CN109577086A - Paper power reinforcing agent and paper - Google Patents
Paper power reinforcing agent and paper Download PDFInfo
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- CN109577086A CN109577086A CN201811128880.5A CN201811128880A CN109577086A CN 109577086 A CN109577086 A CN 109577086A CN 201811128880 A CN201811128880 A CN 201811128880A CN 109577086 A CN109577086 A CN 109577086A
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- starch
- reinforcing agent
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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
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
The purpose of the present invention is to provide the more cheap and superior paper power reinforcing agent of paper power effect and paper compared with previous starch-(methyl) acrylamide polymer.A kind of paper the present invention relates to paper power reinforcing agent and comprising the paper power reinforcing agent, the paper power reinforcing agent includes the reaction product of any one in the polymer (B2) of starch (A) and monomer component (B1) or (B) ingredient, the starch (A) has (methyl) acrylate-based in the molecule, and the monomer component (B1) includes (methyl) acrylamide (b1).
Description
Technical field
The present invention relates to paper power reinforcing agent and paper.
Background technique
All the time, main to use such as (methyl) acrylamide polymer, starch as paper power reinforcing agent.(first
Base) acrylamide polymer price compared with starch is high, but the stationarity for being fixed on paper pulp is high, it is showed a small amount of addition
Excellent paper power effect out.On the other hand, starch is although cheap, but paper pulp is fixed on compared with acrylamide polymer
Stationarity it is low, therefore, need to increase the additive amount relative to pulp solid component to play high paper power effect.
Thus, in order to apply flexibly the advantage of (methyl) acrylamide polymer and starch respectively, for by keeping the two anti-
It answers and relatively inexpensive and high performance paper power reinforcing agent is provided and has carried out various researchs.
Such as it is known that in the aqueous dispersions containing the water dispersible polysaccharides class such as starch will based on acrylamide at
Additive for papermaking (patent document 1,2) obtained from the monomer mixture divided is polymerize；It is previously fabricated to have on side chain
Acrylamide polymer of the vinyl monomer of specific chain transfer substituent group as constituent, makes itself and water dispersible
Polysaccharide-acrylamide polymer (patent document 3) of Grafting Structure obtained from polysaccharide is graft-polymerized.In addition,
The applicant discloses starch made of being modified it with the bridging property vinyl monomer with chain transfer substituent group and makes
Additive for papermaking (patent document 4) obtained from acrylamide polymer (B) reacts in the presence of peroxide.
However, they can be realized improvement to a certain degree in price, aspect of performance, but it is unable to satisfy and wants to realize into one
The demand of low price, the paper industry that further performance improves is walked, people are seeking relatively inexpensive and high performance papermaking
Chemicals.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 8-60591 bulletin
Patent document 2: No. 2928785 bulletins of Japanese Patent No.
Patent document 3: No. 3371931 bulletins of Japanese Patent No.
Patent document 4: Japanese Unexamined Patent Publication 2016-069788 bulletin
Summary of the invention
Problems to be solved by the invention
Present invention offer is more cheap compared with previous starch-(methyl) acrylamide polymer and paper power effect is more excellent
Different paper power reinforcing agent and paper.
The method for solving problem
The inventors of the present invention are conceived to the above subject and have made intensive studies, as a result, it has been found that: with (methyl) acrylic acid
Starch made of the ingredient of ester group is modified it can play effect, make the modified starch and the monomer comprising (methyl) acrylamide
Paper power reinforcing agent obtained from any one in the polymer of ingredient or above-mentioned monomer component reacts can solve the above subject, from
And complete the present invention.That is, the present invention relates to paper power reinforcing agent below and paper.
1. a kind of paper power reinforcing agent, it includes any one in starch (A) and monomer component (B1) or its polymer (B2)
Reaction product, the starch (A) have (methyl) acrylate-based in the molecule, and the monomer component (B1) includes (methyl) third
Acrylamide (b1).
2. according to the paper power reinforcing agent of preceding paragraph 1, wherein (A) ingredient is with (methyl) acrylate-based ingredient (a1)
With the reaction product of raw starch.
3. according to the paper power reinforcing agent of preceding paragraph 1 or 2, wherein (a1) ingredient is selected from unsaturated monocarboxylic acid anhydride, unsaturation two
1 kind in carboxylic acid anhydrides, compound and unsaturated isocyanate containing unsaturated glycidyl.
4. the paper power reinforcing agent according to any one of preceding paragraph 1~3, wherein the raw starch of (A) ingredient is enzyme degradation
Starch.
5. the paper power reinforcing agent according to any one of preceding paragraph 1~4, wherein (B1) ingredient includes:
(methyl) acrylamide (b1)；And
Cationic vinyl monomer (b2) and/or anionic property vinyl monomer (b3).
6. also including bridging property vinyl monomer (b4) and chain-transferring agent (b5) according to the paper power reinforcing agent of preceding paragraph 5.
7. the paper power reinforcing agent according to any one of preceding paragraph 1~6, concentration is 20 weight %, temperature is 25 DEG C
Under conditions of viscosity be 100~30,000mPas.
8. a kind of paper, it includes the paper power reinforcing agents described in any one of preceding paragraph 1~7.
The effect of invention
Paper power reinforcing agent according to the present invention, the starch and include acrylamide that intramolecular has (methyl) acrylate-based
Monomer component or its polymer high efficiency react, gained paper power reinforcing agent have excellent paper power effect.
Specific embodiment
Paper power reinforcing agent of the invention includes: in the molecule (hereinafter referred to as with (methyl) acrylate-based starch (A)
(A) ingredient) and monomer component (B1) (hereinafter referred to as (B1) ingredient) or its polymer comprising (methyl) acrylamide (b1)
(B2) reaction product of any one in (hereinafter referred to as (B2) ingredient).
As (A) ingredient, can enumerate for example with (methyl) acrylate-based ingredient (a1) (hereinafter referred to as (a1) at
Point) with the reaction product of raw starch.
(a1) ingredient is in order to which resulting (A) ingredient is played because that efficiently can be directed into acrylamide polymer
Good paper power effect and use.As (a1) ingredient, if having react with the hydroxyl of starch functional group (such as
Carboxyl, glycidyl, isocyanate group etc.), there is no particular limitation, can enumerate for example acrylic acid, methacrylic acid, bar
The unsaturated monocarboxylics such as beans acid, iso-crotonic acid；The unsaturations such as itaconic acid, maleic acid, fumaric acid, muconic acid, citraconic acid, mesaconic acid
Dicarboxylic acids；The unsaturated monocarboxylics acid anhydrides such as acrylic anhydride, methacrylic anhydride, crotonic anhydride, iso-crotonic acid acid anhydride；Itaconic anhydride, horse
Carry out the unsaturated dicarboxylics acid anhydrides such as acid anhydrides, fumaric acid anhydride, muconic acid acid anhydride, citraconic anhydride；Glycidyl acrylate, methacrylic acid
The compound containing unsaturated glycidyl such as ethylene oxidic ester, allyl glycidyl ether；Isocyanate ethyl acrylate,
The unsaturated isocyanates such as isocyanate ethyl methacrylate, 1,1- (double acryloyloxymethyls) ethyl isocyanate
Deng.They may be used singly or in combination of two or more.Wherein, it is come from from by efficiently being imported to raw starch
(a1) (methyl) of ingredient is acrylate-based and make the reactivity of itself and (B1) ingredient or (B2) ingredient also excellent, result obtains
From the perspective of paper power reinforcing agent plays excellent paper power effect, it is preferably selected from unsaturated monocarboxylic acid anhydride, unsaturated dicarboxylic
1 kind in acid anhydride, compound and unsaturated isocyanate containing unsaturated glycidyl, it is more preferably selected from itaconic anhydride, Malaysia
1 kind in acid anhydrides, glycidyl acrylate, glycidyl methacrylate and isocyanate ethyl methacrylate.
It as raw starch, is not particularly limited, various known objects can be used, can enumerate for example by corn, Ma Ling
The unmodified starch that potato, cassava, wheat, rice, sago palm, waxy corn, high amylose starches obtain；Cationic starch, oxidation
Starch, phosphoric acid modification starch, carboxymethylated starch, amine modified starch, hydroxyethyl starch, Carbamoylethyl starch, cyanogen
Modified starches such as base ethylated starch, two hydroformylation starch, acetic acid modified starch, TEMPO oxidized starch etc..They can individually make
With can also combine two or more.Furthermore it is also possible to use commercially available product.
In addition, can be used and unmodified starch or modified starch etc. are carried out degradation treatment and obtained as raw starch
Product (hereinafter referred to as degradable starch).It as degradable starch, is not particularly limited, can enumerate for example makes inorganic peroxide
The peroxide degradation starch for acting on above-mentioned raw materials starch and being handled；Above-mentioned raw materials starch is handled with enzyme and is obtained
The enzymatic degradation of starch etc. arrived.The degradable starch can be by will include that the aqueous solution of starch and degradation agent heats at 60~100 DEG C
30~60 minutes are stirred to manufacture.
It as the inorganic peroxide for manufacturing peroxide degradation starch, is not particularly limited, can enumerate for example
Hypochlorite, peroxydisulfate (ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate etc.), hydrogen peroxide etc..The peroxide can be single
Solely uses or combine two or more.In turn, it can also be combined into hydrogen peroxide at least one kind of water-soluble in ferric sulfate and copper sulphate
Property heavy metallic salt simultaneously uses.Among these, it is preferable to using at least any in ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate
Kind.
As the enzyme for manufacturing enzymatic degradation of starch, it is preferable to use the alphalise starch of for example various bacteriums, animals and plants institute output
Enzyme.
In paper power reinforcing agent of the invention, will not excessively be thickened from reaction solution when being reacted with (a1) ingredient, gained (A) at
The viscosity divided also is easy from the perspective of being lower, preferably enzymically modified starch.
As the dosage of (a1) ingredient and raw starch, it is not particularly limited, in terms of solids by weight, raw starch/
(a1) ingredient=50/50~99.9/0.1 or so, preferably 92/8~99.5/0.5 or so, more preferably 96/4~99/1 left side
It is right.By being set as above-mentioned numberical range, it is not susceptible to thicken when reacting with (B1) ingredient or (B2) ingredient.
It as the manufacturing method of (A) ingredient, is not particularly limited, can enumerate for example makes raw starch be dispersed in solvent
In, (a1) ingredient is then mixed, and (excellent with 5~90 DEG C of temperature or so (preferably 5~30 DEG C or so) reactions 5~300 minutes or so
Select 15~120 minutes or so) etc..It should be noted that can be carried out by being added dropwise with (methyl) acrylate-based ingredient
Addition.(A) ingredient obtained by this manufacturing method has (methyl) acrylate-based in the molecule, therefore, with (B1) ingredient
Or the reaction of (B2) ingredient is excellent, final paper power reinforcing agent also plays good paper power effect.
As above-mentioned solvent, be not particularly limited, can be suitably used water (ion exchange water, pure water, tap water etc.),
Organic solvent etc..As organic solvent, as long as being easy that raw starch is dissolved or dispersed under conditions of room temperature or heating, do not have
It is particularly limited to, such as dimethyl sulfoxide, N-2- methyl pyrrolidone, n,N-Dimethylformamide, N, N- diformazan can be enumerated
Yl acetamide, acetonitrile etc..They may be used singly or in combination of two or more.In addition, in the present invention, it can be without molten
Attached (a1) ingredient is blown under conditions of agent into powdered starch, but it is preferable to use above-mentioned solvents, wherein from reduction carrying capacity of environment
From the perspective of, preferably water.In addition, the dosage as solvent, is not particularly limited, (a1) ingredient and raw starch are considered
Reactivity, concentration are preferably adjusted to 0.1~50 weight % or so.
It as the physical property of gained (A) ingredient, is not particularly limited, plays excellent paper power from final paper power reinforcing agent
From the perspective of effect, for example, 15 weight % of concentration, the viscosity at 25 DEG C of temperature are usually 50~30,000mPas or so,
Preferably 100~25,000mPas or so.
(B1) ingredient is the monomer component comprising (methyl) acrylamide (b1), as an example therein, includes (methyl)
Acrylamide (b1) (hereinafter referred to as (b1) ingredient), cationic vinyl monomer (b2) (hereinafter referred to as (b2) ingredient) and yin from
Sub- sex ethylene base monomer (b3) (hereinafter referred to as (b3) ingredient).
As (b1) ingredient, refer to acrylamide, Methacrylamide.
It as (b2) ingredient, is not particularly limited, various known objects can be used, from playing excellent paper power effect
Viewpoint is set out, and is preferably comprised: the quaternary salt of the vinyl monomer of tertiary-amino-containing and/or the vinyl monomer.As tertiary-amino-containing
Vinyl monomer concrete example, be not particularly limited, can enumerate such as (methyl) acrylic acid N, N- dimethylamino ethyl ester,
(methyl) acrylic acid N, N- diethylamino ethyl ester, N, N- dimethylaminopropyl (methyl) acrylamide, N, N- diethyl amino
Base propyl (methyl) acrylamide etc..In addition, the quaternary salt as the vinyl monomer, can enumerate the ethylene for tertiary-amino-containing of sening as an envoy to
Quaternary ammonium salt made of base monomer is reacted with quaternising agents etc..In addition, can be the inorganic acids such as hydrochloride, sulfate as quaternary salt
Salt；The acylates such as acetate.It as above-mentioned quaternising agents, is not particularly limited, such as methyl chloride, benzyl chloride, sulphur can be enumerated
Dimethyl phthalate, epoxychloropropane etc..These (b2) ingredients can be used alone, and can also combine two or more.Wherein, preferred (first
Base) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino ethyl ester the quaternary salt of benzyl chloride.
It as (b3) ingredient, is not particularly limited, various known objects can be used, from playing excellent paper power effect
Viewpoint is set out, and the vinyl monomer with carboxyl is preferably comprised.As above-mentioned vinyl monomer, such as (methyl) third can be enumerated
The α such as olefin(e) acid, crotonic acid, β-unsaturated monocarboxylic；The α such as maleic acid, fumaric acid, itaconic acid, muconic acid, citraconic acid, β-unsaturation
Dicarboxylic acids；The organic systems such as vinyl sulfonic acid, styrene sulfonic acid sulfonic acid or sodium salt, the sylvite of above-mentioned acid etc..They can be independent
It uses, can also combine two or more.Wherein, preferably acrylic acid and/or itaconic acid.
(b1) containing ratio of ingredient, (b2) ingredient and (b3) ingredient is not particularly limited, and increases from gained paper power is played
It, will be in (B1) ingredient from the perspective of ionic (cationic, anionic property, the both sexes) and excellent paper power effect of strong agent
Whole monomer components are set as 100 moles of %, respectively following setting.
<the case where cationic>
(b1) ingredient: it is usually 70~99.5 moles of % or so, preferably 79.5~99 moles of % or so, is more preferably
83.5~98.5 moles of % or so
(b2) ingredient: being usually 0.5~30 mole of % or so, preferably 1~20 mole of % or so, more preferably 1.5
~15 moles of % or so
<the case where anionic property>
(b1) ingredient: it is usually 75~99.5 moles of % or so, preferably 79.5~99 moles of % or so, is more preferably
83.5~98.5 moles of % or so
(b3) ingredient: being usually 0.5~25 mole of % or so, preferably 0.8~20 mole of % or so, more preferably 1
~15 moles of % or so
<the case where both sexes>
(b1) ingredient: be usually 45~99 moles of % or so, preferably 60~98 moles of % or so, more preferably 75~
97 moles of % or so
(b2) ingredient: being usually 0.5~30 mole of % or so, preferably 1~20 mole of % or so, more preferably 1.5
~15 moles of % or so
(b3) ingredient: being usually 0.5~25 mole of % or so, preferably 0.8~20 mole of % or so, more preferably 1
~15 moles of % or so
In turn, bridging property vinyl monomer can be properly mixed for the purpose for adjusting weight average molecular weight, in (B1) ingredient
(b4), chain-transferring agent (b5).
It as (b4) ingredient, is not particularly limited, can enumerate such as vinyl hexanediacetate, decanedioic acid diethyl enester
Divinyl base ester；Diethylene glycol list (methyl) acrylate, triethylene glycol list (methyl) acrylate, tetraethylene glycol list (methyl)
The polyethyleneglycols such as acrylate (methyl) acrylate；Ethylene glycol two (methyl) acrylate, diethylene glycol two (methyl) third
The polyethylene glycol such as olefin(e) acid ester two (methyl) acrylate；(methyl) acrylic acid 2- hydroxy methacrylates, methoxy poly (ethylene glycol) list (first
Base) it is acrylate, polytrimethylene glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, poly-
Ethylene glycol propylene glycol list (methyl) acrylate etc. polyalkylene glycol monos (methyl) acrylate；N- (1,1- dimethyl -3- oxygen
For butyl) acrylamide, n-isopropyl acrylamide, N hydroxymethyl acrylamide, N- allyl (methyl) acrylamide, 2- third
The N- such as acrylamide -2- methyl propane sulfonic acid and its salt replace (methyl) acrylamide；N,N-DMAA, N, N- diethyl
Acrylamide, N, the N, N- such as N- diallyl (methyl) acrylamide replace (methyl) acrylamide；N, N '-di-2-ethylhexylphosphine oxide (first
Base) acrylamide, N, the N, N '-such as N '-ethylenebis (methyl) acrylamide replace (methyl) acrylamide；Divinylbenzene,
1,3,5- triacryl hexahydro -1,3,5-triazines, triallyl isocyanurate, triallyltrimelitate, triallylamine, four
The aromatic multi-vinyl based compound of methylol methane tetraacrylate, four allyl ester of pyromellitic acid etc.；(methyl) acrylic acid alkene
Propyl ester, triacryl formal etc..They may be used singly or in combination of two or more.Wherein, from appropriateness adjustment weight
From the perspective of average molecular weight, paper power effect are also excellent, preferably N, N- replace (methyl) acrylamide, more preferable N, N- dimethyl
Acrylamide.
(b4) containing ratio of ingredient is not particularly limited, from the viewpoint of paper power effect, by always containing for (B1) ingredient
There is ratio to be set as 100 moles of %, usually 0~10 mole of % or so, preferably 0.02~5 mole of % or so, more preferably 0.1
~2 moles of % or so.
(b5) ingredient can obtain that the polymer chain before cross-linking reaction becomes shorter, viscosity is low and the higher copolymerization of molecular weight
Object.It as (b5) ingredient, is not particularly limited, the thio-alcohol such as 2 mercapto ethanol, n-dodecyl mercaptan can be enumerated；α-
The methallyls such as methyl styrene dimer object, Sodium methallyl sulfonate, methallyl sulfonic acid potassium, methallyl sulfonic acid ammonium
Base sulfonate；Ethyl alcohol, isopropanol, amylalcohol etc. do not have the alcohols of allyl；Carbon tetrachloride, ethylo benzene, cumene, 2,4- bis-
Phenyl -4-methyl-1-pentene etc..They may be used singly or in combination of two or more.Wherein, from adjusting paper power enhancing
From the perspective of the weight average molecular weight and viscosity of agent, preferably methallyl sulfonate, more preferably methallyl sulfonic acid
Sodium.
About the containing ratio of (b5) ingredient, from the viewpoint of paper power effect, total containing ratio of (B1) is set as 100
Mole %, usually 0~20 mole of % or so, preferably 0.1~10 mole of % or so, more preferably 0.2~5 mole of left side %
It is right.
In addition, (B1) ingredient can be containing the ingredient (b6) other than (b1) ingredient~(b5) ingredient (hereinafter referred to as
(b6) ingredient).It as (b6) ingredient, is not particularly limited, such as styrene, α-methylstyrene, vinyl first can be enumerated
The aromatic vinyl monomers such as benzene；(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (first
Base) (methyl) alkyl acrylate such as butyl acrylate, (methyl) acrylic acid-2-ethyl caproite, (methyl) cyclohexyl acrylate；
Vinyl carboxylates such as vinyl acetate, vinyl propionate etc..They may be used singly or in combination of two or more.
(b6) containing ratio of ingredient is not particularly limited, and total containing ratio of (B1) ingredient is set as 100 moles of %, leads to
It is often 5 moles of % or less, preferably 1 mole of % or less.
(B2) ingredient is the polymer of above-mentioned (B1) ingredient, ionic according to its and be classified as nonionic acrylamide
Polymer, anionic property acrylamide polymer, cationic acrylamide polymer, the polymerization of both sexes acrylamide
Object.In addition, the monomer component as formation (B2) ingredient, can enumerate above-mentioned (b1)~(b6) ingredient, they containing than
Rate is set according to the ionic of (B2) ingredient also as described above.
It as the manufacturing method of (B2) ingredient, is not particularly limited, can enumerate: in the presence of such as polymerization initiator
Conventionally known monomer dropping polymerization, polymerization or the side that is composed them while put into monomer solution together
Method etc..Manufacturing condition is also not particularly limited, for example, temperature is usually 30~90 DEG C or so, preferably 70~90 DEG C or so, when
Between be usually 15 minutes~10 hours or so, preferably 30 minutes~5 hours or so.It should be noted that being mixed as monomer
Solvent used in liquid as long as each monomer component is made to dissolve or disperse, and does not cause adverse effect to polymerization reaction, just without spy
It does not limit, it is usually preferred to use water.
It as polymerization initiator, is not particularly limited, can enumerate such as ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate
Persulfate；The azo compounds such as bis- (2- amidine propane) hydrochlorides of 2,2 '-azos；Hydrogen peroxide etc..They can be independent
It uses, can also combine two or more.Wherein, from the viewpoint of carrying out the polymerization reaction of polymeric composition (A) sufficiently, preferably
Ammonium persulfate, potassium peroxydisulfate and/or 2, bis- (2- amidine propane) hydrochlorides of 2 '-azos.In addition, the addition for polymerization initiator
Method is not particularly limited, and can suitably select to add together or add or be continuously added dropwise by several times etc..In addition, polymerization initiator
Dosage be also not particularly limited, relative to whole 100 parts by weight of monomer component, usually 0.001~5 parts by weight or so, excellent
It is selected as 0.01~1 parts by weight or so.
In turn, although can be used for example from the viewpoint of the free radical for being easy to produce peroxide for option
The bisulfites such as the sulphite such as sodium sulfite, sodium hydrogensulfite, triethanolamine, cuprous sulfate, ferric sulfate etc..
It should be noted that may include in (B2) ingredient obtained from by the above-mentioned manufacture method unreacted (b1)~
(b6) ingredient.
It as the physical property of (B2) ingredient, is not particularly limited, for example, being seeped from the viewpoint of paper power effect based on gel
The weight average molecular weight of saturating chromatography (GPC) method is usually 50,000~10,000,000 or so, preferably 100,000~8,000,
000 or so.In addition, the form as (B2) ingredient, is desired for aqueous solution.
In addition, the viscosity as (B2) ingredient, in terms of the aqueous solution (25 DEG C of temperature) that concentration is 20 weight %, usually 50
~50,000mPas or so, preferably 100~30,000mPas or so.
It as the manufacturing method of paper power reinforcing agent, is not particularly limited, can enumerate for example makes (A) ingredient and (B1) ingredient
The process to react.
The usage rate of (A) ingredient and (B1) [(b1) ingredient~(b6) ingredient total weight] in the manufacturing method does not have
It is particularly limited to, from the viewpoint of paper power effect, preferably (A)/(B1)=5/95~95/5 or so in terms of solids by weight,
More preferably 10/90~90/10 or so.
In addition, being not particularly limited as manufacturing condition, it is desirable to (A) ingredient and (B1) ingredient ((b1) ingredient
The mixed liquor of~(b6) ingredient) in add polymerization initiator, temperature is 50~90 DEG C or so, the time is 15 minutes~6 hours
It is carried out under conditions of left and right.The type and dosage of polymerization initiator are as shown above.It should be noted that during fabrication, Ke Yixiang
(A) (B1) ingredient is directly added in ingredient, can also be added by being added dropwise.It should be noted that in the present invention, from obtaining height
From the perspective of the reaction product of molecular weight, the mixed liquor of (A) ingredient and (B1) ingredient is preferably added dropwise to the process in solvent.
As the manufacturing method of other paper power reinforcing agents, the work that send as an envoy to (A) ingredient and (B2) ingredient react can be enumerated
Sequence.
The usage rate of (A) ingredient and (B2) in the manufacturing method is not particularly limited, and goes out from the viewpoint of paper power effect
Hair, in terms of solids by weight, preferably (A)/(B2)=5/95~95/5 or so, more preferably 10/90~90/10 or so.
It as manufacturing condition, is not particularly limited, it is desirable to be added into (A) ingredient and the mixed liquor of (B2) ingredient
Peroxide and/or azo compound are 50~90 DEG C or so (preferably 70~90 DEG C or so) in temperature and carry out 5 minutes~3
Hour or so (preferably 15 minutes~2 hours or so).It, can be by (A) ingredient together or by several times it should be noted that during fabrication
It is added in (B2) ingredient, and then can be added by being added dropwise.
It as peroxide, is not particularly limited, such as ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, peroxide can be enumerated
Change hydrogen etc., in addition, azo compound is also not particularly limited, such as 2 can be enumerated, bis- (2- amidine propane) salt of 2 '-azos
Hydrochlorate etc..They may be used singly or in combination of two or more.In addition, their dosage is also not particularly limited, relatively
In total 100 parts by weight of (A) ingredient and (B2) ingredient, usually 0.001~5 parts by weight or so, preferably 0.01~1 weight
Part or so.In turn, can optionally employ the bisulfites such as the sulphite such as sodium sulfite, sodium hydrogensulfite, triethanolamine,
Cuprous sulfate, ferric sulfate etc..
The concentration of paper power reinforcing agent as obtained from these manufacturing methods is not particularly limited, from the viewpoint of transportation cost
It sets out, usually 5~50 weight % or so, preferably 10~50 weight % or so.In addition, as other physical property, without spy
It does not limit, for example, concentration is that the viscosity of the aqueous solution (25 DEG C of temperature) of 20 weight % is usually from the viewpoint of paper power effect
100~30,000mPas or so, preferably 200~25,000mPas or so.
In above-mentioned paper power reinforcing agent, in the range of not departing from the purpose of the present invention/effect, it can according to need and cooperate
Various additives.It as additive, is not particularly limited, such as defoaming agent, preservative, chelating agent, water-soluble aluminum can be enumerated
Compound, saltcake, urea, ammonium sulfate, sodium chloride etc..
Paper bag of the invention contains above-mentioned paper power reinforcing agent.It as its production method, can enumerate: in advance by paper power reinforcing agent
After the dilution such as ion exchange water, inside add into starting pulps slurry or be coated on body paper surface, so by they combine and
At method etc..
In the case where adding inside, paper power reinforcing agent of the invention is added to pulp and carries out copy paper.The enhancing of paper power
The dosage of agent is not particularly limited, and is 0.01~4 weight % or so relative to the solids by weight of pulp.In addition, paper
The type of slurry slurry is also not particularly limited, and can enumerate the chemical pulps such as LBKP, NBKP；The mechanical pulps such as GP, TMP；Old paper
Paper pulp etc..In addition, it is interior when adding, it can separately add aluminum sulfate, aluminium hydroxide etc.；Sulfuric acid, sodium hydroxide as pH adjusting agent
Deng；Sizing agent, wet paper power agent；As the talcum of filler, clay, kaolin, titanium dioxide and calcium carbonate etc..
In the case where surface is coated with, body paper surface is applied to by various known approaches.Increase as the paper power before coating
The viscosity of strong agent (coating fluid), usually under the concentration of 5 weight %, be 1~50mPas at 50 DEG C.As the type of body paper,
The uncoated paper using lumber fibre cellulose fiber as raw material can be used to be not particularly limited as apparatus for coating, can enumerate
Such as bar coater, knife type coater, Kohler coater, casting machine, door roller coating machine, scraper plate coating machine, double roller size presser,
Bar type meter etc..In addition, the coating weight (solid component) of paper power reinforcing agent is also not particularly limited, usually 0.001~2g/
m2Left and right, preferably 0.005~1g/m2Left and right.
Paper of the invention is available for various products, can be used, for example, as coating body paper, paper for newspapers, liner, core, paper tube,
Print writing paper, foam paper, PPC paper, InkJet paper, thermal paper etc..
Embodiment
Hereinafter, enumerating embodiment and comparative example specifically describes the present invention.It should be noted that part and % are based on weight
Measure benchmark.It should be noted that for convenience, for monomer etc., being indicated as follows with referred to as.
AM: acrylamide
AA: acrylic acid
IA: itaconic acid
DM:(methyl) acrylic acid N, N- dimethylamino ethyl ester
The benzyl chloride quaternaries of DML:DM
DMAA:N, N- dimethylacrylamide
SMAS: Sodium methallyl sulfonate
APS: ammonium persulfate
GMA: glycidyl methacrylate
GA: glycidyl acrylate
MAA: maleic anhydride
IAA: itaconic anhydride
IEMA: isocyanate ethyl methacrylate
PO: propylene oxide
(viscosity)
Using Brookfield type viscosimeter (Toki Sangyo Co., Ltd.'s system), measurement adjusts gluing to 25 DEG C of sample
Degree.
(weight average molecular weight)
By gel permeation chromatography (GPC) method, molecular weight is measured using following determination conditions.
GPC main body: TOSOH Co., Ltd's system
Chromatographic column: TOSOH Co., Ltd's system, guard column PWXL 1 and GMPWXL 2 (temperature is 40 DEG C)
Eluent: 0.5mol/L acetate buffer (0.5mol/L acetic acid (Wako Pure Chemical Industries, Ltd.'s system)+
0.5mol/L sodium acetate (KISHIDA CHEMICAL corporation) aqueous solution, pH are about 4.2)
Flow velocity: 0.8mL/ minutes
Detector:
VISCOTECH corporation, TDA MODEL301 (concentration detector and 90 ° of light scattering detectors and viscosity detector
(temperature is 40 DEG C)) RALLS method
Measurement sample: sample concentration is adjusted to after 0.5%, comprising cationic ingredient, adds hydrogen-oxygen
Change sodium water solution until pH reaches 10~12, after being impregnated 1 hour in 80 DEG C or more of hot bath, is adjusted to sulfuric acid
PH6~8 are diluted to 0.025% with eluent, to be measured.
Synthesis example 1
Solid component concentration is added into the reaction unit for having blender, thermometer, reflux cooling tube, nitrogen ingress pipe
100.0 parts of cornstarch (trade name " cornstarch ", prince's cornstarch Co. Ltd. system), alpha-amylase (quotient for 88%
The name of an article " KREASTASE L1 ", Amano Enzyme corporation) 0.03 part and 480 parts of ion exchange water, 75 DEG C are warming up to, stirring
After forty minutes, 90 DEG C are warming up to, is futher stirred 10 minutes.After being cooled to 30 DEG C, pH is adjusted to 48% sodium hydroxide and is reached
11, add 1.0 parts of GMA.In turn, it is stirred 1 hour in 30 DEG C, is diluted to concentration with ion exchange water and reaches 15%, to obtain
(A-1) ingredient.The viscosity of gained starch (A-1) is shown in table 1 (following same).
Synthesis example 2~7,10~13
Be set as composition shown in table 1, synthesized using method identical with synthesis example 1, obtain (A-2)~(A-7),
(A-10)~(A-13) ingredient.
Synthesis example 8
Solid component concentration is added into the reaction unit for having blender, thermometer, reflux cooling tube, nitrogen ingress pipe
For 88% 100.0 parts of cornstarch (trade name " cornstarch ", prince's cornstarch Co. Ltd. system) and ion exchange water
480 parts, 90 DEG C are warming up to, is futher stirred 10 minutes.After being cooled to 30 DEG C, pH is adjusted to 48% sodium hydroxide and reaches 11,
1.0 parts of GMA of addition.In turn, it is stirred 1 hour in 30 DEG C, is diluted to concentration with ion exchange water and reaches 15%, to obtain (A-
8) ingredient.
Synthesis example 9
Solid component concentration is added into the reaction unit for having blender, thermometer, reflux cooling tube, nitrogen ingress pipe
For 88% 100.0 parts of cornstarch (trade name " cornstarch ", prince's cornstarch Co. Ltd. system), 1.0 parts of APS and
480 parts of ion exchange water, 90 DEG C are warming up to, is stirred 40 minutes.After being cooled to 30 DEG C, pH is adjusted to 48% sodium hydroxide and is reached
11, add 1.0 parts of GMA.In turn, it is stirred 1 hour in 30 DEG C, is diluted to concentration with ion exchange water and reaches 15%, to obtain
(A-9) ingredient.
Compare synthesis example 1
Add into the reaction unit for having blender, thermometer, reflux cooling tube, nitrogen ingress pipe and three dropping funels
Reinforcing body constituent concentration be 88% 100 parts of cornstarch (trade name " cornstarch ", prince's cornstarch Co. Ltd. system),
0.03 part and 480 parts of ion exchange water of alpha amylase (trade name " KREASTASE L1 ", Amano Enzyme corporation), heating
To 75 DEG C, stirring after forty minutes, is warming up to 90 DEG C, futher stirs 10 minutes, be diluted to concentration with ion exchange water and reach
15%, to obtain (C-1) ingredient.
Compare synthesis example 2
It other than (a1) ingredient is changed to PO, is synthesized in the same manner as synthesis example 1, obtains (C-2) ingredient.
Compare synthesis example 3
Compare in synthesis example 1, the type of raw starch is changed to cationic starch (trade name " CS-1 ", waste river
Learn Industrial Co., Ltd's system), and synthesized, obtain (C-3) ingredient.
[table 1]
The dosage of degradation agent in ※ table and (a1) ingredient is indicated with the numerical value of the weight relative to water-containing material starch.
Embodiment 1-1 (mixed liquor (hereinafter referred to as preparation method 1) that (A) ingredient and (B1) ingredient is added dropwise)
It is thrown into the reaction unit for having blender, thermometer, reflux cooling tube, nitrogen ingress pipe and two dropping funels
Enter 268.4 parts of ion exchange water, after being passed through the oxygen that nitrogen removes in reaction system, is heated to 85 DEG C.Separately to dropping funel
(1) in investment 284.8 parts of 50%AM aqueous solution, 10.4 parts of IA, 9.6 parts of 80%AA, 41.8 parts of DM, 62.8 parts of 60%DML,
193.1 parts of 8.8 parts of SMAS, 1.32 parts of DMAA and ion exchange water, 416.7 parts of (A-1) ingredient prepared in advance.In addition, to
0.2 part and 60 parts of ion exchange water of investment APS in dropping funel (2).Then, 3 hours time-consuming by dropping funel (1) and (2)
It is added dropwise into reaction unit.After completion of dropwise addition, 0.1 part and 5.0 parts of ion exchange water of investment APS, and stir 1 hour.It is cold
But to 75 DEG C, 0.1 part of investment APS, with 5.0 parts of ion exchange water and after stirring 1 hour, is diluted to concentration with ion exchange water and reaches
To 20%, reaction product is obtained.
Embodiment 1-2~1-30, comparative example 1-1~1-3
It is set as composition shown in table 2, is synthesized by preparation method 1, respectively obtains reaction product.
Embodiment 2-1 (makes (A) ingredient and (B2) ingredient react (hereinafter referred to as preparation method 2))
It is thrown into the reaction unit for having blender, thermometer, reflux cooling tube, nitrogen ingress pipe and two dropping funels
Enter 300.0 parts of ion exchange water, after being passed through the oxygen that nitrogen removes in reaction system, is heated to 85 DEG C.Separately to dropping funel
(1) in investment 284.8 parts of 50%AM aqueous solution, 10.4 parts of IA, 9.6 parts of 80%AA, 41.8 parts of DM, 62.8 parts of 60%DML,
8.8 parts of SMAS, 1.32 parts of DMAA and 193.1 parts of ion exchange water.In addition, to 0.2 part of investment APS in dropping funel (2) and
60 parts of ion exchange water.Then, it is added dropwise by dropping funel (1) and (2) time-consuming 3 hours into reaction unit.Knot is added dropwise
Shu Hou, 0.1 part of investment APS and 5.0 parts of ion exchange water simultaneously stir 1 hour, obtain polymer (B2-1).Thing is added thereto
After 416.7 parts of (A-1) ingredient first prepared, it is cooled to 75 DEG C and puts into 0.1 part of APS and 5.0 parts of ion exchange water, stirring 1 is small
Shi Hou is diluted to concentration with ion exchange water and reaches 20%, obtains reaction product.
Embodiment 2-2~2-30, comparative example 2-1~2-3
Hereinafter, being set as composition shown in table 2, is synthesized respectively by preparation method 2, obtain reaction product.
[table 2]
(B1) ingredient (polymerize) by embodiment 1-31 in (A) ingredient
It is thrown into the reaction unit for having blender, thermometer, reflux cooling tube, nitrogen ingress pipe and two dropping funels
Enter 416.7 parts of (A-1) ingredient prepared in advance, after being passed through the oxygen that nitrogen removes in reaction system, until being heated to 85 DEG C.Separately
Row to 284.8 parts of 50%AM aqueous solution of investment in dropping funel (1), 10.4 parts of IA, 9.6 parts of 80%AA, 41.8 parts of DM,
62.8 parts of 60%DML, 8.8 parts of SMAS, 1.32 parts of DMAA and 193.1 parts of ion exchange water.In addition, in dropping funel (2)
Put into 0.2 part and 60 parts of ion exchange water of APS.Then, through dropping funel (1) and (2) time-consuming 3 hours into reaction unit
It is added dropwise.After completion of dropwise addition, 0.1 part and 5.0 parts of ion exchange water of investment APS is stirred 1 hour.It is cooled to 75 DEG C and puts into
After 0.1 part and 5.0 parts of ion exchange water of APS, stirring 1 hour, concentration is diluted to ion exchange water and reaches 20%, obtain anti-
Answer product.
Embodiment 1-32~1-33, comparative example 1-4
It is set as composition shown in table 3, is synthesized in the same manner as embodiment 1-31, respectively obtains reaction product.
[table 3]
(method of evaluating performance 1)
The old paper of cardboard is beaten with Niagara (NIAGARA) formula beater, it is free to Canadian standard is adjusted to
Spend (C.S.F) 370ml paper pulp in add aluminum sulfate 1.5%, added to adjust pH 5% sodium hydrate aqueous solution to
pH6.7.Then, it is added using each reaction product obtained in each embodiment and comparative example as paper power reinforcing agent relative to paper pulp
1.0%, after stirring, 180g/m is reached with base weight using TAPPI sheet material machine2Mode carry out papermaking, with 5kg/cm2It carries out 2 minutes
Pressurizing and dehydrating.Then, 3 minutes dry at 105 DEG C using rotary-type drying machine, in 20 DEG C of temperature, the condition of humidity 65%
Relative humidity 24 hours.
(relative breakdown intensity)
It using each test paper obtained in the above method, is measured according to JIS P 8131, with relative breakdown intensity
(kPa·m2/ g) it indicates.Show the result in table 4 and 5 (following same).
(relative tensile strength)
Using each test paper obtained in the above method, it is measured according to JIS P 8113, with relative tensile strength
(Nm/g) it indicates.
(opposite compressive strength)
It using each test paper obtained in the above method, is measured according to JIS P 8126, with opposite compressive strength
(N·m2/ g) it indicates.
[table 4]
[table 5]
[method of evaluating performance 2]
(preparation of coating fluid)
Using reaction product shown in table 6 as paper power reinforcing agent, it is diluted to concentration respectively with ion exchange water and reaches 5%,
Coating fluid is prepared respectively.
(production of coating paper)
For body paper (base weight 150g/m obtained from the old paper paper pulp of cardboard is manufactured paper with pulp2), it is reached with solid-state adhesion amount
To 0.50g/m2Mode, with bar coater, on the two sides of body paper, coating is heated to 50 DEG C of above-mentioned coating fluid, with 105 DEG C of rotation
Formula drum dryer makes it dry 1 minute, to obtain coating paper.It should be noted that the solid-state adhesion amount of coating fluid be by
It is coated with the calculated value of paperboard weight of front and back.
(viscosity of coating fluid)
Using Brookfield viscometer (Toki Sangyo Co., Ltd.'s system), measurement is heated to 50 DEG C of above-mentioned coating fluid, and (concentration is
5.0%) viscosity.Show the result in table 6 (following same).
(opposite compressive strength)
Using by each test paper obtained by the above method, it is measured according to JIS P 8126, it is strong with opposite compression
Spend (Nm2/ g) it indicates.
(internal intensity)
It is measured internal intensity (N/m) using by each coating paper obtained by the above method according to J.Tappi No.18-2.
[table 6]
Claims (8)
1. a kind of paper power reinforcing agent, it includes reacting for starch (A) and any one in monomer component (B1) or its polymer (B2)
Product, the starch (A) have (methyl) acrylate-based in the molecule, and the monomer component (B1) includes (methyl) acryloyl
Amine (b1).
2. paper power reinforcing agent according to claim 1, wherein (A) ingredient is with (methyl) acrylate-based ingredient (a1)
With the reaction product of raw starch.
3. paper power reinforcing agent according to claim 2, wherein (a1) ingredient is selected from unsaturated monocarboxylic acid anhydride, unsaturated dicarboxyl
1 kind in acid anhydrides, compound and unsaturated isocyanate containing unsaturated glycidyl.
4. paper power reinforcing agent described in any one of claim 1 to 3, wherein the raw starch of (A) ingredient is enzyme degradation
Starch.
5. paper power reinforcing agent according to any one of claims 1 to 4, wherein (B1) ingredient includes:
(methyl) acrylamide (b1)；And
Cationic vinyl monomer (b2) and/or anionic property vinyl monomer (b3).
6. paper power reinforcing agent according to claim 5 also includes bridging property vinyl monomer (b4) and/or chain-transferring agent (b5).
7. paper power reinforcing agent described according to claim 1~any one of 6, concentration is 20 weight %, temperature is 25 DEG C
Under conditions of viscosity be 100mPas~30,000mPas.
8. a kind of paper, it includes paper power reinforcing agents according to any one of claims 1 to 7.
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| JP2017189163A JP7047310B2 (en) | 2017-09-28 | 2017-09-28 | Paper strength enhancer and paper |
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| JPH11241294A (en) * | 1998-02-20 | 1999-09-07 | Seiko Kagaku Kogyo Co Ltd | Paper-strengthening agent for paper making and production of strengthened paper |
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| CN104420396A (en) * | 2013-09-02 | 2015-03-18 | 荒川化学工业株式会社 | Paper strengthening agent and papermaking method using same |
| CN105463935A (en) * | 2014-09-30 | 2016-04-06 | 荒川化学工业株式会社 | Papermaking additive and paper obtained by using same |
| CN105735039A (en) * | 2014-12-25 | 2016-07-06 | 荒川化学工业株式会社 | Additive for making paper and paper obtained by using additive |
| CN105980428A (en) * | 2014-12-08 | 2016-09-28 | 播磨化成株式会社 | Acrylamide polymer, paper strength enhancing agent, and paper |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5434409A (en) * | 1977-08-23 | 1979-03-13 | Sanyo Chemical Ind Ltd | Internally adding and treating agent for paper making |
| JPH059891A (en) * | 1990-11-29 | 1993-01-19 | Honen Corp | Method of improving paper strength |
| JPH10259590A (en) * | 1997-03-21 | 1998-09-29 | Misawa Ceramics Corp | Improving agent for surface paper quality using modified starch |
| FI113968B (en) * | 2001-05-23 | 2004-07-15 | Raisio Chem Oy | Solution polymer stabilized with a cationic polysaccharide |
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2017
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11241294A (en) * | 1998-02-20 | 1999-09-07 | Seiko Kagaku Kogyo Co Ltd | Paper-strengthening agent for paper making and production of strengthened paper |
| CN102603977A (en) * | 2012-02-28 | 2012-07-25 | 杭州杭化播磨造纸化学品有限公司 | Preparation method of water-solubility amylum-acrylamide copolymer and application of water-solubility amylum-acrylamide copolymer |
| CN104420396A (en) * | 2013-09-02 | 2015-03-18 | 荒川化学工业株式会社 | Paper strengthening agent and papermaking method using same |
| CN105463935A (en) * | 2014-09-30 | 2016-04-06 | 荒川化学工业株式会社 | Papermaking additive and paper obtained by using same |
| CN105980428A (en) * | 2014-12-08 | 2016-09-28 | 播磨化成株式会社 | Acrylamide polymer, paper strength enhancing agent, and paper |
| CN105735039A (en) * | 2014-12-25 | 2016-07-06 | 荒川化学工业株式会社 | Additive for making paper and paper obtained by using additive |
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| JP2019065406A (en) | 2019-04-25 |
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