CN105229227B - Wrinkle processing bonding agent and crimped paper manufacture method - Google Patents
Wrinkle processing bonding agent and crimped paper manufacture method Download PDFInfo
- Publication number
- CN105229227B CN105229227B CN201480029409.4A CN201480029409A CN105229227B CN 105229227 B CN105229227 B CN 105229227B CN 201480029409 A CN201480029409 A CN 201480029409A CN 105229227 B CN105229227 B CN 105229227B
- Authority
- CN
- China
- Prior art keywords
- bonding agent
- wrinkle processing
- water
- wrinkle
- solid content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- D21H21/146—Crêping adhesives
-
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/52—Epoxy resins
-
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
-
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
-
- 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
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/57—Polyureas; Polyurethanes
-
- 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
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/005—Mechanical treatment
Abstract
Even if the purpose of the present invention is that the coating epithelium dissolution that the moisture providing when a kind of papermaking l Water Paper excellent in adhesion between fleece etc. to bring produces the most easily makes paper depolymerization, can form good wrinkle and can alleviate the wrinkle processing bonding agent that blade coating cutter wears away because formed epithelium is soft.Wrinkle processing bonding agent contains polyamide polyamine epichlorohydrin resins (A) and/or polyamide polyamine polyureas epichlorohydrin resins (B) and softening agent (C), it is characterized in that, this wrinkle processing bonding agent meets all specified conditions.
Description
Technical field
The present invention relates to manufacture toilet paper (toilet paper), napkin (tissue paper), handkerchief paper (towel paper)
With the wrinkle processing bonding agent used when the paper such as sanitary paper such as paper for kitchen (kitchen paper).
Background technology
When manufacturing the sanitary papers such as toilet paper, napkin, handkerchief paper, paper for kitchen, in order to give soft to goods
Soft or bulkiness (bulky), (wrinkle adds to implement to give the operation of the most very thin wrinkle (crepe) to fleece
Work).Wrinkle processing is to be made up of such a operation: wet fleece is dried toward the Yankee with drying process
Device (yankee dryer) and known rotating cylinder formula copy paper exsiccator is bonding, after drying, with blade coating cutter from dry
Dry device surface scraping fleece, gives wrinkle to fleece.
Generally, when carrying out wrinkle processing, it is coated with wrinkle processing bonding agent toward dryer surface, is allowed to shape
Become epithelium.Epithelium in dryer surface is favorably improved the fleece bonding force to Yankee dryer, protection
Dryer surface does not contact blade coating cutter (doctor blade).
About wrinkle processing bonding agent, once it was suggested such as polyamide polyamine epichlorohydrin resins
(polyamidepolyamine epihalohydrin resin) or polyamide polyamine polyureas epichlorohydrin resins
(polyamidepolyaminepolyurea epihalohydrin resin) that thermosetting resin (such as sees patent
Document 1,2,3).On the other hand, also attempted being used in plasticizer wrinkle processing bonding agent.Such as,
It was suggested and allowed adipic acid (adipic acid) and methyl diaminourea propylamine (methylbis (aminopropylamine))
Product and epoxychloropropane (epichlorohydrin) reaction obtain polyamine epichlorohydrin resin
(polyamide epichlorohydrin resin), more dark conjunction of the plasticizer of this resin and polyhydric alcohol system is made
Bonding agent (such as sees patent documentation 4).But, when using these wrinkle processing bonding agents, when Yankee is done
When the resistance to water of the epithelium formed on dry device is weak or because epithelium is weak to the cementability of fleece, it may appear that
The problem that fleece can not be carried out equably wrinkle processing.
Prior art document
Patent documentation
Patent documentation 1: No. 2688950 publication of Japanese invention patent
Patent documentation 2: No. 4831523 publication of Japanese invention patent
Patent documentation 3: No. 5191046 publication of Japanese invention patent
Patent documentation 4: Unexamined Patent 09-041297 publication
The content of invention
Technical problem
Even if the purpose of the present invention is that when a kind of papermaking of offer between fleece l Water Paper excellent in adhesion etc.
The coating epithelium dissolution that the moisture brought produces the most easily makes paper depolymerization, can form good wrinkle and because of institute
Form epithelium softness and the wrinkle processing bonding agent of blade coating cutter abrasion can be alleviated.
Technical scheme
The present inventor, in order to solve the problems referred to above, studies with keen determination, itself found that: specific wrinkle adds
Work bonding agent, excellent in adhesion between fleece, good wrinkle can be formed, then reach the present invention.
That is, the present invention provides following technical scheme:
<1>a kind of wrinkle processing bonding agent, containing polyamide polyamine epichlorohydrin resins (A) and/or polyamides
Amine polyamine polyureas epichlorohydrin resins (B) and softening agent (C), it is characterised in that meet following (1)～(5)
All conditions:
(1) the Azetidinium base in wrinkle processing bonding agent solid content 1g is 0～0.2mEq；
(2) wrinkle processing bonding agent intrinsic viscosity is 0.20～0.55dL/g；
(3) softening agent (C) meets following (i) and (ii): being liquid at (i) boiling point more than 150 DEG C and 80 DEG C, (ii) is water
Insoluble aliphatic polyhydric alcohol (polyol) or NHD (polyethylene glycol dimethyl ether)；
(4) mass ratio is [resin (A) and/or resin (B)]: [softening agent (C)]=100:0.5～70；
(5) resistance to water of method evaluation calculated as described below is 40～100%；
<resistance to water computational methods>
The culture dish (Petri dish) (weight W1 (g)) of the uniform epithelium defining weight 0.05g being modulated is put into
Tea-bag (tea bag) (weight W2 (g)), is placed in 50 DEG C of water the lower immersion of stirring 5 minutes, is allowed to dry, presses
Each tea-bag (weight W3 (g)) measures the weight of above-mentioned culture dish, obtains resistance to water from following formula (1)
Formula (1) resistance to water (%)=100-{ (W1+W2)-W3}/0.05 × 100
In formula, W1 (g) is the weight of the metal culture dish having made epithelium modulation, and W2 (g) is the weight of tea-bag,
W3 (g) is for soaking dried tea-bag and the weight of culture dish.
<2>the wrinkle processing bonding agent as described in above-mentioned<1>, wherein, the weight average of wrinkle processing bonding agent
Molecular weight is 1,000,000～5,000,000.
<3>a kind of crimped paper manufacture method, wherein, processes with viscous including the wrinkle described in above-mentioned<1>or<2>
Connecing agent and being coated with toward dryer surface and meet relative fiber web area solid content is 0.01～500mg/m2Work
Sequence.
<4>the crimped paper manufacture method as described in above-mentioned<3>, wherein, uses softening agent as the interior medicine that adds,
Paper is sanitary paper.
The effect of invention
Even if the moisture that when being provided that a kind of papermaking, between fleece, l Water Paper excellent in adhesion etc. brings produces
Coating epithelium dissolution the most easily make paper depolymerization, can be formed good wrinkle and because formed epithelium softness and can
Alleviate the wrinkle processing bonding agent of blade coating cutter abrasion.
Specific embodiment
The present invention is at least to contain polyamide polyamine epichlorohydrin resins (A) and/or polyamide polyamine polyureas ring
The wrinkle processing bonding agent of oxygen halopropane resin (B) and softening agent (C).That is, following embodiment is included:
At least contain the wrinkle processing bonding agent of polyamide polyamine epichlorohydrin resins (A) and softening agent (C)；At least
Containing polyamide polyamine polyureas epichlorohydrin resins (B) and softening agent (C)；Certainly also have, at least contain polyamides
Amine polyamine epichlorohydrin resins (A), polyamide polyamine polyureas epichlorohydrin resins (B) and softening agent (C)
Wrinkle processing bonding agent.
Specifically, it is the wrinkle processing at least containing polyamide polyamine epichlorohydrin resins (A) and softening agent (C)
With bonding agent, wherein, polyamide polyamine epichlorohydrin resins (A) is to allowing polyalkylene polyamine
The polyamide polyamine that (polyalkylene polyamine) (a) and dicarboxylic acids class (b) react and obtain
(polyamidepolyamine) epoxyhalopropane (epihalohydrin) (c) (x), is allowed to react and obtain.Or
Person, is at least to contain polyamide polyamine polyureas epichlorohydrin resins (B) and softening agent (C), wherein, polyamide
Polyamine polyureas epichlorohydrin resins (B) is to allow polyamide polyamine polyureas
(polyamidepolyaminepolyurea) (y) and epoxyhalopropane (c) react and obtain, and polyamide polyamine gathers
Urea (y) allows polyalkylene polyamine (a), dicarboxylic acids class (b) and ureas (d) react and to obtain.Certainly, also may be used
Being at least to contain polyamide polyamine epichlorohydrin resins (A), polyamide polyamine polyureas epichlorohydrin resins
(B) and softening agent (C), wherein, polyamide polyamine epichlorohydrin resins (A) is to allowing polyalkylene polyamine (a)
The polyamide polyamine (x) reacted with dicarboxylic acids class (b) and obtain, allows epoxyhalopropane (c) react and to obtain
's；Polyamide polyamine polyureas epichlorohydrin resins (B) is to allow polyamide polyamine polyureas (y) and epoxyhalopropane (c)
React and obtain, and polyamide polyamine polyureas (y) is to allow polyalkylene polyamine (a), dicarboxylic acids class (b) and urea
Class (d) is reacted and is obtained.
Polyalkylene polyamine (a) used in the present invention, as long as have the alkylidene of more than at least 2 in molecule
With the thing of the amino of more than 2, such as can include diethylenetriamines (diethylenetriamine), three
Ethylene tetra (triethylenetetramine), tetraethylenepentamine (tetraethylenepentamine), five ethyls six
Amine (pentaethylenehexamine), Hexaethyl seven amine (hexaethyleneheptamine), dipropyl triamine
(dipropylenetriamine), tripropyl tetramine (tripropylenetetramine), imino-bis-propylamine
Etc., (iminobispropylamine) these both can be used alone wherein a kind also can and with more than two kinds.These are worked as
In, because of excellent in adhesion, preferably diethylenetriamines, trien, tetraethylenepentamine, particularly preferred two is sub-
Ethyl triamine.These both can be used alone wherein a kind also can and with more than two kinds.Additionally can also be with poly-alkylene
Base polyamine (a) is used together ethylenediamine (ethylene diamine), propane diamine (propylene diamine) or six methylenes
Alkylenediamine (alkylene diamine) class, the episilon amino caproic acid such as base diamidogen (hexamethylene diamine)
The aminocarboxylic acids of carbon number 1～6 such as (ε-aminocaproic acid), epsilon-caprolactams (ε-caprolactam) are that
Lactams (lactam) class of the amino carboxylic acid of carbon number 1～6.
As dicarboxylic acids class (b) used in the present invention, can include in molecule have 2 dicarboxylic acids and/
Or derivatives thereof.Such as the monomer of these dicarboxylic acids or diester or anhydride can be included as derivant.
As dicarboxylic acids, such as can include malonic acid (malonic acid), succinic acid, 1,3-propanedicarboxylic acid (glutaric acid),
Adipic acid (adipic acid), 1,5-pentanedicarboxylic acid. (pimelic acid), suberic acid (suberic acid), Azelaic Acid (azelaic
Acid), decanedioic acid (sebacic acid), tridecandioic acid (brassylic acid), dodecanedioic acid (dodecanedioic
Acid) etc., from industrial point of view, the preferably dicarboxylic acids of carbon number 5～10.It addition, as the list of dicarboxylic acids
Body or diester preferably enumerate lower alcohol (first, second, the third) ester of carbon number 1～5, particularly preferred carbon number 1～3
Lower alcohol (first, second, third) ester.As anhydride, the intramolecular dehydration condensation substance of free acid can be included, this
Outer also have and the condensation substance of low-grade carboxylic acid, preferably with the condensation substance etc. of the low-grade carboxylic acid of carbon number 1～5.As from
Especially preferred dicarboxylic acids class (b) of industrial point of view, can include adipic acid, Glutaric Acid Dimethyl ester (glutaric
Acid dimethyl ester), dimethyl adipate (adipic acid dimethyl ester).Above-mentioned dicarboxylic acids class (b)
1 kind can be used or and use two or more.Also have, it is possible to do not hindering in the range of effect of the present invention, replace two
Unit carboxylic acids (b) a part and use in citric acid or trimellitic acid (trimellitic acid) etc., molecule and have 3
Above carboxylic acid and/or its carboxylate or there is the derivant of its anhydride.
As ureas (d) used in the present invention, urea, thiourea (thiourea), guanylurea such as can be included
(guanylurea), phenylurea (phenylurea), MU (methylurea), dimethyl urea (dimethylurea)
Deng, wherein, from the particularly preferred urea of industrial point of view.A part as these ureas (d), it is possible to substituted urea class (d)
And use the compound of the unsubstituted amide groups of N that can make amide exchange reaction with amino with more than 1,
Such as aliphatic amide type or the benzamide such as acetamide (acetamide), propionic acid amide. (propionamide)
(benzamide), the aromatic amides class etc. such as phenyl acetamide (phenylacetamide).
Epoxyhalopropane (c) used in the present invention can include epoxychloropropane, epoxy bromopropane
(epibromohydrin) etc., but from industrial point of view, preferred epoxychloropropane.
Polyamide polyamine epichlorohydrin resins (A) in the present invention is to allow polyalkylene polyamine (a) and binary carboxylic
The resin that the polyamide polyamine (x) that acids (b) reaction obtains reacts with epoxyhalopropane (c) and obtains.
The polyamide polyamine epichlorohydrin resins (A) of the present invention, preferably rubs by polyalkylene polyamine (a) 38～58
Your %, dicarboxylic acids class (b) 37～55 moles of %, epoxyhalopropane (c) 1～14 moles of % react, accordingly
The wrinkle processing bonding agent with excellent epithelium characteristic can be obtained.Particularly preferably polyalkylene polyamine (a) 43～
54% mole, dicarboxylic acids class (b) 42～52 moles of %, epoxyhalopropane (c) 1～10 moles of %.
Polyamide polyamine polyureas epichlorohydrin resins (B) in the present invention is to allow polyalkylene polyamine (a), binary
Polyamide polyamine polyureas (y) that carboxylic acids (b) and ureas (d) reaction obtain reacts with epoxyhalopropane (c) and obtains
Resin.Polyalkylene polyamine (a), dicarboxylic acids class (b), ureas (d) reaction can with random order or with
Shi Jinhang reacts.Such as, polyalkylene polyamine (a), dicarboxylic acids class (b) and ureas (d) simultaneous reactions can be allowed；
Or, first allow polyalkylene polyamine (a) and ureas (d) react and obtain polyalkylene polyamine polyureas (polyalkylene
Polyamine polyurea) (z), allow this polyalkylene polyamine polyureas (z) and dicarboxylic acids class (b) react the most again.
Further, it is also possible to first allow polyalkylene polyamine (a) and dicarboxylic acids class (b) react and obtain polyamide polyamine
(x), then allow this polyamide polyamine (x) and ureas (d) react.
Polyamide polyamine polyureas epichlorohydrin resins (B) of the present invention, preferably by polyalkylene polyamine (a) 28～
58 moles of %, dicarboxylic acids class (b) 24～55 moles of %, 37 moles of below % of ureas (d), epoxyhalopropane (c) 1～
11 moles of % react, and can obtain the wrinkle processing bonding agent with excellent epithelium characteristic accordingly.Especially
Preferably polyalkylene polyamine (a) 33～54%, dicarboxylic acids class (b) 28～52 moles of %, 35 moles of % of ureas (d)
Below, epoxyhalopropane (c) 1～10 moles of %.
Polyalkylene polyamine (a) and dicarboxylic acids class (b) or polyalkylene polyamine (a) and ureas (d), polyamide
The condensation reaction of polyamine (x) and ureas (d), is that heating carries out being dehydrated and/or dealcoholysis and/or deamination reaction.From reaction
Controlling viewpoint, reaction temperature 110～250 DEG C, response time 1～8 hours are best.Now, as polycondensation
Reaction catalyst can be used alone or in combination of two kinds or more sulphuric acid, benzenesulfonic acid (benzenesulfonic acid),
The sulphonic acids such as p-methyl benzenesulfonic acid (p-toluenesulfonic acid) or phosphoric acid, phosphonic acids (phosphonic acid),
Phosphoric acid class, other well-known catalysts such as hypophosphorous acid (hypophosphorous acid).
When allowing polyamide polyamine (x) and/or polyamide polyamine polyureas (y) react with epoxyhalopropane (c), reactant liquor is dense
Degree is preferably 10～80 mass %；Reaction temperature, owing to depending on reaction density, so needing suitably to adjust,
Generally preferably carry out at 5～90 DEG C.
About the reaction of polyamide polyamine (x) and/or polyamide polyamine polyureas (y) with epoxyhalopropane (c), gained gathers
Amide polyamine epichlorohydrin resins (A) and/or polyamide polyamine polyureas epichlorohydrin resins (B), by holding
Continue and be reacted to the viscosity benchmark at 25 DEG C of the aqueous solution by solid content 15 mass % and have 10～350mPa
Viscosity in the range of s, preferably 50～250mPa s, can obtain the resin that bonding force is excellent.Reactant liquor viscosity
If having arrived in this range of viscosities, reactant liquor being added water and carries out cooling etc. and allow reaction stop, resin (A) can be obtained
And/or the aqueous solution of resin (B).
The aqueous solution of wrinkle processing bonding agent of the present invention, for improving storage stability or controlling epithelium formation,
PH can be adjusted.PH adjusts and can carry out by adding pH regulator.As pH regulator, such as
Can preferably include: the such as mineral acid such as hydrochloric acid, sulphuric acid, nitric acid, phosphoric acid, the most halogen-containing
Mineral acid；The organic acid such as formic acid, acetic acid；Sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide,
The inorganic alkali such as sodium carbonate, potassium carbonate；Ammonia, diethylamine, triethylamine, propylamine, butylamine, di-iso-butylmanice
(diisobutylamine), azanol (hydroxyamine), ethanolamine (ethanolamine), diethanolamine
(diethanolamine) mono-amine compound such as.
In the solid content 1g of wrinkle processing bonding agent of the present invention, Azetidinium base is necessary for 0～0.2mEq,
Preferably 0～0.1mEq.In solid content 1g, Azetidinium base (AZR made in brief note the most sometimes) is more than 0.2mEq
Time, moistening paper power effect can be embodied as wrinkle processing bonding agent when using, can be to the hydrolysis of toilet paper etc.
Property brings harmful effect.
The intrinsic viscosity of wrinkle processing bonding agent be necessary for 0.20～0.55dL/g, preferably 0.25～
0.5dL/g.Here, intrinsic viscosity system depends on the molecular weight of the macromolecular chain of independent dissolution, shape in solvent
Physical quantity with size.If in this scope, then it is easy for when using as wrinkle processing bonding agent being formed and glues
The epithelium that connecing property is excellent.
Contained by wrinkle processing bonding agent, softening agent (C) must be: for liquid at (i) boiling point more than 150 DEG C and 80 DEG C
Body；And (ii) is water solublity aliphatic polyol or NHD.
Can preferably include as above-mentioned softening agent (C): ethylene glycol (ethylene glycol), diethylene glycol
(diethylene glycol), tri ethylene glycol (triethylene glycol), Polyethylene Glycol (polyethylene
Glycol), propylene glycol (propylene glycol), dipropylene glycol (dipropylene glycol), glycerol (glycerol),
1,3 butylene glycol (1,3-butanediol), 1,4-butanediol (1,4-butanediol), diethylene glycol dimethyl ether
(diethylene glycol dimethyl ether), TRIGLYME (triethylene glycol dimethyl
Ether), tetraethyleneglycol dimethyl ether (tetraethylene glycol dimethyl ether) etc., particularly preferred poly-second two
Alcohol, diethylene glycol dimethyl ether, TRIGLYME.
Wrinkle processing bonding agent of the present invention, mass ratio must be " resin (A) and/or resin (B) ": " softening agent
(C) "=100:0.5～70.Preferred mass ratio is " resin (A) and/or resin (B) ": " softening agent (C) "=100:5～
30, more preferably 100:5～20.The mass ratio of softening agent (C), if less than 0.5, then can not get softening coating
The effect of epithelium；And if during more than 70, then cementability is remarkably decreased.
Wrinkle processing bonding agent of the present invention, the resistance to water that (1) is obtained as the following formula in following resistance to water is evaluated must
Must be 40～100%.
Tea-bag (weight put into by the culture dish (weight W1 (g)) of the uniform epithelium defining weight 0.05g being modulated
Amount W2 (g)), it is placed in 50 DEG C of water the lower immersion of stirring 5 minutes, is allowed to dry, by each tea-bag (weight W3 (g))
Measure the weight of above-mentioned culture dish, obtain resistance to water from following formula (1)
Formula (1) resistance to water (%)=100-{ (W1+W2)-W3}/0.05 × 100
In formula, W1 (g) is the weight of the metal culture dish having made epithelium modulation, and W2 (g) is the weight of tea-bag,
W3 (g) is for soaking dried tea-bag and the weight of culture dish.
If resistance to water is in above-mentioned scope, then the coating epithelium dissolution that the moisture that l Water Paper etc. bring produces is few, just holds
In Yankee dryer, easily form coating epithelium.
The weight average molecular weight of wrinkle processing bonding agent of the present invention, in order to obtain the cementability of excellence, is preferably
1000000～5,000,000, particularly preferred 1,500,000～4,500,000.Weight average molecular weight in the present invention, is according to implementing
Mensuration described in example.
As the concrete grammar that wrinkle processing bonding agent of the present invention is coated with toward paper, have in manufacturing process in poplar
Method that base exsiccator front is sprayed toward l Water Paper, directly toward the method for Yankee dryer surface injection with by upper
State the method that these Combination of Methods are carried out.Preferably directly toward the method for Yankee dryer surface injection, because holding
Easily obtain the effect as wrinkle processing bonding agent.
For wrinkle processing bonding agent of the present invention, in order to control bonding to Yankee dryer surface of fleece
Power, can and with wrinkle processing releasing agent (release agent).As wrinkle processing releasing agent, such as can example
Enumerate silicone oil (silicone oil), hydrocarbon ils (hydrocarbon oil), oxidized petroleum waves (oxidized wax), paraffin (paraffin
Wax), Tissuemat E (polyethylene wax), cationic surfactant, anionic surfactant,
Amphoteric surfactant etc..These can be used alone or in combination of two kinds or more.
When wrinkle processing bonding agent of the present invention directly sprays toward the surface of Yankee dryer, preferably wrinkle is added
Work bonding agent dilutes 10～1000 times, and emitted dose is set to 0.01～500mg/m by resin solid content benchmark2,
Especially preferably it is set to 0.1～300mg/m2, be so readily obtained be suitable to wrinkle processing be coated with epithelium uniformly.
If outside this scope, then will not be sufficiently formed coating epithelium, or coating epithelium has dirt accumulation, all can make
Obtain wrinkle processing and become difficulty.
The using method of wrinkle processing bonding agent in the present invention, although above-mentioned say be on paper be coated with, but
As alternate manner, it is possible to add (inside adding) toward paper stock (pulp) and use, or in add and both be coated with
Dual-purpose.When inside adding wrinkle processing bonding agent, generally, relative paper pulp solid content is by wrinkle processing bonding agent
Solid content 0.01～1 mass %, preferably 0.01～0.5 the ratio of mass % be advisable toward adding in paper.
As the paper being adapted in use to wrinkle processing bonding agent of the present invention to carry out wrinkle processing, from feel viewpoint,
Preferably the grammes per square metre of paper is 10～45g/m2, density is 0.1～0.4g/cm3If, toilet paper or napkin be then 0.2～
0.3g/cm3.It addition, being longitudinally dried breaking length (JIS P 8113) is 0.3～2.5km, if toilet paper or napkin
Words, from water-disintegrable viewpoint, preferably 0.2～0.8km.Further, when making sanitary paper use, from use
When wipe the viewpoint of effect, absorption of water (Japanese Industrial Standards JIS S 3104) be preferably paper using 2 stacked 1～
10 seconds.
Wrinkle processing bonding agent of the present invention is used to carry out the paper of wrinkle processing, preferably toilet paper, napkin, hands
The sanitary papers such as towel paper, paper for kitchen, as paper pulp raw material, can contain kraft pulp or sulfite pulp etc.
High receipts are bleached or do not bleached to bleaching or non-bleached chemical paper pulps, ground wood pulp, mechanical pulp or thermo-mechanical pulp etc.
The old paper paper pulp such as rate paper pulp, old newspaper, outdated magazine, old corrugated paper or old deinking paper.Additionally, it is possible to containing upper
State paper pulp raw material and polyamide (polyamide), polyimides (polyimide), polyester (polyester), polyene
And the mixture of the synthetic fibers such as polyvinyl alcohol (polyvinyl alcohol) (polyolefine).
When manufacturing the paper that use wrinkle processing bonding agent of the present invention carries out wrinkle processing, it is possible in order to realize respectively
Physical property kind required by paper, uses softening agent, filler, sizing agent as required, is dried paper power reinforcing agent, wet
Moisten paper power reinforcing agent, and stay reinforcing agent, bulking agent, thickness of paper reinforcing agent, opaque agent and drainability to strengthen
The additives such as agent.These both can be used alone also can and with more than two kinds.Wherein, excellent in order to obtain feel
Paper, preferably in add or add outward softening agent.
As softening agent, fatty acid amide epichlorohydrin resins (fatty acid amide can be included
Epihalohydrin resin) (S1), there is quaternary ammonium salt (S2), fatty acid and/or the aliphatic of alkyl and/or thiazolinyl
The alkylene oxide (alkylene oxide) reactant (S3) etc. of alcohol.Preferred fatty acid amide epoxy halogen in the middle of these
Propane resin (S1), because of its in the present invention soft effect excellent.These both can be used alone also can and with two kinds
Above.Generally, relatively solid content 0.01～1 mass %, preferably 0.01～0.5 mass % can be pressed by paper pulp solid content
Ratio make an addition to paper.
Embodiment
Embodiment exemplified below and comparative example specifically describe the present invention, but the present invention is not by these example institutes
Limit.It addition, in each example, unless otherwise specified, " % " all represents " quality % ".
Embodiment 1
<manufacture of polyamide polyamine (x-1)>
Two are put into sub-toward the four mouthfuls of round-bottomed flasks possessing thermometer, reflux condenser, blender and nitrogen conduit
Ethyl triamine (being the most sometimes abbreviated work " DETA ") 103g (1mol), 95% sulphuric acid 0.52g (0.005mol), one
Limit stirring interpolation adipic acid 146g (1mol) on one side, under nitrogen flowing, by the water that generated outside system
Discharging while heating up, after reacting 3 hours at 175 DEG C, gradually adding water, being adjusted to solid content 35%, gathered
Amide polyamine aqueous solution (x-1).
<manufacture of wrinkle processing bonding agent>
Epoxychloropropane 7.4g (0.08mol) is added toward polyamide polyamine aqueous solution (x-1) full dose obtained above,
It is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, solid content is adjusted to 15%, rise
After temperature to 70 DEG C, terminate reaction when viscosity reaches 45mPa s, obtain polyamide polyamine epichlorhydrin tree
Fat (A-1).Then, add propylene glycol 12g as softening agent (C) and (make relative resin (A-1) solid content 100 mass %
It is 5 mass %), obtain being adjusted to by solid content the wrinkle processing bonding agent of 15% with water.
Embodiment 2
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-1) full dose obtained the same manner as in Example 1
12g (0.13mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, solid content is adjusted
Whole is 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 470mPa s, obtains polyamide and gathers
Amine epichlorohydrin resin (A-2).Then, add propylene glycol 99g as softening agent (C) and (make relative resin (A-2)
Solid content 100 mass % is 30 mass %), obtain solid content being adjusted to the wrinkle processing of 15% with viscous with water
Connect agent.
Embodiment 3
<manufacture of polyamide polyamine (x-2)>
Two are put into sub-toward the four mouthfuls of round-bottomed flasks possessing thermometer, reflux condenser, blender and nitrogen conduit
Ethyl triamine 108g (1.05mol), 95% sulphuric acid 0.52g (0.005mol), stir and add adipic acid
146g (1mol), under nitrogen flowing, discharges the water generated while heating up, at 175 DEG C outside system
After reacting 6 hours, gradually add water, be adjusted to solid content 35%, obtain polyamide polyamine aqueous solution (x-2).
<manufacture of wrinkle processing bonding agent>
Epoxychloropropane 18.5g (0.2mol) is added toward polyamide polyamine aqueous solution (x-2) full dose obtained above,
It is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, solid content is adjusted to 15%, rise
After temperature to 70 DEG C, terminate reaction when viscosity reaches 50mPa s, obtain polyamide polyamine epichlorhydrin tree
Fat (A-3).Then, adding glycerol (glycerine) 61g as softening agent (C) (makes relative resin (A-3) admittedly contain
Measuring 100 mass % is 20 mass %), obtain with 15% sulphuric acid and water pH is adjusted to 5, solid content is adjusted to
The wrinkle processing bonding agent of 15%.
Embodiment 4
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-2) full dose obtained the same manner as in Example 3
7.4g (0.08mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 20mPa s, obtain polyamide and gather
Amine epichlorohydrin resin (A-4).Then, add glycerol 58g as softening agent (C) and (make relative resin (A-4)
Solid content 100 mass % is 20 mass %), obtain solid content being adjusted to the wrinkle processing of 15% with viscous with water
Connect agent.
Embodiment 5
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-2) full dose obtained the same manner as in Example 3
14.8g (0.16mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 510mPa s, obtain polyamide
Polymeric amine epichlorohydrin resin (A-5).Then, add glycerol 60g as softening agent (C) and (make relative resin (A-5)
Solid content 100 mass % is 20 mass %), obtain solid content being adjusted to the wrinkle processing of 15% with viscous with water
Connect agent.
Embodiment 6
<manufacture of polyamide polyamine polyureas (y-1)>
Two are put into sub-toward the four mouthfuls of round-bottomed flasks possessing thermometer, reflux condenser, blender and nitrogen conduit
Ethyl triamine 105g (1.02mol), 95% sulphuric acid 0.52g (0.005mol), stir and add adipic acid
146g (1mol), under nitrogen flowing, discharges the water generated while heating up, at 175 DEG C outside system
After reacting 6 hours, gradually add water, be adjusted to solid content 98%.Then, interpolation urea 12g (0.2mol), 125 DEG C
After lower reaction 2 hours, gradually add water, be adjusted to solid content 35%, obtain polyamide polyamine polyureas aqueous solution
(y-1)。
<manufacture of wrinkle processing bonding agent>
Epoxychloropropane is added toward polyamide polyamine polyureas aqueous solution (y-1) full dose obtained above
8.3g (0.09mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 95mPa s, obtain polyamide and gather
Amine polyureas epichlorohydrin resin (B-1).Then, add glycerol 59g as softening agent (C) and (make relative resin
(B-1) solid content 100 mass % is 20 mass %), obtain being adjusted to by solid content the wrinkle processing of 15% with water
Use bonding agent.
Embodiment 7
<manufacture of polyamide polyamine polyureas (y-2)>
Two are put into sub-toward the four mouthfuls of round-bottomed flasks possessing thermometer, reflux condenser, blender and nitrogen conduit
Ethyl triamine 105g (1.02mol), 95% sulphuric acid 0.52g (0.005mol), stir and add adipic acid
146g (1mol), under nitrogen flowing, discharges the water generated while heating up, at 175 DEG C outside system
After reacting 6 hours, gradually add water, be adjusted to solid content 98%.Then, interpolation urea 24g (0.4mol), 125 DEG C
After lower reaction 2 hours, gradually add water, be adjusted to solid content 35%, obtain polyamide polyamine polyureas aqueous solution
(y-2)。
<manufacture of wrinkle processing bonding agent>
Epoxychloropropane is added toward polyamide polyamine polyureas aqueous solution (y-2) full dose obtained above
8.3g (0.09mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 65mPa s, obtain polyamide and gather
Amine polyureas epichlorohydrin resin (B-2).Then add glycerol 60g and (make relative resin (B-2) solid content 100
Quality % is 20 mass %), obtain being adjusted to by solid content the wrinkle processing bonding agent of 15% with water.
Embodiment 8
<manufacture of polyamide polyamine (x-3)>
Two are put into sub-toward the four mouthfuls of round-bottomed flasks possessing thermometer, reflux condenser, blender and nitrogen conduit
Ethyl triamine 101g (0.98mol), 95% sulphuric acid 0.52g (0.005mol), stir and add adipic acid
146g (1mol), under nitrogen flowing, discharges the water generated while heating up, at 175 DEG C outside system
After reacting 6 hours, gradually add water, be adjusted to solid content 35%, obtain polyamide polyamine aqueous solution (x-3).
<manufacture of wrinkle processing bonding agent>
Epoxychloropropane 5.6g (0.06mol) is added toward polyamide polyamine aqueous solution (x-3) full dose obtained above,
It is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, solid content is adjusted to 15%, rise
After temperature to 70 DEG C, terminate reaction when viscosity reaches 60mPa s, obtain polyamide polyamine epichlorhydrin tree
Fat (A-6).Then glycerol 56g (making relative resin (A-6) solid content 100 mass % is 20 mass %) is added,
Obtain being adjusted to by solid content the wrinkle processing bonding agent of 15% with water.
Embodiment 9
<manufacture of polyamide polyamine (x-4)>
Two are put into sub-toward the four mouthfuls of round-bottomed flasks possessing thermometer, reflux condenser, blender and nitrogen conduit
Ethyl triamine 108g (1.05mol), 95% sulphuric acid 0.52g (0.005mol), stir and add adipic acid
146g (1mol), under nitrogen flowing, discharges the water generated while heating up, at 175 DEG C outside system
After reacting 6 hours, gradually add water, be adjusted to solid content 35%, obtain polyamide polyamine aqueous solution (x-4).
<manufacture of wrinkle processing bonding agent>
Epoxychloropropane 11.1g (0.12mol) is added toward polyamide polyamine aqueous solution (x-4) full dose obtained above,
It is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, solid content is adjusted to 15%, rise
After temperature to 70 DEG C, terminate reaction when viscosity reaches 60mPa s, obtain polyamide polyamine epichlorhydrin tree
Fat (A-7).Then, add glycerol 59g as softening agent (C) and (make relative resin (A-7) solid content 100 mass %
It is 20 mass %), obtain being adjusted to by solid content the wrinkle processing bonding agent of 15% with water.
Embodiment 10
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-4) full dose obtained the same manner as in Example 9
11.1g (0.12mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 80mPa s, obtain polyamide and gather
Amine epichlorohydrin resin (A-8).Then, add propylene glycol 59g as softening agent (C) and (make relative resin (A-8)
Solid content 100 mass % is 20 mass %), obtain solid content being adjusted to the wrinkle processing of 15% with viscous with water
Connect agent.
Embodiment 11
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-4) full dose obtained the same manner as in Example 9
11.1g (0.12mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 80mPa s, obtain polyamide and gather
Amine epichlorohydrin resin (A-9).Then, add Polyethylene Glycol (degree of polymerization 200) 59g as softening agent (C) (to make
Resin (A-9) solid content 100 mass % relatively is 20 mass %), obtain, with water, solid content is adjusted to 15%
Wrinkle processing bonding agent.
Embodiment 12
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-4) full dose obtained the same manner as in Example 9
11.1g (0.12mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 80mPa s, obtain polyamide and gather
Amine epichlorohydrin resin (A-10).Then, add diethylene glycol dimethyl ether 59g as softening agent (C) and (make phase
It is 20 mass % to resin (A-10) solid content 100 mass %), obtain, with water, solid content is adjusted to 15%
Wrinkle processing bonding agent.
Embodiment 13
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-4) full dose obtained the same manner as in Example 9
11.1g (0.12mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 80mPa s, obtain polyamide and gather
Amine epichlorohydrin resin (A-11).Then, add TRIGLYME 59g as softening agent (C) and (make phase
It is 20 mass % to resin (A-11) solid content 100 mass %), obtain, with water, solid content is adjusted to 15%
Wrinkle processing bonding agent.
Comparative example 1 (more than the AZR amount of wrinkle processing bonding agent during over range)
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-1) full dose obtained the same manner as in Example 1
37g (0.4mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, solid content is adjusted
Whole is 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 100mPa s, obtains polyamide and gathers
Amine epichlorohydrin resin (A-12).Then, add propylene glycol 64g as softening agent (C) and (make relative resin (A-12)
Solid content 100 mass % is 20 mass %), add 15% sulphuric acid and water, obtain pH be adjusted to 3.2, solid content
It is adjusted to the wrinkle processing bonding agent of 15%.
Comparative example 2 (being equivalent to the embodiment 1 of the Japanese invention patent the 4831523rd of prior art)
<manufacture of polyamide polyamine polyureas (y-3)>
Two are put into sub-toward the four mouthfuls of round-bottomed flasks possessing thermometer, reflux condenser, blender and nitrogen conduit
Ethyl triamine 105.3g (1.02 moles), stirs and adds adipic acid 146.1g (1 mole), while will
The water generated is discharged while heating up outside system, reacts 3 hours at 170 DEG C.Then, reactant liquor is cooled down
To 130 DEG C, add urea 12g (0.2 mole), after this temperature carries out 2 hours deamination reactions, gradually add water,
Polyamide polyamine polyureas aqueous solution (y-3) 450g to solid content 50%.
<manufacture of wrinkle processing bonding agent>
Polyamides is put into toward the four mouthfuls of round-bottomed flasks possessing thermometer, reflux condenser, blender and the funnel that drips
Amine polyamine polyureas aqueous solution (y-3) 200g, adds epoxychloropropane 5.5g (the proportioning phase as resin B at 20 DEG C
When in adipic acid 1 mole: epoxychloropropane 0.13 mole), then it is heated to 30 DEG C, is incubated at such a temperature
10 minutes, obtain polyamide polyamine polyureas epichlorohydrin resin (B-3).Then, add water 122g, is heated to
50 DEG C, remain at such a temperature after viscosity reaches 200mPa s (25 DEG C), add 30% sulphuric acid and water, obtain
PH is adjusted to 6, solid content be adjusted to 15% wrinkle processing bonding agent.
Comparative example 3 (being equivalent to the embodiment 1 of the Japanese invention patent the 5191046th of prior art)
Diethylenetriamines is put into toward the four mouthfuls of round-bottomed flasks possessing thermometer, condenser and blender
108.2g (1.05 moles), adipic acid 146.1g (1.00 moles), water 146.1g, carried out at 160～170 DEG C
Dehydration 6 hours, obtains polyamide polyamine aqueous solution.Add water thereto, obtain 50% polyamide polyamine
Aqueous solution (x-5) 440g.Then, put into above-mentioned toward the four-hole boiling flask possessing thermometer, condenser and blender
Polyamide polyamine aqueous solution (x-5) 112.5g and water 241.0g, puts into again epoxychloropropane 10.5g (as Resin A
Proportioning be equivalent to adipic acid 1 mole: epoxychloropropane 0.44 mole).Thereafter, it is warmed up to 50 DEG C, keeps
12 hours, obtain polyamide polyamine epichlorhydrin resin (A-13).Then, under synthermal, 98% sulfur is added
Acid 1.0g (0.01 mole), obtains being adjusted to by solid content the wrinkle processing bonding agent of 15% with water.
Comparative example 4 when over range (intrinsic viscosity of wrinkle processing bonding agent low and)
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-4) full dose obtained the same manner as in Example 9
3.7g (0.04mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, terminates reaction when viscosity reaches 45mPa s, obtain polyamide and gather
Amine epichlorohydrin resin (A-14).Then, add propylene glycol 57g and (make relative resin (A-14) solid content 100
Quality % is 20 mass %), obtain being adjusted to by solid content the wrinkle processing bonding agent of 15% with water.
The comparative example 5 resistance to water evaluation of estimate over range of the wrinkle processing bonding agent (time)
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-4) full dose obtained the same manner as in Example 9
7.4g (0.08mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, adds 98% sulphuric acid 10.8g when viscosity reaches 45mPa s, terminate
Reaction, obtains polyamide polyamine epichlorhydrin resin (A-15).Then, add propylene glycol 58g (to make relatively to set
Fat (A-15) solid content 100 mass % is 20 mass %), obtain with 15% sulphuric acid and water pH is adjusted to 5,
Solid content is adjusted to the wrinkle processing bonding agent of 15%.
Comparative example 6 when over range (intrinsic viscosity of wrinkle processing bonding agent high and)
Epoxychloropropane is added toward polyamide polyamine aqueous solution (x-4) full dose obtained the same manner as in Example 9
14.8g (0.16mol), is warmed up to 30 DEG C, at such a temperature insulation 1 hour.Then, add water, by solid content
It is adjusted to 15%, after being warmed up to 70 DEG C, adds 98% sulphuric acid 10.8g when viscosity reaches 45mPa s, terminate
Reaction, obtains polyamide polyamine epichlorhydrin resin (A-16).Then, add propylene glycol 59g (to make relatively to set
Fat (A-16) solid content 100 mass % is 20 mass %), obtain with 15% sulphuric acid and water pH is adjusted to 5,
Solid content is adjusted to the wrinkle processing bonding agent of 15%.
Synthesis example 1 (being equivalent to the manufacture example of the softening agent of fatty acid amide epoxyhalopropane (S1))
Gradually add toward the tetra-mouthfuls of round-bottomed flasks of 3L possessing thermometer, reflux condenser, blender and the funnel that drips
Add the diethylenetriamines 103g (1mol) as polyalkylene polyamine class, unitary carboxylic as carbon number 6～24
Cocos nucifera oil oleic acid (oleic acid/linoleic acid/Palmic acid (mixing quality the ratio 70/20/10)) 559g (2mol) of acids.It is warmed up to
180 DEG C, the water generated being discharged while being allowed to react 3 hours outside system, obtaining amide compound.
The residue amino amount of obtained amide compound is 2mmol/g.Then, above-mentioned amide compound is added at 50 DEG C
(in bracket, numeric representation is polyoxyethylated flat for thing 100g (as amino 0.16mol), polyoxyethylene (45) stearylamine
The most additional molal quantity.) 5g, water 100g, epoxychloropropane 5.9g (0.064mol) as epoxyhalopropane class,
Stir 30 minutes.Then, place reaction liquid into after reacting 1 hour at 70 DEG C, cool down reactant liquor
Add water adjustment, makes solid content become 30 mass %, obtain concentration 30%, viscosity 350mPa s, melting point 29 DEG C,
The softening agent for paper of particle diameter 4 μm.
<molecular weight determination>
In the present invention, the weight average molecular weight of wrinkle processing bonding agent is to utilize to connect multi-angle light scattering at GPC
The GPC-MALS method of detector is obtained by following condition determination.
GPC main body: Agilent Technologies (Agilent Technologies) makes
LC1100 series chromatographic column (column): Showa Denko K. K SHODEX SB806M HQ
Leacheate: the N/15 phosphate buffer (pH3) containing N/10 sodium nitrate
Detector 1: Wyatt Technology of U.S. multi-angle light diffusion detector DAWN
Detector 2: Showa Denko K. K differential refractive index detector RI-101
<mensuration of intrinsic viscosity>
To the 1N ammonium chloride of the solids level concentration 1%, 0.5%, 0.2% of wrinkle processing bonding agent in embodiment
Aqueous solution uses Ubbelohde viscometer (Ubbelohde viscometer) to seek the reduction ratio viscosity measured at temperature 25 DEG C
(reduced specific viscosity)ηsp/ C, obtains intrinsic viscosity [η].
ηsp/ C=[η]+k ' [η]2×C
In formula, C is concentration, and [η] is intrinsic viscosity, and k ' is Huggins constant
<AZR assay>
Measure the sample of the methanol adding known quantity toward wrinkle processing bonding agent1HNMR, from methanol
AZR amount is obtained with the proton ratio (proton ratio) of AZR.Notice goes out, and sample uses relatively
The solid content 1g of wrinkle processing bonding agent adds the thing of methanol 0.01g.
<resistance to water>
Tea-bag (weight put into by the culture dish (weight W1 (g)) of the uniform epithelium defining weight 0.05g being modulated
Amount W2 (g)), it is placed in 50 DEG C of water the lower immersion of stirring 5 minutes, is allowed to dry, by each tea-bag (weight W3 (g))
Measure the weight of above-mentioned culture dish, obtain resistance to water from following formula (1)
Formula (1) resistance to water (%)=100-{ (W1+W2)-W3}/0.05 × 100
In formula, W1 (g) is the weight of the metal culture dish having made epithelium modulation, and W2 (g) is the weight of tea-bag,
W3 (g) is for soaking dried tea-bag and the weight of culture dish.
<adhesive strength evaluation test>
Toward plate (the area 0.2cm being heated to 100 DEG C2) coating Examples 1～13, the wrinkle of comparative example 1～6 add
Work bonding agent and wrinkle agent CR6154 (Nippon PMC K. K.'s wrinkle processing remover), and make this
Wrinkle processing bonding agent solid content reaches 0.3g/m2, this wrinkle agent effective ingredient reaches 0.25g/m2, it is dried 1 point
Zhong Hou, by coated face with 300gf/cm2Toward plate and half paper (grammes per square metre 30g/m of the 2 μ L water that drip2, thick
0.07mm, 5 μ L difference size (drop size) 12 seconds) pressing, with sonde-type initial bonding strength tester (probe tack
Tester) load necessary when peeling off is evaluated.Evaluation result is shown in Table 1,2.
Notice goes out, and adhesive strength numerical value is the highest more good.It addition, use with by wrinkle because obtaining simply
The tendentiousness that occasion that bonding agent is coated with toward exsiccator is the same, so have employed this test.
<epithelium hardness evaluation method>
Wrinkle processing bonding agent solid content 0.13g part of embodiment 1～13, comparative example 1～6 is contained into internal diameter
The metal culture dish of 6.5cm, heat drying (110 DEG C, 2 hours), modulate the skin of wrinkle processing bonding agent
Film.With pencil press lead for retractable pencil soft or hard 6H, 5H, 4H, 3H, 2H, H, F, HB, B, 2B, 3B, 4B,
The order of 5B, 6B draws the epithelium modulated, and is evaluated the hardness of pencil scar do not occur.Will
6H scar do not occurs be set to 15, draw with the pencil that lead for retractable pencil is soft successively, scar do not occurred in 6B
Be set to 2, by 6B occur scar be set to 1.With numerical value low for " soft ", point 15 grades are evaluated.
Evaluation result is shown in Table 1,2.
<soft>1 ← 2 (6B) ← 7 (B) → 15 (6H)<hard>
The hardness of the pencil that scar do not occur corresponding with numerical value is represented in ()
Note that it is assumed that the abrasion of numerical value the lowest plate are the fewest, therefore preferably, less than 6 are advisable.It addition, because energy is simple
Ground obtains the tendentiousness the same with the occasion being coated with toward exsiccator by wrinkle bonding agent, so have employed this examination
Test.
<modulation of handmade paper and papery evaluation result>
It is measured by internally having added the moistening breaking length of the handmade paper of wrinkle processing bonding agent, can be easy
The ground water-disintegrable the judging to wrinkle processing bonding agent.Toward by bleached kraft pulp (broad leaf tree/coniferous tree=9/1)
The paper stock of concentration 2.4 mass % being adjusted to beating degree (CSF) 400 be added on embodiment 1～13, comparative example 1～
The wrinkle processing bonding agents of 6 modulation, and to make wrinkle processing bonding agent be 0.1 matter relative to paper pulp solid content
Amount %.By square handshcet former copy paper after stirring, obtain grammes per square metre 65g/m2Handmade paper.Gained handmade paper wet
Profit breaking length is shown in Table 3,4.Because moistening breaking length numerical value is the biggest water-disintegrable the poorest, so numerical value is the smaller the better.
It addition, this evaluation is referred to as depolymerization.
Moistening breaking length: on the basis of JIS P8135
It is after 0.1 mass % with the addition of wrinkle processing bonding agent described in table 5 with relative paper pulp solid content, with
In addition to the addition of various softening agent 0.3 mass % described in table 5, all modes as above-mentioned handmade paper are entered
Row modulation, obtains handmade paper.The young's modulus of gained handmade paper is shown in Table 5.
Young's modulus: utilize wild village's business to produce tropism detector SST-2500 and measure ultrasonic propagation velocity V,
Young's modulus is obtained by following formula.Numerical value the lowest expression paper is the most soft.Relatively will not add the paper of softening agent
Young's modulus is denoted as 100.
Young's modulus ∝ ρ V2(ρ: density)
[table 1]
[table 2]
[table 3]
| Embodiment | Wrinkle processing bonding agent | Moistening breaking length (km) |
| 1-1 | Embodiment 1 | 0.05 |
| 2-1 | Embodiment 2 | 0.05 |
| 3-1 | Embodiment 3 | 0.16 |
| 4-1 | Embodiment 4 | 0.02 |
| 5-1 | Embodiment 5 | 0.02 |
| 6-1 | Embodiment 6 | 0.02 |
| 7-1 | Embodiment 7 | 0.02 |
| 8-1 | Embodiment 8 | 0.02 |
| 9-1 | Embodiment 9 | 0.02 |
| 10-1 | Embodiment 10 | 0.02 |
| 11-1 | Embodiment 11 | 0.02 |
| 12-1 | Embodiment 12 | 0.02 |
| 13-1 | Embodiment 13 | 0.02 |
[table 4]
| Comparative example | Wrinkle processing bonding agent | Moistening breaking length (km) |
| 1-1 | Comparative example 1 | 0.21 |
| 2-1 | Comparative example 2 | 0.05 |
| 3-1 | Comparative example 3 | 0.08 |
| 4-1 | Comparative example 4 | 0.03 |
| 5-1 | Comparative example 5 | 0.05 |
| 6-1 | Comparative example 6 | 0.01 |
[table 5]
| Embodiment | Wrinkle processing bonding agent | Softening agent | Young's modulus |
| 1-2 | Embodiment 1 | - | 100 |
| 2-2 | Embodiment 2 | Synthesis example 1 | 94 |
| 3-2 | Embodiment 3 | Softening agent 1 | 97 |
| 4-2 | Embodiment 4 | Softening agent 2 | 96 |
Softening agent 1 ... be equivalent to oleic acid EO (4) PO (12) oleyl ether of softening agent (S3).EO represents epoxy second
Alkane, PO represents expoxy propane, the most additional mole of () interior numeric representation.
Softening agent 2 ... be equivalent to two oleyldimethylammonium chloride (dimethyl dioleyl of softening agent (S2)
ammonium chloride)
Knowable to table 1～4 comparative example with comparative example 1, the amount with the AZR of wrinkle processing bonding agent is many
And the occasion being in outside the scope of the invention is compared, embodiment of the present invention depolymerization and adhesive strength are good, and
Epithelial surfaces is also than the softness of comparative example 1.
Knowable to table 1～4 comparative example with comparative example 2 and 3, compared with the prior art, the present invention implements
Illustrate poly-property and adhesive strength is good, and epithelial surfaces is also than the softness of prior art.
Knowable to table 1～4 comparative example with comparative example 4, the intrinsic viscosity with wrinkle processing bonding agent is low
And the occasion being in outside the scope of the invention is compared, embodiment of the present invention depolymerization and adhesive strength are good.
Knowable to table 1～4 comparative example with comparative example 5, with the resistance to water evaluation of wrinkle processing bonding agent
The occasion that value is in outside the scope of the invention is compared, and embodiment of the present invention depolymerization and adhesive strength are good, and
Epithelial surfaces is also than the softness of comparative example 5.
Knowable to table 1～4 comparative example with comparative example 6, the intrinsic viscosity with wrinkle processing bonding agent is high
And the occasion being in outside the scope of the invention is compared, embodiment of the present invention depolymerization and adhesive strength are good, and
Epithelial surfaces is also than the softness of comparative example 6.
Knowable to the embodiment beyond table 1～4 comparative example 1 with embodiment 2, molecular weight be 1,000,000～
When 5000000, adhesive strength is good, therefore preferably.
Claims (4)
1. a wrinkle processing bonding agent, containing polyamide polyamine epichlorohydrin resins (A) and/or polyamides
Amine polyamine polyureas epichlorohydrin resins (B) and softening agent (C), it is characterised in that meet following (1)～(5)
All conditions:
(1) the Azetidinium base content in wrinkle processing bonding agent solid content 1g is 0～0.2mEq；
(2) wrinkle processing bonding agent intrinsic viscosity is 0.20～0.55dL/g；
(3) softening agent (C) meets following (i) and (ii): be liquid at (i) boiling point more than 150 DEG C and 80 DEG C,
(ii) it is water solublity aliphatic polyol or NHD；
(4) mass ratio is [resin (A) and/or resin (B)]: [softening agent (C)]=100:0.5～70；
(5) resistance to water of method evaluation calculated as described below is 40～100%；
<resistance to water computational methods>
Tea-bag put into by the culture dish of the uniform epithelium defining weight 0.05g being modulated, and is placed on 50 DEG C of water
Soak 5 minutes under middle stirring, be allowed to dry, measure the weight of above-mentioned culture dish by each tea-bag, from following formula
(1) resistance to water is obtained
Formula (1) resistance to water (%)=100-{ (W1+W2)-W3}/0.05 × 100
In formula, W1 (g) is the weight of the metal culture dish having made epithelium modulation, and W2 (g) is the weight of tea-bag,
W3 (g) is for soaking dried tea-bag and the weight of culture dish.
2. the wrinkle processing bonding agent as described in claim 1, it is characterised in that wrinkle is processed with bonding
The weight average molecular weight of agent is 1,000,000～5,000,000.
3. a crimped paper manufacture method, wherein, uses including the wrinkle described in claim 1 or 2 is processed
Bonding agent is coated with toward dryer surface and meets relative fiber web area solid content is 0.01～500mg/m2Work
Sequence.
4. the crimped paper manufacture method as described in claim 3, it is characterised in that use as the interior medicine that adds
Softening agent, paper is sanitary paper, and above-mentioned softening agent is from fatty acid amide epichlorohydrin resins, has alkane
In the group that the alkylene oxide reactant of base and/or the quaternary ammonium salt of thiazolinyl, fatty acid and/or aliphatic alcohol is constituted
At least one selected.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-161557 | 2013-08-02 | ||
| JP2013161557 | 2013-08-02 | ||
| PCT/JP2014/070356 WO2015016350A1 (en) | 2013-08-02 | 2014-08-01 | Adhesive for crepe and method for manufacturing crepe paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105229227A CN105229227A (en) | 2016-01-06 |
| CN105229227B true CN105229227B (en) | 2016-10-12 |
Family
ID=52431873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480029409.4A Active CN105229227B (en) | 2013-08-02 | 2014-08-01 | Wrinkle processing bonding agent and crimped paper manufacture method |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5854167B2 (en) |
| CN (1) | CN105229227B (en) |
| WO (1) | WO2015016350A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016210066A1 (en) * | 2015-06-25 | 2016-12-29 | Georgia-Pacific Chemicals Llc | Creping adhesives containing functionalized crosslinked resins |
| CN108859503A (en) * | 2018-08-10 | 2018-11-23 | 青岛理工大学 | Waste paper recycling pencil process units |
| JP7172292B2 (en) * | 2018-08-30 | 2022-11-16 | 星光Pmc株式会社 | Crepe adhesive and method for producing crepe paper |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141984A (en) * | 1995-04-25 | 1997-02-05 | 赫尔克里斯有限公司 | Wrinkling stripping-agent |
| CN1292839A (en) * | 1998-03-17 | 2001-04-25 | 宝洁公司 | Creping aid and method for creping paper |
| CN101309795A (en) * | 2005-06-30 | 2008-11-19 | 纳尔科公司 | Modified vinylamine/vynylformamide polymers for use as creping adhesives |
| CN101384424A (en) * | 2005-12-29 | 2009-03-11 | 纳尔科公司 | Creping adhesives comprising blends of polyaminoamide epihalolhydrin resins and polyamides |
| CN101636431A (en) * | 2007-01-19 | 2010-01-27 | 赫尔克里士公司 | Creping adhesives made from amine-terminated polyamidoamines |
| JP2010163717A (en) * | 2009-01-15 | 2010-07-29 | Seiko Pmc Corp | Papermaking method includes coating dryer with adhesive for creping |
| CN102695831A (en) * | 2010-01-05 | 2012-09-26 | 纳尔科公司 | Modifying agent for yankee coatings |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6277242B1 (en) * | 2000-02-28 | 2001-08-21 | Calgon Corporation | Creping adhesive containing an admixture of PAE resins |
| CA2798789C (en) * | 2010-05-20 | 2017-02-07 | Georgia Pacific Chemicals Llc | Thermosetting creping adhesive with reactive modifiers |
-
2014
- 2014-08-01 CN CN201480029409.4A patent/CN105229227B/en active Active
- 2014-08-01 JP JP2015501602A patent/JP5854167B2/en active Active
- 2014-08-01 WO PCT/JP2014/070356 patent/WO2015016350A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1141984A (en) * | 1995-04-25 | 1997-02-05 | 赫尔克里斯有限公司 | Wrinkling stripping-agent |
| CN1292839A (en) * | 1998-03-17 | 2001-04-25 | 宝洁公司 | Creping aid and method for creping paper |
| CN101309795A (en) * | 2005-06-30 | 2008-11-19 | 纳尔科公司 | Modified vinylamine/vynylformamide polymers for use as creping adhesives |
| CN101384424A (en) * | 2005-12-29 | 2009-03-11 | 纳尔科公司 | Creping adhesives comprising blends of polyaminoamide epihalolhydrin resins and polyamides |
| CN101636431A (en) * | 2007-01-19 | 2010-01-27 | 赫尔克里士公司 | Creping adhesives made from amine-terminated polyamidoamines |
| JP2010163717A (en) * | 2009-01-15 | 2010-07-29 | Seiko Pmc Corp | Papermaking method includes coating dryer with adhesive for creping |
| CN102695831A (en) * | 2010-01-05 | 2012-09-26 | 纳尔科公司 | Modifying agent for yankee coatings |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015016350A1 (en) | 2015-02-05 |
| JP5854167B2 (en) | 2016-02-09 |
| JPWO2015016350A1 (en) | 2017-03-02 |
| CN105229227A (en) | 2016-01-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI439490B (en) | Creping adhesives made from amine-terminated polyamidoamines | |
| AU710772B2 (en) | Creping release agents | |
| ES2643699T3 (en) | Compositions and methods for making paper products | |
| JP4831523B2 (en) | Creping adhesive, crepe paper manufacturing method, and crepe paper | |
| US20070056706A1 (en) | Use of non-thermosetting polyamidoamines as dry-strength resins | |
| CN105229227B (en) | Wrinkle processing bonding agent and crimped paper manufacture method | |
| ES2230409T3 (en) | RESINS THAT ACT AS MOISTURE RESISTANCE AGENTS AND CRESPING COADYUVANTS AND PROCEDURES TO PREPARE AND USE THE SAME. | |
| TR201806902T4 (en) | Phosphoric acid stabilized creping adhesive. | |
| US10624986B2 (en) | Absorbent materials, products including absorbent materials, compositions, and methods of making absorbent materials | |
| US20170204565A1 (en) | Creping adhesives and methods for making and using same | |
| CA2545476A1 (en) | Paper making process and crosslinking compositions for use in same | |
| EP3313951B1 (en) | Creping adhesives containing functionalized crosslinked resins | |
| US11427738B2 (en) | Use of boronic acid-functionalized polymers as yankee coating adhesives | |
| JP5246594B2 (en) | Creping adhesive, crepe paper manufacturing method, and crepe paper |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |