles of below %, preferably 1 mole below %.During more than 5 moles of %,
The copolymer gel of acquisition, it is not preferable.
As chain transfer monomer, for example, (methyl) allyl sulphonic acid can be enumerated, or above-mentioned sour sodium salt, sylvite etc.
Alkali metal salt and ammonium salt etc..The ratio of chain transfer monomer is not particularly limited, the molal quantity of the polymeric composition relative to polymer A
Summation, usually 0.05% ~ 5 mole of %, preferably 0.2 ~ 3 mole %.During less than 0.05 mole of %, it cannot get sufficient chain tra nsfer effect
Really.In addition, when more than 5 moles of %, reactivity reduction causes the reaction time to extend, it is not preferable.
As nonionic vinyl monomer, (methyl) alkyl-acrylates can be enumerated（Carbon number is 1 ~ 8 alkyl）、
The phenylethylenes such as acrylonitrile, styrene, α-methylstyrene, vinyltoluene, ethyl vinyl toluene and 1-chloro-4-methyl-benzene,
Vinyl acetate, methyl vinyl ether etc..Relative to the molal quantity summation of whole polymeric composition, nonionic vinyl monomer makes
It is usually 30 moles of below %, preferably 10 moles below % with ratio., may the damage present invention when use ratio is more than 30 moles of %
Effect, it is not preferable.
Conventionally known various method synthetic polymer A can be passed through.For example, into predetermined reaction vessel, adding above-mentioned
(methyl) acrylamide, cationic vinyl monomer and anionic vinyl monomer, add contain cross-linkable monomer, chain if necessary
Metastatic monomer, the polymeric composition of other nonionic vinyl monomers and water, add radical polymerization initiator, under agitation,
Progressively heating is reacted.Reaction temperature is normally controlled in 50 ~ 100 DEG C or so, and the reaction time is 1 ~ 5 hour or so.Monomer
Adding method can be according to conventionally known concurrently polymerization（concurrent polymerization）, it is continuous that polymerization etc. is added dropwise is each
The method of kind is carried out.As radical polymerization initiator, the persulfates such as potassium peroxydisulfate, ammonium persulfate, or these over cures can be used
The common radical polymerization initiators such as the oxidation-reduction type polymerization initiator that the reducing agent such as hydrochlorate and sodium hydrogensulfite is combined into.
In addition, in above-mentioned radical polymerization initiator, also can be combined and use azo-initiator.Relative to the gross weight of polymeric composition
Amount, the usage amount of radical polymerization initiator is 0.05 ~ 2.0 weight %, preferably 0.1 ~ 0.5 weight %.During less than 0.05 weight %,
It polymerize itself to carry out not exclusively；During more than 2.0 weight %, it is difficult to obtain the polymer of HMW.In addition, main free radical
After polymerisation, further, it is preferable to by polymerizeing after adding persulfate progress, while unreacted monomer is reduced, enter
Row cross-linking reaction is to increase molecular weight.If in addition, the polymer A finally obtained monomer composition and the scope of ionic equivalent ratio exist
In the scope of the present invention, it is ready for constituting different multiple monomer mixed solutions, them is carried out multistage polymerization progress
Synthesis.
The polymer A obtained according to the method described above can be water miscible (methyl) acrylamide aqueous copolymers solution or
Dispersion liquid.Polymer A weight average molecular weight is not particularly limited, and generally selects 1,000,000 ~ 8,000,000, preferably 1,500,
000~5,000,000（Weight average molecular weight utilizes gel permeation chromatography and light scattering detector according to the method described in embodiment
It is measured）.When weight average molecular weight is more than 1,000,000, the retention rate on paper can be improved, it is ensured that sufficient paper is strong
Effect is spent, when weight average molecular weight is below 8,000,000, paper messy texture, is obtained caused by can preventing compendency from excessively strengthening
Obtain more preferable paper strength effect.
Hygienic Paper additive in the present invention contains polymer A and aluminium compound B（Hereinafter referred to as compound B）.It is used as change
Compound B, can enumerate the polymerization of aluminum sulfate, aluminium chloride, basic aluminum sulfate, basic aluminium chloride, silicic acid aluminum sulfate and above-mentioned substance
Thing.Wherein, it can be used alone a kind, or two or more is applied in combination.Wherein, preferably sulfuric acid aluminium, polyaluminium chloride.
In the hygienic Paper additive of the present invention, polymer A and compound B content ratio are converted into solids by weight
Than, it is necessary to it is polymer A: compound B=95: 5 ~ 40: 60, preferred polymers A: compound B=95: 5 ~ 60: 40.Polymer A
Content ratio more than 95% when, compendency excessively enhancing causes toilet paper messy texture；When content ratio is less than 40%, enhancing
The composition of intensity is very few, and any of the above-described situation can not meet intensity enhancing effect.
If necessary, hygienic Paper additive of the invention contains the water-soluble inorganic electrolyte C in addition to water-soluble aluminium component B
（Hereinafter referred to as electrolyte C）And/or water-soluble organic bath D（Hereinafter referred to as electrolyte D）.Electrolyte C is by improving health
Ion concentration in the Paper additive aqueous solution, electrolyte D is respectively provided with reduction preservation and defended by the chelation with aluminium compound B
The effect of viscosity B coefficent during the raw Paper additive aqueous solution, it is thus possible to improve storage stability and operability.As electrolyte C,
Sodium sulphate, sodium chloride, ammonium sulfate, magnesium sulfate, calcium chloride, sodium phosphate etc. can be enumerated.As electrolyte D, citric acid, amber can be enumerated
Amber acid, malic acid, tartaric acid and above-mentioned sour alkali metal salt, above-mentioned acid（Citric acid, butanedioic acid, malic acid, tartaric acid）Alkali
Earth metal salt, above-mentioned acid（Citric acid, butanedioic acid, malic acid, tartaric acid）Ammonium salt etc..Wherein it is possible to which electrolyte C is used alone
Or any one in electrolyte D, or electrolyte C of more than two kinds or electrolyte D are applied in combination.Further, in electrolyte
It is each free one kind or two or more to be combined using in C and electrolyte D composition.
Polymer A and electrolyte C and/or electrolyte D use ratio is converted into solids by weight than preferably A:（C+
D）=90∶10~60∶40.
In addition, in above-mentioned formula, A is polymer A weight,（C+D）For electrolyte C and electrolyte D total weight, work as list
When solely using C, D, for the weight of composition is used alone.
The compound method of hygienic Paper additive of the present invention is not particularly limited, can after synthetic polymer A with compound B
（If necessary, electrolyte C and/or electrolyte D）Mixing, can also be in compound B（If necessary, electrolyte C and/or electrolyte D）
In the presence of, make the polymerization of polymer A monomer component.In addition it is also possible to advance prepared polymer A and compound B（If necessary,
Electrolyte C and/or electrolyte D is prepared in advance）Water diluent, the mixed preparing before pulp is added to.
The hygienic Paper additive of the present invention, which is added in pulp, to be used for manufacturing toilet paper.As the species of toilet paper,
Paper handkerchief, toilet paper, tissue, napkin paper, face tissue can be enumerated（Chi り Paper）Deng.Quantification of 10 ~ 50g/ of manufactured toilet paper
m2.As the species of paper pulp, the bleaching such as kraft pulp, sulfite pulp or non-bleached chemical paper pulps, ground wood pulp, mechanical pulp,
Thermomechanical pulp etc. is bleached or non-high yield paper pulp bleaching, senior waste paper, old newsprint, the waste and old magazine of the recovery such as milk package box
Waste paper paper pulp of paper, deinking waste paper etc. etc..
The toilet paper of the present invention can be suitably determined according to the species of the species, Papermaking Conditions and toilet paper of above-mentioned pulp
The addition of additive, generally, is scaled the solids by weight of hygienic Paper additive, relative to the solid constituent of pulp
Weight, the addition of hygienic Paper additive of the invention is 0.01 ~ 1.0 weight % or so.When addition is less than 0.01 weight %,
The effect for strengthening paper strength is insufficient；When more than 1.0 weight %, cost is uneconomical, and it is not preferable.In addition, the system of toilet paper
The manufacture made from other paper is different, in the pulp used, hardly uses the pulp containing water soluble aluminum compound.
Although the hygienic Paper additive of the present invention preferably uses the pulp for not containing water soluble aluminum compound, work as in pulp
It can also be used during containing a small amount of water soluble aluminum compound.Specifically, preferably using the water soluble aluminum compound in pulp
Content be less than 0.5% pulp.
When manufacturing toilet paper using the hygienic Paper additive of the present invention, it can be generally applied in combination with other additives.Make
For other additives, it can enumerate：L Water Paper power reinforcing agent, drainage agent, retention agent, dispersant etc..In toilet paper, paper handkerchief is manufactured
When, typically used with l Water Paper power reagents recombination.Species for l Water Paper power reinforcing agent is not particularly limited, typically using polyamides
The epoxychloropropane modified thing of many polyimide resins of amine（PAE resin）.
Embodiment
Hereinafter, the present invention is further illustrated by enumerating embodiment and comparative example, but the present invention is not by this
The restriction of a little examples.In addition, in each case, being such as not particularly limited, " part " and " % " is on the basis of weight.
Items are determined and carried out in accordance with the following methods.
（1）Solids by weight
After being dried 3 hours in drying machine, at 105 DEG C, the solid constituent weight of polymer A and various pulps is determined
Amount.
（2）Viscosity
Using Brookfield viscometer, in 25 DEG C of measure.
（3）Weight average molecular weight
Determined under following condition determination：
GPC main frames：East ソ mono- (strain) are manufactured
Chromatographic column：The guard column PWXL1 roots and GMPWXL2 roots of East ソ mono- (strain) manufactures（40 DEG C of temperature）
Eluent：N/2 acetate buffer solutions（N/2 acetic acid（With light Pure medicines industrial (strain) manufacture）+ N/2 sodium acetates（キ シ ダization
Learn (strain) manufacture）The aqueous solution, pH about 4.2）
Flow velocity：0.8ml/ minutes
Detector：
RALLS methods：The TDA MODEL301 manufactured using PVC ス コテツク societies.Adjust concentration detector, 90 ° of light scattering
The temperature of detector and viscosity detector calculates weight average molecular weight to 40 DEG C according to the measured value that each detector is obtained.
Synthesis example 1
In the reaction unit with agitator, thermometer, reflux condensing tube, nitrogen ingress pipe and 2 dropping funels, plus
Enter 376 parts of ion exchange waters, be passed through after the oxygen that nitrogen is removed in reaction system, be heated to 90 DEG C.In a dropping funel
Add 208 parts of acrylamide, 9.1 parts of 80% acrylic acid, 1.6 parts of methallylsulfonic acid sodium, 0.3 part of DMAA, Asia
0.5 part of bisacrylamide, 26.5 parts of dimethylaminoethyl methacrylate, 60% dimethylaminoethyl methacrylate
534 parts of 79.8 parts of benzyl chloride quaternary ammonium salt aqueous solution and ion exchange water, with 62.5% sulphur acid for adjusting pH to 3.In addition, to another
180 parts of 0.45 part of ammonium persulfate and ion exchange water are added in dropping funel.Next, by two dropping funels into system
Monomer and catalyst is added dropwise, about 3 hours are lasted.Drop finishes, and adds 10 parts of 0.3 part of ammonium persulfate and ion exchange water, and insulation 1 is small
When, 530 parts of ion exchange water is added, solid constituent 15.2%, Brookfield viscometer is obtained and determines viscosity（25℃）For 8,000mPas
The EVA aqueous solution.The monomer composition used during synthetic polymer A（Mole %）With the polymer A of the acquisition character such as institute of table 1
Show.
Synthesis example 2~8, compare synthesis example 1 ~ 3
It is poly- using being synthesized with the identical method of synthesis example 1 in addition to the monomer composition in synthesis example 1 is changed to shown in table 1
Compound A.The polymer A of acquisition character is as shown in table 1.
Table 1
The title of abbreviation in table 1 is as follows：
AM：Acrylamide
DM：Dimethylaminoethyl methacrylate
DML：The benzyl chloride quaternary ammonium salt of dimethylaminoethyl methacrylate
DMC：The chloromethanes quaternary ammonium salt of dimethylaminoethyl methacrylate
BQ：The benzyl chloride quaternary ammonium salt of dimethylaminoethyl acrylate
IA：Itaconic acid（Binary acid）
AA：Acrylic acid
DMAA：DMAA
SMAS：Methallylsulfonic acid sodium
MBAA：Methylene-bisacrylamide
Ionic equivalent compares a2/a3：Polymer A cation equivalent/anion equivalents
Embodiment 1
Using the polymer A obtained in synthesis example 1 and as water soluble aluminum compound B 50% aluminum sulfate aqueous solution according to solid
Body weight ratio of constituents be 90/10, further, polymer A and as water-soluble electrolytes sodium sulphate according to solid constituent weight
Amount obtains the hygienic Paper additive aqueous solution that solids by weight is 18.6% than being mixed for 80/20.
According to the ratio shown in table 2, embodiment 2 ~ 10 and comparative example 1 ~ 9 are prepared using method similarly to Example 1.This
Outside, the solids by weight in 50% aluminum sulfate aqueous solution in table 2 is represented with anhydrous slufuric acid aluminium weight.
Table 2
The title of abbreviation in table 2 is as follows.
Alum：Aluminum sulfate
PAC：Polyaluminium chloride
Performance evaluation I
The L-BKP of sheet is dissociated, by Ni Yajiala（Niagara）Formula beater is beaten, and regulation Canadian standard is dissociated
Degree（According to C.S.F:JIS P-8121）For 520ml, with running water dilute paper pulp to concentration conversion into drying solid composition be 2%.
Relative to pulp, the weight ratio meter converted by solid constituent, the health of each embodiment and the comparative example acquisition of addition 0.4%
Paper additive.Each pulp pH value is about 7.According to TAPPI test method T-205, paper of manufacturing paper with pulp by hand is made with the slurry.Press
According to quantification of 30g/m2Carry out copy paper.
Dried 4 minutes at 105 DEG C using spin-drier.Obtained craft manufactures paper with pulp paper in 23 DEG C, 50%RH condition
Lower control humidity 24 hours, during which determines tensile strength（According to JISP-8113）.As a result it is as shown in table 3.In addition, the He of embodiment 8
In embodiment 10, the epoxychloropropane modified thing using hygienic Paper additive and polyamide polyamines resin is respectively combined（Waste river
Learn the ア ラ Off イ Star Network ス 255 of industrial (strain) system, hereinafter referred to as PAE resin）, in terms of pulp solid constituent, with respectively defending
Raw Paper additive adds 0.15% PAE resin simultaneously.
The performance evaluation I of table 3
| Performance evaluation example | The species of hygienic Paper additive | Specific tensile strength（Nm/g） | Remarks |
| Evaluate example 1 | Embodiment 1 | 38.1 | |
| Evaluate example 2 | Embodiment 2 | 39.2 | |
| Evaluate example 3 | Embodiment 3 | 39.5 | |
| Evaluate example 4 | Embodiment 4 | 40.6 | |
| Evaluate example 5 | Embodiment 5 | 39.5 | |
| Evaluate example 6 | Embodiment 6 | 40.1 | |
| Evaluate example 7 | Embodiment 7 | 37.2 | |
| Evaluate example 8 | Embodiment 8 | 38.5 | |
| Evaluate example 9 | Embodiment 8 | 40.1 | 0.15% PAE resin is applied in combination |
| Evaluate example 10 | Embodiment 9 | 38.3 | |
| Evaluate example 11 | Embodiment 10 | 38.9 | |
| Evaluate example 12 | Embodiment 10 | 40.1 | 0.15% PAE resin is applied in combination |
| Evaluate example 13 | Embodiment 11 | 37.0 | |
| Evaluate example 14 | Embodiment 12 | 41.1 | |
| Comparative evaluation example 1 | Comparative example 1 | 35.6 | |
| Comparative evaluation example 2 | Comparative example 2 | 35.2 | |
| Comparative evaluation example 3 | Comparative example 3 | 34.8 | |
| Comparative evaluation example 4 | Comparative example 4 | 34.9 | |
| Comparative evaluation example 5 | Comparative example 5 | 34.4 | |
| Comparative evaluation example 6 | Comparative example 6 | 34.2 | |
| Comparative evaluation example 7 | Comparative example 7 | 34.7 |
According to table 3, hygienic Paper additive of the invention is regardless of whether contain water soluble aluminum compound, itself and both sexes (methyl)
When the ratio of acrylamide polymer deviates particular range, the monomer composition with both sexes (methyl) acrylamide polymer is inclined
Compared during from particular range, hence it is evident that can assign paper higher dry paper intensity.
Performance evaluation II
The L-BKP of sheet is dissociated, by Ni Yajiala（Niagara）Formula beater is beaten, and regulation Canadian standard is dissociated
Degree（With C.S.F:On the basis of JIS P-8121）For 500ml, drying solid is converted into running water dilution paper pulp to pulp density
Composition is 2%.According to shown in table 4, aluminum sulfate is added into ready paper pulp（It is anhydrous）Afterwards, relative to pulp, by solid
The weight ratio meter of composition conversion, the hygienic Paper additive of each embodiment and the comparative example acquisition of addition 0.4%.Each pulp
PH value is about 6.5.According to JIS P-8121, the drainage amount of the paper pulp is determined.Further, according to TAPPI test methods T-
205, make paper of manufacturing paper with pulp by hand with the paper pulp.According to quantification of 30g/m2Copy paper is carried out, using spin-drier at 105 DEG C
Dry 4 minutes.Obtained craft paper of manufacturing paper with pulp controls humidity 24 hours under conditions of 23 DEG C, 50%RH, during which determines tensile strength
（According to JIS P-8113）With the quality of paper.As a result it is as shown in table 4.
The quality for paper of manufacturing paper with pulp by hand is evaluated as follows.
Change the light luminance through paper of manufacturing paper with pulp by hand, be placed into OBS image processing systems Hyper700（Limited commercial firm
OBS is manufactured）, the deviation of Luminance Distribution is determined, the coefficient of variation is scaled.The coefficient of variation is smaller, and paper quality is better.
From table 4, it can be seen that in the pulp of the hygienic Paper additive of the addition present invention, the amount of aluminum sulfate 0 ~
It is optimal in the range of 0.4 weight % or so.
Performance evaluation III
The hygienic Paper additive aqueous solution prepared in embodiment is preserved at 40 DEG C, determines the feelings that its viscosity is changed over time
Condition, as a result as shown in table 5.As shown in table 5, its viscosity stability can be improved containing electrolyte C in hygienic Paper additive.
The performance evaluation II of table 4
The viscosity stability in the daytime for the hygienic Paper additive that the performance evaluation III of table 5 is prepared
Claims (14)
1. a kind of hygienic Paper additive, containing both sexes (methyl) acrylamide polymer A and water soluble aluminum compound B, the two
Content ratio be converted into solids by weight ratio for A: B=95: 5~40: 60, wherein, both sexes (methyl) acrylamide gathers
Compound A is containing 62~98.95 moles of % of (methyl) acrylamide a1,0.55~20 mole of % of cationic vinyl monomer a2
What the monomer component copolymerization with 0.5~18 mole of % of anionic vinyl monomer a3 was obtained, cationic vinyl monomer a2 and the moon
Ionic vinyl monomers a3 ionic equivalent ratio is 1.1~40, and
Further containing the water-soluble inorganic electrolyte C in addition to above-mentioned water soluble aluminum compound B and/or water-soluble organic bath
D。
2. health Paper additive as claimed in claim 1, wherein, above-mentioned both sexes (methyl) acrylamide polymer A contains
Cross-linked structure.
3. health Paper additive as claimed in claim 2, wherein, above-mentioned both sexes (methyl) acrylamide polymer A list
Body composition contains (methyl) ALS and DMAA.
4. health Paper additive as claimed in claim 2 or claim 3, wherein, above-mentioned both sexes (methyl) acrylamide polymer A's
Weight average molecular weight is 1,000,000~8,000,000.
5. health Paper additive as claimed in claim 1 or 2, wherein, above-mentioned water soluble aluminum compound B is selected from aluminum sulfate, chlorine
Change more than a kind in the group that aluminium, basic aluminum sulfate, basic aluminium chloride, the polymer of silicic acid aluminum sulfate and above-mentioned substance are constituted.
6. health Paper additive as claimed in claim 1 or 2, wherein, the above-mentioned water-soluble nothing in addition to water soluble aluminum compound B
More than a kind in the group that machine electrolyte C is constituted selected from sodium sulphate, sodium chloride, ammonium sulfate, magnesium sulfate, calcium chloride and sodium phosphate.
7. health Paper additive as claimed in claim 1 or 2, wherein, above-mentioned water-soluble organic bath D be selected from citric acid,
More than a kind in the group that butanedioic acid, malic acid, tartaric acid and above-mentioned sour alkali metal salt, alkali salt and ammonium salt are constituted.
8. health Paper additive as claimed in claim 1 or 2, wherein, above-mentioned both sexes (methyl) acrylamide polymer A with
The content ratio of water-soluble inorganic electrolyte C and/or water-soluble organic bath D in addition to water-soluble aluminium component B are converted into solid
Body weight ratio of constituents is A: (C+D)=90: 10~60: 40.
9. a kind of toilet paper manufacture method, it is characterised in that the hygienic Paper additive described in claim 1 or 2 is added to paper
Copy paper is carried out in slurry slurry.
10. toilet paper manufacture method as claimed in claim 9, it is characterised in that using the solid relative to pulp into
The content for the water soluble aluminum compound divided in weight, pulp is less than 0.5% pulp.
11. toilet paper manufacture method as claimed in claim 9, it is characterised in that relative to the solid constituent weight of pulp
Amount, the hygienic Paper additive described in addition addition claim 1 or 2 with 0.01~1.0 weight % scopes.
12. toilet paper made from a kind of toilet paper manufacture method by described in claim 9.
13. toilet paper as claimed in claim 12, wherein, quantification of 10~50g/m of toilet paper2。
14. the toilet paper as described in claim 12 or 13, wherein, above-mentioned toilet paper is times in paper handkerchief, toilet paper and tissue
Meaning is a kind of.
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| JP6795790B2 (en) * | 2016-06-23 | 2020-12-02 | 荒川化学工業株式会社 | Manufacturing method of paper |
| CN110055818B (en) * | 2019-04-16 | 2020-01-10 | 济宁南天农科化工有限公司 | Papermaking reinforcing agent and preparation method and application thereof |
| CN113445355B (en) * | 2020-03-27 | 2024-03-26 | 中顺洁柔纸业股份有限公司 | Composition, method for producing same, toilet paper with same, and processing method using same |
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