CN106012660B - Paperboard manufacture method - Google Patents
Paperboard manufacture method Download PDFInfo
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- CN106012660B CN106012660B CN201610357232.1A CN201610357232A CN106012660B CN 106012660 B CN106012660 B CN 106012660B CN 201610357232 A CN201610357232 A CN 201610357232A CN 106012660 B CN106012660 B CN 106012660B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Abstract
The present invention is a kind of paperboard manufacture method, it is characterised in that add the paper additive processed containing polymer in pulp, uses the pulp that copy paper pH in pulp after addition is 6.5~8.5；(methyl) allyl sulphonic acid and/or its salt (D) and monomer (B) or the synthesis of acetaldehyde acids of repeat unit shown in formula (B) can be formed by polymerizeing that the monomer total amount that it with the monomer total amount that the monomer (A) of formula (A) repeat unit can be formed by polymerization, is existed in relative polymerization system be 1~20 mole of % cationic vinyl monomer (C) that the polymer, which is, existed in relative polymerization system is 0.01~5 mole of %, and there is formula (B) repeat unit.The present invention improves effect with excellent paper power and stays raising effect.R in formula1Represent H or CH3 R in formula2Represent H or CH3, R3Represent H, Na, K or NH4。
Description
The present invention be Application No. 201280017556.0, the applying date be May 29, entitled " paperboard in 2012
The divisional application of the patent application of manufacture method ".
Technical field
The present invention relates to paperboard manufacture method, used more particularly, to (methyl) acrylamide based copolymer paper i.e. processed has been used
Additive, and stay and intensity excellent paperboard manufacture method.
Background technology
In paperboard manufacture, due to being difficult to obtain high-quality paperboard, so being usually to be manufactured under acidity.But it is near
Year, because the ingredients calcium carbonate in the old paper as paperboard raw material has increase to be inclined to, the pH of copy paper system is difficult to reduce, so because of sulphur
Sulfate ion increase and the increase of calcium carbonate content that sour aluminium or sulfuric acid usage amount increase or closure are caused, cause sulfuric acid
The reactant of aluminium and calcium carbonate is that calcium sulfate (gypsum) increases in copy paper system, and it separates out in copy paper process and produces fouling
(scale troubles)。
To solve these problems, it is thus proposed that using pH6.5~8.5,50~400ppm of basicity, electrical conductivity 50~
250mS/m pulp, and add jelly and paper power agent is added to pulp and carries out the paperboard manufacturer of copy paper interior
Method (for example reference can be made to patent document 1).Somebody proposes such paperboard manufacture method：In the carbon containing more than 5 weight %
The pulp of sour calcium adds paper processed, and with medicine, under conditions of pH5~8, wet type is copied in the paperboard manufacture method of system, above-mentioned system
Paper medicine using cationic coagulating agent, paper power reinforcing agent, aluminum sulfate, cementing agent, cationic and is stayed agent and anionic property
And stay agent, and above-mentioned aluminum sulfate addition is 0.5~4 weight % with respect to adiabatic drying pulp weight, also in paper medicine processed
Addition step on, addition aluminum sulfate and cementing agent be (for example using the addition aluminum sulfate before above-mentioned cementing agent is added or simultaneously
Reference can be made to patent document 2).
However, according to method set forth above, although the problem of can solve the problem that generation fouling, but it is due to copy paper pH
Property, hardly cause that paper power reinforcing agent and stays deteriorations with aluminum sulfate, it is impossible to the paper power enhancing for giving full play to paper power reinforcing agent is imitated
Really.
On the other hand, can also occur to produce in raw material condition deterioration, paper machine high speed, paper process processed in general papermaking
Plain boiled water in be mingled with object amount increase or copy paper pH change etc. about paper quality problems.To solve these problems, someone
Propose the excellent paper additive processed containing the Polyacrylamide resin for possessing particular configuration of various paper power enhancing effects
(for example reference can be made to patent document 3).But but can't see such record and enlightenment：When the method for the proposition is applied to copy paper pH
For 6.5~8.5 but hardly use aluminum sulfate this non-general paperboard manufacture method when, paper power reinforcing agent stay improve, paper
Power enhancing effect becomes excellent.In general, the occasion paper power reinforcing agent of aluminum sulfate is hardly used under copy paper pH6.5~8.5
And stay variation, the paper power enhancing effect of paper power reinforcing agent to give full play to.
Prior art document
Patent document
Patent document 1:Japanese Patent Laid-Open 2007-186822 publications
Patent document 2:Japanese Patent Laid-Open 2007-154349 publications
Patent document 3:Japanese Patent Laid-Open 2000-008293 publications
The content of the invention
Technical problem
The object of the invention is that offer one kind can solve to occur scale problems and descend to stay in copy paper pH6.5~8.5
With the paperboard manufacture method of excellent strength.
Solution
Inventor has found to utilize and specific paper processed is made an addition into pulp with additive, copied through constantly studying with keen determination, finally
Paper pH is 6.5~8.5 paperboard manufacture method, and can not only solve generation scale problems can also accomplish to stay raising effect and paper
Power improves excellent effect, completes the present invention.
That is, the object of the invention is realized as follows：
A kind of paperboard manufacture methods of the ＞ of ＜ 1, it is characterised in that there is structure shown in formula (B) in pulp addition
(methyl) acrylamide based copolymer is paper additive processed, uses the paper that copy paper pH in pulp after addition is 6.5~8.5
Starch slurry；(methyl) the acrylamide based copolymer is by least to that can form the monomer of structure shown in formula (A)
(A), the monomer total amount existed in relative polymerization system is 1~20 mole of % cationic vinyl monomer (C), relative polymerization system
The monomer total amount of interior presence is polymerize for 0.01~5 mole of % (methyl) allyl sulphonic acid and/or its salt (D) to be obtained.
R in formula1Represent H or CH3
R in formula2Represent H or CH3, R3Represent H, Na, K or NH4
A kind of paperboard manufacture methods of the ＞ of ＜ 2, it is characterised in that add paper processed described in above-mentioned ＞ of ＜ 1 with adding in pulp
Plus agent；On the pulp after addition by following conditions obtain stay increase rate (Re) be more than 3%, the paper pulp after addition
The copy paper pH of slurry is 6.5~8.5；Use the pulp；
The condition is：
(i) the pulp temperature that Canadian Standard Freeness is adjusted to 300ml 1 mass % is adjusted to 25 DEG C；
(ii) the dynamic capacity of returns tester (dynamic drainage tester) for possessing 40 mesh metallic screens is taken,
It is stirred with 600rpm；
(iii) the paper additive processed that relative paper pulp solid content is 0.5 mass % is added；
(iv) paper additive processed is added after 1 minute to start after draining, draining 50g, then draining 150g, then in filtrate
Solids level concentration (b) is measured；
(v) using solids level concentration in the filtrate determined in solids level concentration (a) in the pulp before draining and (iv),
Calculated by following formula and stay rate；
And stay rate (R)=(a-b)/a × 100 (%)
(vi) using with the addition of paper additive processed when stay rate (Rs) and do not have addition paper additive processed when stay
Rate (R0), calculated by following formula and stay increase rate (Re).
And stay increase rate (Re)=(Rs-R0)/R0× 100 (%)
Paperboard manufacture methods of the ＞ of ＜ 3 according to the above-mentioned ＞ of ＜ 1 or the ＞ of ＜ 2, it is characterised in that above-mentioned paper addition processed
Agent be with structure (methyl) acrylamide based copolymer shown in formula (B), and it be by monomer carry out copolymerization and obtain
Arrive；It is 1 that the monomer, which contains the monomer (A) that can form structure shown in formula (A), the monomer total amount existed in relative polymerization system,
The monomer total amount existed in~20 moles of % cationic vinyl monomer (C), relative polymerization system is 0.01~5 mole of %'s
(methyl) allyl sulphonic acid and/or its salt (D) and containing the monomer (B) of structure shown in formula (B) can be formed.
Paperboard manufacture methods of the ＞ of ＜ 4 according to any one of the above-mentioned ＞ of the ＞ of ＜ 1 to ＜ 3, it is characterised in that monomer
(A) it is (methyl) acrylamide, monomer (B) is 2-(methyl) acryloyl amine-n-glycolics (2- (meth) acryl
Amide-N-glycolic acid) class.
Paperboard manufacture methods of the ＞ of ＜ 5 according to any one of the above-mentioned ＞ of the ＞ of ＜ 1 to ＜ 4, it is characterised in that above-mentioned system
Paper is by making acetaldehyde acids and structural response shown in formula (A) and constituting with structure shown in formula (B) with additive
(methyl) acrylamide based copolymer.
Paperboard manufacture methods of the ＞ of ＜ 6 according to any one of the above-mentioned ＞ of the ＞ of ＜ 1 to ＜ 5, it is characterised in that paper processed is used
Additive be the monomer total amount that also further exists in relative polymerization system for used in the range of 0.5~10 mole of % it is cloudy from
(methyl) acrylamide based copolymer obtained from sub- sex ethylene base monomer (E).
Paperboard manufacture methods of the ＞ of ＜ 7 according to the above-mentioned ＞ of ＜ 6, wherein, above-mentioned anionic property vinyl monomer (E) is
Unsaturated monocarboxylic acid or unsaturated dicarboxylic acid.
Paperboard manufacture methods of the ＞ of ＜ 8 according to any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 7, it is characterised in that paper processed
It is that the monomer total amount that also further exists in relative polymerization system is to use in the range of 0.001~2 mole of % with additive
(methyl) acrylamide based copolymer obtained from bridging property vinyl monomer (F).
Paperboard manufacture methods of the ＞ of ＜ 9 according to any one of the above-mentioned ＞ of 1 ＞ of ＜~＜ 8, it is characterised in that paper pulp
Slurry contains aluminium compound；With respect to pulp solid content, the ratio of occupying of aluminium compound is scaled 0.1 mass % by aluminum oxide
Below.
The effect of the present invention
During existing method manufacture paperboard, copy paper pH is 6.5~8.5, hardly with aluminum sulfate, paper power reinforcing agent stay change
Difference, the paper power enhancing effect of paper power reinforcing agent can not give full play to.And asked in accordance with the invention it is possible to provide and can solve generation fouling
Inscribe and paper power reinforcing agent stay take a turn for the better, the paperboard manufacture method that paper power enhancing effect is excellent.
Brief description of the drawings
Fig. 1 is dynamic drainage instrument sketch plan.
Specific embodiment
The present invention is a kind of paperboard manufacture method, it is characterised in that have structure shown in formula (B) in pulp addition
(methyl) acrylamide based copolymer be paper additive processed, the use of copy paper pH in pulp after addition is 6.5~8.5
Pulp；(methyl) the acrylamide based copolymer is by least to that can form the monomer of structure shown in formula (A)
(A), the monomer total amount existed in relative polymerization system is 1~20 mole of % cationic vinyl monomer (C), relative polymerization system
The monomer total amount of interior presence is polymerize for 0.01~5 mole of % (methyl) allyl sulphonic acid and/or its salt (D) to be obtained.
R in formula1Represent H or CH3
R in formula2Represent H or CH3, R3Represent H, Na, K or NH4
Currently preferred mode is：A kind of paperboard manufacture method, it is characterised in that add above-mentioned ＜ 1 in pulp
Paper additive processed described in ＞；On the pulp after addition by following conditions obtain stay increase rate (Re) for 3% with
On, the copy paper pH of the pulp after addition is 6.5~8.5；Use the pulp；
The condition is：
(i) the pulp temperature that Canadian Standard Freeness is adjusted to 300ml 1 mass % is adjusted to 25 DEG C；
(ii) the dynamic capacity of returns tester for possessing 40 mesh metallic screens is taken, is stirred with 600rpm；
(iii) the paper additive processed that relative paper pulp solid content is 0.5 mass % is added；
(iv) paper additive processed is added after 1 minute to start after draining, draining 50g, then draining 150g, then in filtrate
Solids level concentration (b) is measured；
(v) using solids level concentration in the filtrate determined in solids level concentration (a) in the pulp before draining and (iv),
Calculated by following formula and stay rate；
And stay rate (R)=(a-b)/a × 100 (%)
(vi) using with the addition of paper additive processed when stay rate (Rs) and do not have addition paper additive processed when stay
Rate (R0), calculated by following formula and stay increase rate (Re).
And stay increase rate (Re)=(Rs-R0)/R0× 100 (%)
In paperboard manufacture method of the present invention, paperboard can enumerate lining body paper, core raw paper, paper tube base paper, plasterboard body paper,
Coated white, uncoated blank, chipboard etc..
Pulp used in the present invention can be by obtained from the slurrying such as paper pulp raw material industrial water.It is used as paper pulp
Raw material can use kraft pulp or sulfite pulp etc. to bleach or non-bleached chemical paper pulps, ground wood pulp, mechanical pulp or pre-
Thermomechanical pulp etc. is bleached or non-high yield paper pulp bleaching, upper white old paper, old newspaper, outdated magazine, old corrugated paper or the old paper of deinking etc.
Any one of old paper paper pulp.Preferably use more than 50% old paper paper pulp.In addition, can also be used as above-mentioned paper pulp raw material
State the mixture of paper pulp raw material and polyamide, polyester, polyene etc..Further, the primary raw material for pulp has filler, as
Filler can enumerate calcium carbonate, carclazyte, talcum powder, chalk, titanium oxide, white carbon etc..
(methyl) that is added in the present invention as paper additive processed toward pulp though the amount of acrylamide based copolymer
It is not particularly limited, but preferably adds 0.05~2.0 mass % with respect to pulp solid content.(methyl) acrylamide based copolymer
As long as addition can just realize the object of the invention well within the above range, can well realize and stay raising effect and paper
Power improves effect, but also it is dirty not result in the equipment such as paper machine.
In the present invention, preferably toward pulp with respect to pulp solid content by aluminum oxide conversion 0.1 mass % of addition with
Lower aluminium compound.Aluminum sulfate, polyaluminium chloride, sodium aluminate etc. can be enumerated as aluminium compound.
In addition, in the range of bad influence is not caused to effect of the present invention, cementing agent can also be added to pulp, wet
Profit paper power agent, pitch control additive, coagulating agent, drainage agent, and stay adding required for the papermaking such as agent, dyestuff, agent of sizing mixing, pH regulators
Plus agent.
In the present invention, paper processed is not particularly limited with the addition place of additive, can for example enumerate slurry pond (mixing
Chest), machine chest (machine chest), header box, fan pump, mesh screen, back flow water pump etc..It is preferred that slurry pond, machine chest.
In the present invention, copy paper pH refers to that the pH of the pulp before paper machine dehydration, copy paper pH are 6.5~8.5.In addition,
Pulp pH before paper machine dehydration, for general actual machine, equivalent to the pH of entrance.
Paper processed of the invention used with additive be with structure (methyl) acrylamide based copolymer shown in formula (B),
It is by least to that can form monomer (A), the relative polymerization of structure shown in formula (A) to be somebody's turn to do (methyl) acrylamide based copolymer
The monomer total amount existed in system is 1~20 mole of % cationic vinyl monomer (C), in relative polymerization system presence monomer
Total amount is polymerize for 0.01~5 mole of % (methyl) allyl sulphonic acid and/or its salt (D) to be obtained.
R in formula1Represent H or CH3
R in formula2Represent H or CH3, R3Represent H, Na, K or NH4
(methyl) propylene can be enumerated as the monomer (A) used in the present invention that can form structure shown in formula (A)
Acid amides.This description of (methyl) acrylamide represents to include two kinds of acrylamide and Methacrylamide.In the present invention, (methyl)
Both acrylamide and Methacrylamide or one can be used to make monomer (A) to synthesize for acrylamide based copolymer.
In the present invention, as the monomer (B) of structure shown in formula (B) can be formed, can enumerate 2 shown in formula (B1)-
(methyl) acryloyl amine-n-ethanol acids, can for example enumerate 2-acryloyl amine-n-glycolic, 2-methacryl
The salt of amine-N-glycolic or these sodium, potassium, ammonium etc..
R in formula2Represent H or CH3, R3Represent H, Na, K or NH4
(methyl) acrylamide polymer that there is structure shown in formula (B) as being synthesized without above-mentioned monomer (B)
Method can enumerate it is as follows：
(1) acetaldehyde acids is made and by polymerized monomer (A), cationic vinyl monomer (C) and (methyl) pi-allyl
The method of structural response shown in formula (A) formed by sulfonic acid and/or its salt (D)；
(2) monomer (A), cationic vinyl monomer (C), (methyl) allyl sulphonic acid and/or its salt (D) and second are made
The method of aldehydic acid class reaction.
In addition, following (methyl) the acrylamide based copolymer formula of (B) that will be used sometimes as paper processed with additive
Shown structure makees referred to as (B) composition of the material after Dan Ti Change are calculated.As acetaldehyde acids, glyoxalic acid and its sodium, potassium, ammonium etc. can be enumerated
Salt.
As the cationic vinyl monomer (C) that can be used in the present invention, it can for example include:(methyl) acrylic acid two
Methylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylate propyl ester, (methyl) propylene
Sour diethylamino propyl ester, dimethylaminopropyl (methyl) acrylamide or diethyl amino propyl (methyl) acrylamide,
Cyclopolymers of alkyldiallylamine, dialkyl group allyl amine, diallylamine, allyl amine etc. have tertiary amino, secondary amino group, primary amino radical
Vinyl monomer；Or the inorganic acid or even organic acid salt of these hydrochloric acid, sulfuric acid, formic acid, acetic acid etc.；Or by containing
Araalkyl, the diformazans such as halogenated alkane, benzyl chloride, the cylites such as the vinyl monomer and chloromethane, bromomethane of tertiary amino
Base sulfuric acid, diethyl sulfuric acid, epichlorohydrin, 3- chlorine-2-hydroxyls hydroxypropyltrimonium chloride, glycidyltrialkylammonium ammonium chloride etc.
Quaternizing agent reacts the obtained vinyl monomer containing quaternary ammonium salt, for example 2- hydroxy-ns, N, N, N ', N '-pentamethyl-N '-[3-
{ (1- oxygen -2- acrylic) amino } propyl group]-the ammonium of 1,3- propane dichloride two etc.；(methyl) allyl halide and dimethylamino alkane
Reactant of base alcohol etc..These can be used alone one or more and are used in combination.
As (methyl) allyl sulphonic acid (salt) (D) that can be used in the present invention, allyl sulphonic acid, methyl can be enumerated
Alkali metal salts or ammonium salts such as sodium salt, the sylvite of allyl sulphonic acid and allyl sulphonic acid and methallylsulfonic acid etc..
As unsaturated monocarboxylic acid, no can be used in the anionic property vinyl monomer (E) that use of the present invention
Saturated dicarboxylic acid, unsaturated tricarboxylic acid, unsaturated quaternary carboxylic acid, unsaturated sulfonic acid, unsaturated phosphonic acids and these salt,
It can be used alone one kind among these or and with two or more.
As the unsaturated monocarboxylic acid and its esters among these can enumerate acrylic acid, methacrylic acid and these
The alkali metal class or ammonium salt etc. such as sodium, sylvite.
As the example of unsaturated dicarboxylic acid and its esters can enumerate maleic acid, fumaric acid, itaconic acid, citraconic acid and
The alkaline metal salts such as these sodium, sylvite or ammonium salt etc..Propylene can be enumerated as the example of unsaturated tricarboxylic acid and its esters
Tricarboxylic acids, 3- butene-1s, 2,3- tricarboxylic acids, 4- amylenes -1,2, the alkaline metal salt such as 4- tricarboxylic acids and these sodium, sylvite or
Ammonium salt etc..
1- amylene -1 can be enumerated as the example of unsaturated quaternary carboxylic acid and its esters, Isosorbide-5-Nitrae, 4- tetrabasic carboxylic acids, 4- amylene -1,
2,3,4- tetrabasic carboxylic acids and 3- hexenes -1,1, the alkaline metal salt such as 6,6- tetrabasic carboxylic acids and these sodium, sylvite or ammonium salt etc..
Vinyl sulfonic acid, styrene sulfonic acid, 2- acrylamide-2-methyl propane sulfonics can be enumerated as the example of unsaturated sulfonic acid
And the alkali metal salts or ammonium salt such as these sodium, sylvite etc..
The example of unsaturated phosphonic acids can enumerate vinyl phosphonate, α-alkali such as phenyl vinyl phosphonic acids and these sodium, sylvite
Metallic salt or ammonium salt etc..
In above-mentioned anionic property vinyl monomer, effect is improved from paper quality He Longitude Economic viewpoints, particularly preferably unsaturated
Monocarboxylic acid, unsaturated dicarboxylic acid, specially acrylic acid, itaconic acid and its esters.
Ethylene glycol two (methyl) propylene can be included as the bridging property vinyl monomer (F) that can be used in the present invention
Double (methyl) acrylic amide, the adipic acids two such as acid esters etc. two (methyl) esters of acrylic acid, di-2-ethylhexylphosphine oxide (methyl) acrylamide
The divinyl such as vinyl acetate esters, urethane acrylate (urethane acrylate) class, (methyl) allyl acrylate,
Diallyl phthalate ester, (methyl) glycidyl acrylate, N substitutions (methyl) acrylamide, 1,3,5- triacryls six
Hydrogen-S- triazines (1,3,5-triacryloylhexahydro-S-triazine), triallyl isocyanurate, N, N- diene
2~4 functions such as propylacrylamide, tetramethylol methane tetraacrylate (tetramethylolmethan tetraacrylate)
Multi-functional vinyl monomer as sex ethylene base monomer.
Polymerization initiator used in the present invention, is not particularly limited, and can be used known.It can for example include:Over cure
The persulfates such as sour sodium, potassium peroxydisulfate and ammonium persulfate；Hydrogen peroxide, benzoyl peroxide, TBHP and two uncles
The peroxide such as butylperoxide；The bromate such as sodium bromate and potassium bromate；Sodium perborate, potassium perborate and ammonium pertorate were waited
Borate；The percarbonate such as SODIUM PERCARBONATE, potassium percarbonate and percarbonic acid ammonium；Peroxophosphoric acid sodium, potassium superphosphate and ammonium superphosphate were waited
Phosphate.Both can be used alone a kind and also can and with two or more., also can be with going back though these polymerization initiators can be used alone
Former agent combination is used as redox system polymerization initiator.In addition, for example azo can also be used as polymerization initiator
Bis-isobutyronitrile, 2, -2- amidine propanes the hydrochloride of 2 '-azo two, 2,2 '-azo two -2,4- methyl pentane nitriles, 4,4 '-azo two -
The azo-compound such as 4- cyanopentanoic acids and its salt, these both can be used alone a kind and also can and with two or more.
And can be included as reducing agent：Sulphite, bisulfites or N, N, N ', N '-tetramethylethylenediamine etc. has
Machine amine, 2, the reduced sugar such as azo-compound, the aldose such as -2- amidine propane hydrochlorides of 2 '-azo two etc..These reducing agents both can be single
Solely using a kind also can and with two or more.
Furthermore it is also possible to use alkyl hydrosulfide (alkyl mercaptan) class, thioglycolic acid and its ester as needed
Chain-transferring agent known to class, isopropanol, allyl alcohol etc..
On being tied in the present invention as formula (A) contained by (methyl) acrylamide based copolymer of paper additive processed Suo Shi
The content ratio of structure, although be not particularly limited, it is preferred that structure shown in mutual-through type (A) is when Dan Ti Change are calculated as 70 moles of %
~99 moles of %.Although the content ratio of structure shown in above-mentioned formula (A), which departs from above range, can also realize the object of the invention,
It is that can especially play paper power if within the above range to improve effect.
On being tied in the present invention as formula (B) contained by (methyl) acrylamide based copolymer of paper additive processed Suo Shi
The content ratio of structure, although be not particularly limited, it is preferred that it is 0.5~30 that structure shown in mutual-through type (B), which is when Dan Ti Change are calculated,
Mole %.Although the content ratio of said structure, which departs from above range, can also realize the object of the invention, if in above range
It inside then can especially play and stay raising effect and paper power to improve effect.And if more than 30 moles %, can not see and cost
The attachment to paper pulp being adapted is improved to improve effect, and stay raising effect, paper power to improve effect.
In order to obtain (methyl) acrylamide based copolymer in the present invention as paper additive processed, cationic ethene
The usage amount of base monomer (C) monomer is usually 1~20 mole of %, preferably 2~15 moles %.Although cationic vinyl monomer
(C) usage amount, which departs from above range, can also realize the object of the invention, but can especially be given full play to if within the above range
Paper power improves effect.
In order to obtain (methyl) acrylamide based copolymer in the present invention as paper additive processed, (methyl) pi-allyl
The usage amount of sulfonic acid and/or its salt (D) is usually 0.01~5 mole of %, preferably 0.05~2 mole %.Although (methyl) allyl
The usage amount of base sulfonic acid and/or its salt (D), which departs from above range, can also realize the object of the invention, but if within the above range
Especially so that paper additive viscosity processed adjustment becomes easy, and if more than higher limit, can not often expect and usage amount
Increase be adapted stay raising effect enhancing.
In order to obtain (methyl) acrylamide based copolymer in the present invention as paper additive processed, anionic property ethene
The usage amount of base monomer (E) is usually 0.5~10 mole of %, preferably 1~10 mole %.Although anionic property vinyl monomer
(E) usage amount, which departs from above range, can also realize the object of the invention, but paper processed can be especially played if within the above range
Effect is improved with the paper power of additive.
In order to obtain (methyl) acrylamide based copolymer in the present invention as paper additive processed, bridging property vinyl
The usage amount of monomer (F) is usually 0.001~2 mole of %, preferably 0.001~1 mole %.Although bridging property vinyl monomer
(F) usage amount, which departs from above range, can also realize the object of the invention, but paper processed is easily adjusted if within the above range and is used
The viscosity of additive.
The manufacture method of (methyl) acrylamide polymer is not particularly limited, and can use known various sides
Method.For example, under the inert gas environments such as nitrogen, toward the reaction vessel with mixer and thermometer in put into above-mentioned monomer and
Solvent is water (and can also using organic solvent as needed), and chain-transferring agent can be also put into as needed, further, can be with root
According to needing to modulate pH by the acid such as sulfuric acid, hydrochloric acid or these pH regulators of alkali such as sodium hydroxide, potassium hydroxide, ammonium.Thereafter
Polymerization initiator is added, makes reaction 1~5 hour at 20~90 DEG C of reaction temperature, it becomes possible to obtain purpose thing (methyl) propylene
Acid amides based copolymer.Furthermore it is also possible to as needed, while toward the monomer that drips in reaction vessel, water, chain-transferring agent, pH adjustment
Part or all of agent, polymerization initiator are while polymerization.
(methyl) acrylamide based copolymer for example monomer available (A), cationic vinyl monomer (C), (methyl) alkene
Propyl sulfonic acid and/or its salt (D) and acetaldehyde acids are manufactured.
More specifically, (methyl) acrylamide based copolymer can be obtained by following (a) or (b) method：
(a) by cationic vinyl of the monomer total amount existed in monomer (A), relative polymerization system for 1~20 mole of %
The monomer total amount existed in monomer (C), relative polymerization system is 0.01~5 mole of % (methyl) allyl sulphonic acid and/or its salt
And acetaldehyde acids puts into same reaction vessel and reacts them (D).
(b) make glyoxalic acid similar by sun of the monomer total amount existed in monomer (A), relative polymerization system for 1~20 mole of %
The monomer total amount existed in ionomeric ethylene base monomer (C), relative polymerization system is 0.01~5 mole of % (methyl) pi-allyl sulphur
Structural response shown in polymer formula of (A) obtained from acid and/or the polymerization of its salt (D), imports formula (B) knot accordingly
Structure.
Reaction condition in above two manufacture method is not particularly limited, but generally reaction temperature is 20~90 DEG C, instead
30 points~10 hours or so between seasonable.
(methyl) acrylamide based copolymer is typically to be supplied with the state of the aqueous solution containing it in the present invention.On this
The concentration of contained (methyl) acrylamide based copolymer is not particularly limited in the aqueous solution, but is examined from cost of transportation, processing mode
Consider, preferably 10~40 mass %.On the viscosity of (methyl) acrylamide based copolymer, consider from pump liquid, preferably 25 DEG C
100~20000mPas of lower brookfield viscosity.
On the molecular weight of (methyl) acrylamide based copolymer, it is not particularly limited, but preferred GPC-MALS measure
Weight average molecular weight 500,000~10,000,000.When weight average molecular weight within the above range when, can play well stay raising effect and
Paper power improves effect.When weight average molecular weight it is too small and during less than 500,000, stay, that paper power improves effect is not good；But it is excessive and exceed
When 10000000, sometimes strong toward coagulability during pulp addition, to paper, paper power bring harmful effect.
By following conditions obtain stay increase rate, preferably (Re) is more than 3% paperboard manufacture method.More preferably stay
Increase rate (Re) is 3%~20%, even more preferably 5%~15%.And stay increase rate to be represented through the micro- of twine mesh
The index of the ratio of thin paper pulp, and stays increase rate (Re) when being more than 3%, it is possible to reduce through the fine paper pulp of metallic sieve purpose
Tail off and cause on metallic screen that point water is poor, in extrusion process the problems such as felt hair blocking mesh.In addition, dynamic drainage instrument (Dynamic
Drainage Jar) sight using TAPPI T261CM-00 (Fine fraction by weight of paper stock
By wet screening) described in that device for providing of Fig. 1.
The condition is：
(i) the pulp temperature that Canadian Standard Freeness is adjusted to 300ml 1 mass % is adjusted to 25 DEG C；
(ii) take possess mixer (3 blade), the interior bore of 40 mesh metallic screens is (4 inches) of 10.16cm dynamic filter
Water instrument, is stirred with 600rpm；
(iii) the paper additive processed that relative paper pulp solid content is 0.5 mass % is added；
(iv) paper additive processed is added after 1 minute to start after draining, draining 50g, then draining 150g, then in filtrate
Solids level concentration (b) is measured；
(v) using solids level concentration in the filtrate determined in solids level concentration (a) in the pulp before draining and (iv),
Calculated by following formula and stay rate；
And stay rate (R)=(a-b)/a × 100 (%)
(vi) using with the addition of paper additive processed when stay rate (Rs) and do not have addition paper additive processed when stay
Rate (R0), calculated by following formula and stay increase rate (Re).
And stay increase rate (Re)=(Rs-R0)/R0× 100 (%)
Embodiment
Illustrate embodiment of the present invention below according to embodiment, but the present invention is not limited by these embodiments.
Production Example 1
Ion exchange is put into 1 liter of four-hole boiling flask with mixer, thermometer, reflux condensing tube and nitrogen ingress pipe
Water 610.1g, 50% acrylamide aqueous solution 315.17g, dimethylaminoethyl methacrylate 19.28g, 2-acryloyl
Amine-N-glycolic 14.22g, 1,3,5- triacryl hexahydros -1,3,5-triazines (triacrylformal) 0.06g, methyl
ALS 1.97g, then puts into 30% aqueous sulfuric acid 15.93g, takes pH3.0,60 are warming up in a nitrogen environment
℃.Then, added as polymerization initiator and 90 DEG C, insulation are warming up under 5% ammonium persulfate aqueous solution 5.59g, nitrogen environment.It is poly-
Run jointly after 1 hour beginning, 5% ammonium persulfate 11.17g of additional addition, reaction stops polymerization after starting after 2 hours.Obtained after cooling
Solid content 20.1%, viscosity (at 25 DEG C use Bu Shi rotation viscometers) 7500mPas, pH2.9 contain aqueous solutions of polymers.
Resulting character containing aqueous solutions of polymers is as shown in table 2.
Production Example 2~8, compare Production Example 1~3
As shown in table 1, in addition to species, the mol ratio of (A)~(F) compositions are changed, carry out with the behaviour as Production Example 1
Make, obtain containing aqueous solutions of polymers.Resulting character containing aqueous solutions of polymers is as shown in table 2.
Production Example 9
Ion exchange is put into 1 liter of four-hole boiling flask with mixer, thermometer, reflux condensing tube and nitrogen ingress pipe
Water 576.0g, 50% acrylamide aqueous solution 315.23g, dimethylaminoethyl methacrylate 19.28g, 50% glyoxalic acid
14.53g, methallylsulfonic acid sodium 2.33g, then put into 30% aqueous sulfuric acid 15.25g, take pH3.0, in nitrogen environment
Under be warming up to 60 DEG C.Then, added as polymerization initiator under 5% ammonium persulfate aqueous solution 5.59g, nitrogen environment and be warming up to 90
DEG C, insulation.After polymerization starts 1 hour, 5% ammonium persulfate 11.17g of additional addition, reaction stops polymerization after starting after 2 hours.
Obtained after cooling solid content 20.0%, viscosity 6400mPas, pH2.8 contain aqueous solutions of polymers.Resulting contains polymer
Aqueous solution character is as shown in table 2.
Production Example 10
As shown in table 1, in addition to species, the mol ratio of (A)~(F) compositions are changed, carry out with the behaviour as Production Example 9
Make, obtain containing aqueous solutions of polymers.Resulting character containing aqueous solutions of polymers is as shown in table 2.
Table 1
It is as follows that dummy suffix notation in table 1 characterizes the meaning.
AAm：Acrylamide
AGA：2-acryloyl amine-n-glycolic
Gly：Glyoxalic acid
DM：Dimethylaminoethyl methacrylate
DMBz：Dimethylaminoethyl methacrylate benzyl chloride quaternary ammonium compound
DABz：Acrylate benzyl chloride quaternary ammonium compound
IA：Itaconic acid
AA：Acrylic acid
SMAS：Methallylsulfonic acid sodium
TAF：1,3,5- triacryl hexahydro -1,3,5-triazines
The hollow column of table 1 represents not use tie element
In addition, each into its composition species is represented with above-mentioned dummy suffix notation in subfield, what is recorded on the right side of dummy suffix notation is it
Component molar %.Further, the C compositions of Production Example 5 give 3 kinds, are added a mole % to represent with dummy suffix notation and are listed in a line.
Table 2
The measure of weight average molecular weight is to utilize the GPC-MALS in GPC connection multi-angle light diffusion detectors in Production Example
Method is carried out.Condition determination is as follows.
GPC main bodys：Agilent Technologies (Agilent Technologies) LC1100 series processed
Splitter：Showa Denko K. K SHODEXSB806MHQ
Leacheate：The N/15 phosphate buffers (pH3) of the sodium nitrate containing N/10
Flow velocity：1.0ml/ point
Detector 1：Wyatt Technology of U.S. manufacture multi-angle light diffusion detector DAWN
Detector 2：Showa Denko K. K differential refractive index detector RI-101
Experiment 1 on staying rate
Dynamic drainage instrument input toward the interior bore 10.16cm (4 inches) for possessing 40 mesh metallic screens is obtained from old corrugated paper
, beating degree (Canadian Standard Freeness) be adjusted to 300ml, the mass % of pulp density 1.0 pulp (pulp
Temperature is 25 DEG C) 800g.Now, the stirring rotation number (paddle is 3 propeller blades) of dynamic drainage instrument is set to 600rpm.Paper
Starch slurry and put into 1 point after 10 seconds, obtained by addition is diluted to 0.8 mass % Production Example 1~10 and compares Production Example 1~3
Paper additive 5g (making paper additive processed be 0.5 mass % with respect to the addition of paper pulp solid content) processed.In addition, without system
5g water is added during paper additive.(now pulp pH is 7.5) opens dynamic drainage after paper additive processed is added 1 minute
The plug that instrument bottom is set, discharge 50g filtrates (this filtrate is discarded).150g filtrates are further discharged again, and the filtrate is used into White
Man (Whatman) No.41 filter paper processed attracts filtering, and solid content in filtrate has been reclaimed accordingly.Residue on filter paper is existed
After being dried under conditions of 105 DEG C, 1.5 hours, weight is determined, solid content (b) in filtrate has been obtained accordingly.The also row of determining in addition
The solid content (a) of pulp before liquid, has been calculated by following formula and has stayed rate (R).
And stay rate (R)=(a-b)/a × 100 (%)
Be used without add paper additive processed when stay rate (R0) and with the addition of in Production Example 1~10 and compare manufacture
During paper additive processed obtained by example 1~3 stay rate (Rs), calculated by following formula and stayed increase rate (Re).As a result such as
Shown in table 3.
And stay increase rate (Re)=(Rs-R0)/R0× 100 (%)
Experiment 2 on staying rate
Except pulp put into 10 seconds after with the addition of 5g be diluted to 2.4 mass % aluminum sulfate and in addition to, carried out with pass
Operation as the experiment 1 of rate is stayed (now pulp pH is 6.2).As a result it is as shown in table 3.
Table 3
Embodiment 1
300ml, pulp density 2.4 are adjusted to toward obtained from old corrugated paper, beating degree (Canadian Standard Freeness)
Quality % pulp addition aluminum sulfate, it is 0.5 mass % to make relative paper pulp solid content.Then, addition is in Production Example 1~10
With compare the paper additive processed obtained by Production Example 1~3, it is 0.5 mass % to make relative paper pulp solid content, or without,
It is stirred.After the pulp is agitated, diluted with pH7.0 water, pulp density is become after 0.8 mass % (now paper
The pH of slurry is starched 7.0), to carry out copy paper with TheNoble＆Wood company systems handshcet former, after extruding with cylindrical drier existed
100 DEG C of dryings 100 seconds, obtain grammes per square metre 80g/m2(ash component, which is determined, in breaking factor and paper uses) and 150g/m2It is (stronger than compressing
Degree determine use) handmade paper.Resulting paper stock has carried out various measure after damping in 24 hours under the conditions of 23 DEG C, RH50%.
Paper processed similarly carrying out with additive is not added.
In addition, the adding rate of above-mentioned medicine is the solid content weight ratio of relative paper pulp adiabatic drying weight.
Measurement result is as shown in table 4.Determined shown in table 4 is that standard is carried out according to following method.
Breaking factor JIS P 8112
Specific compress strength JIS P 8126
Ash component .JIS P 8128 in paper
Embodiment 2
Except pulp density is diluted into 0.8 matter without aluminum sulfate (adding rate is 0 mass %), with pH7.5 water
Measure % (now the pH of pulp be 7.5) and outer, carry out operation the same manner as in Example 1.Measurement result is as shown in table 4.
In the inventive method, preferably pulp contains solid content, aluminium compound in aluminium compound, and relative pulp
Ratio of occupying be scaled by aluminum oxide below 0.1 mass %.When containing aluminium compound in pulp, with the present invention
What paper processed was brought with additive stays effect and paper power enhancing effect more to improve this advantage.Sulphur can be enumerated as aluminium compound
Sour aluminium, polyaluminium chloride, sodium aluminate etc..
Table 4
From result shown in table 3 and 4 it will be evident that according to the paperboard manufacture method of the present invention, and staying raising, intensity to carry
It is high, it is believed that productivity, Quality advance in being manufactured to paperboard have great role.
Claims (8)
1. a kind of paperboard manufacture method, it is characterised in that have in the pulp addition using more than 50% old paper paper pulp logical
(methyl) acrylamide based copolymer of structure shown in formula (B) is paper additive processed, is pressed on the pulp after addition
State condition acquisition stay increase rate (Re) be more than 3%, use copy paper pH in pulp after addition be 6.5~8.5 paper
Starch slurry；(methyl) the acrylamide based copolymer is by least to that can form the monomer of structure shown in formula (A)
(A), the monomer total amount existed in relative polymerization system is 1~20 mole of % cationic vinyl monomer (C), relative polymerization system
The monomer total amount of interior presence is polymerize for 0.01~5 mole of % (methyl) allyl sulphonic acid and/or its salt (D) to be obtained；
R in formula1Represent H or CH3
R in formula2Represent H or CH3, R3Represent H, Na, K or NH4
The condition is：
(i) the pulp temperature that Canadian Standard Freeness is adjusted to 300ml 1 mass % is adjusted to 25 DEG C；
(ii) the dynamic capacity of returns tester for possessing 40 mesh metallic screens is taken, is stirred with 600rpm；
(iii) the paper additive processed that relative paper pulp solid content is 0.5 mass % is added；
(iv) paper additive processed is added after 1 minute to start after draining, draining 50g, then draining 150g, then to containing admittedly in filtrate
Amount concentration (b) is measured；
(v) using solids level concentration in the filtrate determined in solids level concentration (a) in the pulp before draining and (iv), under
State formula and calculate and stay rate；
And stay rate (R)=(a-b)/a × 100 (%)
(vi) using with the addition of paper additive processed when stay rate (Rs) and do not have addition paper additive processed when stay rate
(R0), calculated by following formula and stay increase rate (Re)
And stay increase rate (Re)=(Rs-R0)/R0× 100 (%).
2. paperboard manufacture method according to claim 1, it is characterised in that paperboard is lining body paper, core raw paper, paper tube
Body paper, plasterboard body paper, coated white, uncoated blank or chipboard.
3. paperboard manufacture method according to claim 1 or 2, it is characterised in that above-mentioned paper processed is to have to lead to additive
(methyl) acrylamide based copolymer of structure shown in formula (B), and it is by obtained from monomer progress copolymerization；The monomer
It is 1~20 mole of % containing the monomer total amount that can be formed the monomer (A) of structure shown in formula (A), exist in relative polymerization system
Cationic vinyl monomer (C), the monomer total amount that exists in relative polymerization system for 0.01~5 mole of % (methyl) allyl
Base sulfonic acid and/or its salt (D) and containing the monomer (B) of structure shown in formula (B) can be formed.
4. paperboard manufacture method according to claim 3, it is characterised in that monomer (A) is (methyl) acrylamide, monomer
(B) it is 2-(methyl) acryloyl amine-n-ethanol acids.
5. paperboard manufacture method according to claim 1 or 2, it is characterised in that above-mentioned paper processed is by making with additive
(methyl) acrylamide with structure shown in formula (B) that acetaldehyde acids is constituted with structural response shown in formula (A) is common
Polymers.
6. paperboard manufacture method according to claim 1 or 2, it is characterised in that paper processed is also further to exist with additive
In relative polymerization system exist monomer total amount be 0.5~10 mole of % in the range of used anionic property vinyl monomer (E)
Obtained from (methyl) acrylamide based copolymer.
7. paperboard manufacture method according to claim 6, it is characterised in that above-mentioned anionic property vinyl monomer (E) is
Unsaturated monocarboxylic acid or unsaturated dicarboxylic acid.
8. paperboard manufacture method according to claim 1 or 2, it is characterised in that paper processed is also further to exist with additive
The monomer total amount existed in relative polymerization system is has used bridging property vinyl monomer (F) in the range of 0.001~2 mole of %
Obtained (methyl) acrylamide based copolymer.
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| JP2007186821A (en) * | 2006-01-13 | 2007-07-26 | Seiko Pmc Corp | Method for producing paperboard and paperboard |
| JP5609253B2 (en) * | 2010-05-13 | 2014-10-22 | 星光Pmc株式会社 | Paperboard manufacturing method |
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| US4289676A (en) * | 1979-05-19 | 1981-09-15 | Basf Aktiengesellschaft | Binders, impregnating agents and coating agents based on an aqueous dispersion of an amide-containing copolymer |
| CN1109893A (en) * | 1993-12-24 | 1995-10-11 | 三井东压化学株式会社 | Acrylamide polymers and use thereof |
| CN1636026A (en) * | 2002-02-22 | 2005-07-06 | 星光Pmc株式会社 | (meth)acrylamide polymer, process for production thereof, paper making chemicals, papers containing the same |
| JP5024719B2 (en) * | 2005-11-04 | 2012-09-12 | 荒川化学工業株式会社 | Paper manufacturing method |
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| CN101906734A (en) * | 2009-06-05 | 2010-12-08 | 星光Pmc株式会社 | Additive for papermaking |
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| CN103459716A (en) | 2013-12-18 |
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| JP5924594B2 (en) | 2016-05-25 |
| CN102808354A (en) | 2012-12-05 |
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| WO2012164916A1 (en) | 2012-12-06 |
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