WO2002088467A1 - Clarificateur de papier et procede de production de papier transparent - Google Patents

Clarificateur de papier et procede de production de papier transparent Download PDF

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Publication number
WO2002088467A1
WO2002088467A1 PCT/JP2002/004174 JP0204174W WO02088467A1 WO 2002088467 A1 WO2002088467 A1 WO 2002088467A1 JP 0204174 W JP0204174 W JP 0204174W WO 02088467 A1 WO02088467 A1 WO 02088467A1
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WIPO (PCT)
Prior art keywords
group
carbon atoms
paper
compound
monovalent hydrocarbon
Prior art date
Application number
PCT/JP2002/004174
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English (en)
Japanese (ja)
Inventor
Tatsuo Uchida
Shinichi Umeya
Original Assignee
Nicca Chemical Co., Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2001128414A external-priority patent/JP4713008B2/ja
Priority claimed from JP2002113896A external-priority patent/JP4162421B2/ja
Priority claimed from JP2002116624A external-priority patent/JP4298217B2/ja
Application filed by Nicca Chemical Co., Ltd. filed Critical Nicca Chemical Co., Ltd.
Publication of WO2002088467A1 publication Critical patent/WO2002088467A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
    • C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
    • C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/3332—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing carboxamide group
    • 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
    • D21H21/26—Agents rendering paper transparent or translucent

Definitions

  • the present invention relates to a paper clarifying agent and a method for producing a transparent paper.
  • paper usually contains 40 to 50% of air, and the difference in the refractive index between the contained air and the cellulose fiber makes the paper look white and has opacity. Therefore, a transparent paper can be obtained by infiltrating a compound having a refractive index close to that of the cellulose fiber to fill the voids of the paper.
  • Such transparent paper is used, for example, in tracing paper and window parts of envelopes with windows.
  • envelopes with windows have been cut out from a part of the envelope paper and pasted with a transparent film such as cellophane, or a resin dissolved in an organic solvent (for example, acrylic resin, rosin resin, polyester).
  • a transparent film such as cellophane, or a resin dissolved in an organic solvent (for example, acrylic resin, rosin resin, polyester).
  • Resin, urethane resin, petroleum hydrocarbon resin, polymer alicyclic compound or wax is applied to a part of the envelope paper, and the part is heated to make the resin penetrate into the paper and make it transparent. It is manufactured by methods such as
  • the former method requires complicated processes such as cutting out the window and gluing the film, so that the working efficiency is low.
  • the resin used does not show water solubility, or even if it is water soluble, it is only slightly dispersed or emulsified, and it does not dissolve even in alkaline water such as sodium hydroxide aqueous solution. Since recycling is difficult, it is necessary to separate window envelopes from newspapers and advertising paper when collecting used paper, which increases costs. In addition, if waste paper is not properly separated at the time of recovery, scum derived from resin pitch or wax will be generated when disintegrated with pulp or the like, which not only causes troubles during papermaking but also However, many problems occur, such as recycle paper flipping the ink.
  • the present invention solves the above-mentioned drawbacks of the envelope with a window, namely, the problems of the manufacturing process and the work of collecting used paper, the problem of recycling, and the problem of quality. It is an object of the present invention to provide a paper clarifying agent which has no stickiness on the surface, facilitates removal of the clarifying agent, and can obtain a transparent paper having good paper recycling properties. It is another object of the present invention to provide a method for producing transparent paper using such a paper clarifying agent.
  • the present inventors have conducted extensive research to achieve the above object, and as a result, have found that the above object can be achieved by an aqueous compound having a predetermined chemical structure having an oxyalkylene chain, and completed the present invention.
  • the present invention provides the following paper clarifying agents) to (f).
  • a paper clarifying agent comprising an aqueous compound represented by the following general formula (1) and having a melting point of 40 ° C. or more (hereinafter, referred to as “compound 1”).
  • R 0 is a m-valent hydrocarbon group having 1 to 22 carbon atoms or a heterocyclo m-valent anorecono-residue having 6 to 12 carbon atoms
  • 1 is a _0-group or - ⁇ 00-group
  • A is an alkylene group having 2 to 4 carbon atoms
  • Z 1 is a hydrogen atom, an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or a group represented by CONH—R 2
  • m is 1 to: LO
  • n is a number such that n Xm is 25 to 700.
  • R 2 is a group represented by a monovalent hydrocarbon group having 1 to 22 carbon atoms, and m Zn Xm A and m X 1 may be the same or different. Good. When m is 2, R ° may be a single bond. ]
  • a clarifying agent for paper comprising:
  • R. I a m-valent hydrocarbon group having 1 to 22 carbon atoms or a heterocyclo m-valent alcohol residue having 6 to 12 carbon atoms
  • 1 is a -0 group or - ⁇ 00- group
  • A is a 2 to 4 carbon atom group.
  • Alkylene group Z 1 is a hydrogen atom, an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or a group represented by one CONH—R 2
  • m is 1 to: the number of L 0, j is 0 to ( The number of m-1), and n is a number such that n Xm is 25 to 700.
  • R 2 is a monovalent hydrocarbon group having 1 to 22 carbon atoms, and (m—; j) Zn Xm A and m X 1 may be the same or different. If m is 2, R. May be a single bond.
  • a paper clarifying agent comprising an aqueous compound represented by the following general formula (3) and having a melting point of 40 ° C. or more (hereinafter, referred to as “compound 3”).
  • R 1 is a monovalent hydrocarbon group having 1 to 22 carbon atoms or an alkoxyalkyl group having 2 to 22 carbon atoms
  • Z 1 is a hydrogen atom, an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or Is a group represented by one CONH—R 2
  • a 1 is an alkylene group having 2 to 4 carbon atoms
  • k is a number of 1 to 3
  • n is a number such that nX k is 25 to 700.
  • R 2 is a monovalent hydrocarbon group having 1 to 22 carbon atoms
  • k Z 1 (3-k) R 1 and n X k A 1 may be the same or different. Good. ]
  • compound 4 A paper clarifying agent comprising an aqueous compound having a melting point of 40 ° C. or higher (hereinafter referred to as “reactant 4”).
  • 1 1 is a monovalent hydrocarbon group or alkoxy Shiarukiru group with carbon number 2-2 2 1 to 22 carbon atoms
  • Z 2 is a hydrogen atom, Ashiru group, a monovalent hydrocarbon having 1 to 2 2 carbon atoms group group or represented in one CONH-R 2
  • a 1 is an alkylene group having 2 to 4 carbon atoms
  • k is the number of. 1 to 3
  • n is n X k is the number such that 2 5-700, Are respectively shown.
  • at least one of k Z 2 is a hydrogen atom
  • 12 is a monovalent hydrocarbon group having 1 to 22 carbon atoms.
  • k Z 2 , (3 ⁇ k) R 1, and n X k A 1 may be the same or different, respectively.
  • a paper clearing agent comprising an aqueous compound represented by the following general formula (5) and having a melting point of 40 ° C. or higher (hereinafter, referred to as “compound 5”).
  • R 1 . And R 11 each independently represent a divalent hydrocarbon group of from 1 to 1 2 carbon atoms, monovalent hydrocarbon group of R 2 1 and R 22 1 to 6 carbon atoms independently, A 1 Q, A 11 and A 12 are each independently an alkylene group having 2 to 4 carbon atoms; Z 1 Q , Z 11 and Z 12 are each independently a hydrogen atom, an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or H- group represented by R 30, p denotes the number of Less than six, q and r is the number of independently 0 to 2, s, t and u each number of independently 1 to 700 are respectively.
  • R30 is a monovalent hydrocarbon group having 1 to 22 carbon atoms
  • sXp + tXq + uXr is a number of 25 to 700.
  • compound 6 a compound represented by the following general formula (6)
  • reactant 6J an aqueous compound having a melting point of 40 ° C. or higher
  • each R 1Q and R 11 are independently a monovalent hydrocarbon group of R 2 1 and R 22 1 to 6 carbon atoms each independently, A 1Q, A 11 and A 12 are each independently an alkylene group having 2 to 4 carbon atoms;
  • Z 20 , Z 21 and Z 22 are each independently a hydrogen atom, an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or indicates a group represented by one CON H_R 3Q, p is the number of Less than six, q and r is the number of independently 0 to 2, s, t and u each number of independently 1 to 700 are respectively.
  • p Z 2 °, q Z 21 and r Z 22 is a hydrogen atom, and R 3 ° is the number of carbon atoms:! ⁇ 22 monovalent hydrocarbon groups, sXp + tXq + uXr are numbers from 25-700. Also p z 2 . , Q Z 21 , r Z 22 , (2-q) R
  • the clarifying agent for paper of the present invention contains the above-described compound or reactant, it has excellent transparency, does not have stickiness on the surface of the transparent paper, can easily remove the clarifying agent, and can remove paper. It becomes possible to obtain transparent paper having good cycleability.
  • the present invention also provides a method for producing transparent paper, which comprises an adhesion step of adhering the paper clarifying agent of the present invention to paper.
  • the compound 1 includes a compound represented by the following general formula (1a) (hereinafter referred to as “compound la”) and a compound represented by the following general formula (lb) (hereinafter referred to as “compound lb J”). ).
  • compound la is represented by R.
  • M-hydric alcohol having OH and m OH in the present invention, alkylphenol such as noyulphenol and tamylphenol, and phenol are considered to be included in the monohydric alcohol. The same applies hereinafter.
  • Compound 1 is a compound obtained by adding n Xm mole of an alkylene oxide of AO to an m-valent alcohol or m-valent carboxylic acid, wherein Z 1 is A monovalent hydrocarbon group having 1 to 22 carbon atoms or one CONH—R 2 When it is a group represented, it is a compound in which the terminal of the compound thus obtained is acylated, etherified or urethanized, respectively.
  • an alkylene oxide for example, after sufficiently dehydrating the m-valent alcohol and a base catalyst (such as potassium hydroxide and sodium hydroxide) at high temperature and reduced pressure, There is a method in which an alkylene oxide is added at 150 ° C. and added (single addition, block or random addition).
  • a base catalyst such as potassium hydroxide and sodium hydroxide
  • Compound 1a includes polyoxyalkylene dalicol, and such a compound can be obtained by a known method for synthesizing a non-ionic surfactant. That is, using a high-pressure reactor, diethylene glycol and a base catalyst (such as potassium hydroxide and sodium hydroxide) are sufficiently dehydrated at high temperature and reduced pressure, and then ethylene oxide and propylene oxide at 80 to 200 ° C.
  • the compound 1a ie, a polyoxyalkylenedarilicol, can be obtained by a method of independently adding, blocking, or randomly adding an alkylene oxide such as butylene oxide.
  • Examples of such compounds include Pull-out Eck F-68 (Asahi Denka Co., Ltd.), PEG1540, PEG2000, PEG4000, PEG6 000 (Sanyo Kasei Kogyo Co., Ltd., and Sanyo Yushi Co., Ltd.) May be used.
  • an alkylene oxide to an m-valent carboxylic acid for example, a high-pressure reactor is used, and an m-valent carboxylic acid and a base catalyst (for example, potassium hydroxide and sodium hydroxide) are heated at a high temperature and under a reduced pressure. After sufficient dehydration, a method of adding an alkylene oxide to perform addition (single addition, block or random addition) can be mentioned.
  • a similar compound can also be obtained by reacting an m-valent carboxylic acid with a polyoxyalkylene glycol at a reaction temperature of 110 to 130 ° C. for 2 to 3 hours under a catalyst of concentrated sulfuric acid. Can be.
  • Examples of the method of acylation include esterification at 130 to 250 ° C using carboxylic acid, and ester exchange at 80 to 150 ° C using carboxylic acid ester.
  • Examples of the etherification method include a method of reacting an alcohol under a catalyst such as concentrated sulfuric acid and a method of reacting glycidyl ether.
  • a method of urethanization for example, a method of reacting mono'socyanate can be mentioned.
  • polyoxyalkylene structure portion is composed of one kind of oxyalkylene.
  • polyoxyethylene e.g, polyoxyethylene
  • oxyalkylenes e.g, polyoxyethylene / polyoxypropylene
  • each of a plurality of polyoxyalkylene structures may be the same or different.
  • the oxyalkylene is preferably oxyethylene.
  • the number of moles of oxyethylene in the total moles of oxyalkylene is preferably 60% or more.
  • n is preferably a number such that n Xm is 40 to 500.
  • the acryl group as Z 1 is an acryl group having 2 to 22 (preferably 2 to 18) carbon atoms (acetyl group, propionyl group, butyryl group, otatanyl group, lauroyl group, myristoyl group, palmitoyl group, stear port)
  • the monovalent hydrocarbon group as Z 1 is preferably a monovalent hydrocarbon group having 1 to 20 (preferably 1 to 18) carbon atoms.
  • R 2 is preferably a monovalent hydrocarbon group having 1 to 18 (preferably 6 to 18) carbon atoms.
  • the Z 1 in the compound 1, Ashiru group, by a monovalent hydrocarbon group or a group represented by a CONH- R 2 of from 1 to 22 carbon atoms further toward the water resistance of the transparent sheet
  • the transparency of the transparent paper becomes more resistant to rain and snow.
  • the hygroscopicity is restricted, and the stability of the transparent paper can be improved.
  • R. I a m-valent hydrocarbon group having 1 to 22 carbon atoms or a heterocyclo m-valent alcohol residue having 6 to 12 carbon atoms.
  • a heterocyclo m-valent alcohol residue having 6 to 12 carbon atoms means m hydroxyl groups from a heterocycloalcohol having 6 to 12 carbon atoms (an alcohol having a heterocyclic mouth ring such as sorbitan). It means the residue excluding, and the hetero atom in the heterocyclyl ring is preferably an oxygen atom.
  • R 0 is preferably a monovalent hydrocarbon group having 1 to 22 carbon atoms.
  • the monovalent hydrocarbon group having 1 to 22 carbon atoms may be saturated or unsaturated, and may be linear or branched.
  • Such groups include, for example, saturated hydrocarbon groups such as methyl group, ethyl group, propyl group, isopropyl group, amyl group, octyl group, lauryl group, myristyl group, palmityl group, stearyl group and behenyl group; Bull, aryl, 2-pentenyl, oleyl, elaidinole, 9,12-octadecadieninole, 9,12,1
  • Unsaturated hydrocarbon groups such as 5-octadecatrienyl group and 13-docosenyl group; fuel groups and alkylphenyl groups.
  • sorbitan residue is a residue obtained by removing m hydroxyl groups from sorbitan; the same applies hereinafter; a linear or branched m-valent carbon having 2 to 6 carbon atoms It is a hydrogen group or an m-valent hydrocarbon group having a benzene skeleton having 6 to 18 carbon atoms, and m is particularly preferably a number of 2 to 4.
  • the polyoxyalkylene structure in Compound 1 is particularly preferably polyoxyethylene or a polyoxyethylene Z polyoxypropylene block copolymer.
  • the molar number of oxyethylene in the total molar number of oxyethylene and oxypropylene is 60% or more.
  • the clarifying agent can be more easily removed, and the recyclability of the paper can be further improved.
  • the melting point of the compound increases, and the stickiness of the transparent paper surface tends to be further reduced.
  • compound 1 is wherein m is 2; Is an ethylene group or a propylene group (preferably an ethylene group), AO is oxyethylene and / or oxypropylene (that is, A is an ethylene group and Z or a propylene group), and oxyethylene and moles of Okishiechiren to the total number of moles of propylene is at 6 0% or more (i.e., 6 0% of the total number of moles of ethylene and propylene groups are located at an ethylene group), Z 1 is ⁇ Shi / Les group Is a compound.
  • Such a compound has an oxyethylene structure and thus is excellent in water solubility and makes it possible to particularly improve the recyclability of transparent paper. Further, since it has an acyl group, the durability of the transparent paper against rain, snow, and the like can be significantly improved. In other words, they exhibit the opposite performances of high water solubility and excellent durability in a well-balanced manner.
  • Compound 1 has a melting point of 40 ° C. or higher, but preferably has a melting point of 40 to 90 ° C., and more preferably 45 to 70 ° C. If the melting point is lower than 40 ° C., the transparent paper becomes sticky. Further, Compound 1 is an aqueous compound, but it is preferable that Compound 1 is a compound that gives a transparent aqueous solution when mixed with water so as to be 1% by weight. This is because, when it is strong, the recyclability of the paper becomes better.
  • the average molecular weight of the compound 1 is preferably not more than 20,000, more preferably from 2,000 to 15,500. If the average molecular weight is more than 200, 000, application to paper tends to be difficult.
  • Reactant 2 is a reaction product of a compound selected from the group consisting of polyvalent carboxylic acids, polyisocyanates and polyglycidyl ethers, and compound 2a or compound 2b shown below.
  • compound 2a is represented by R.
  • I a compound in which nXm mole of an alkylene oxide of AO is added to 1 mole of an m-hydric alcohol having m and OH, and a part of the terminal hydrogen atom is Z 1 .
  • a compound in which a mole of an alkylene oxide of AO is added by n ⁇ m mole to 1 mole of a m-valent carboxylic acid provided with m COOH and a terminal hydrogen atom is partially Z 1 .
  • each of the m existing n's may be the same number or different numbers.
  • reaction between compound 2a or compound 2b and the polyvalent carboxylic acid occurs between the former terminal OH and the latter CO OH group, and the reaction forms an esternole bond.
  • the reaction of compound 2a or compound 2b with the polyisocyanate occurs between the former terminal OH and the latter NCO group, and a urethane bond is formed by the reaction.
  • the reaction between compound 2a or compound 2b and polydaricidyl ether occurs between the terminal OH of the former and the glycidyl group of the latter to form a 10_CH 2 —CH (OH) — bond.
  • the reaction between 2b and the polyisocyanate is preferably 1 mol per 2 mol of the former, and the reaction between compound 2a or compound 2b and polydaricidyl ether is 2 mol per mol of the former.
  • the latter is preferably 1 mol.
  • the polyvalent rubonic acid is preferably a dicarboxylic acid, and the polyglycidyl ether is preferably a diglycidyl ether.
  • alkylene oxide to m-valent alcohol or m-valent carboxylic acid is as described above. Can be performed in the same manner as described above.
  • the reaction of compound 2a or compound 2b with polyvalent carboxylic acid can be performed, for example, by using an acid catalyst such as sulfuric acid or p-toluenesulfonic acid, a Lewis acid catalyst such as zinc acetate, sodium hydroxide, sodium carbonate, or the like.
  • the reaction can be carried out at 100 ° C. (at up to 300 ° C.) at normal pressure and reduced pressure in the presence of a base catalyst.
  • the reaction between compound 2a or compound 2b and the polyisocyanate compound is carried out, for example, by adding the polyisocyanate compound little by little while keeping compound 2a or compound 2b at 50 to 80 ° C. After the addition, the reaction can be carried out at 80 to 100 ° C. for 6 to 10 hours.
  • any known reaction conditions can be employed for the reaction between compound 2a or compound 2b and polydaricidyl ether.
  • polyoxyalkylene structures obtained by adding a mole of anolexylene oxide as AO, and the polyoxyalkylene structure portion is composed of one kind of oxyalkylene.
  • oxyalkylene Eg, polyoxyethylene
  • two or more oxyalkylenes eg, polyoxyethylene polyoxypropylene
  • they may form a block copolymer or a random copolymer.
  • each of a plurality of polyoxyalkylene structures may be the same or different.
  • the oxyalkylene is preferably oxyethylene, and when oxyalkylene other than oxyethylene is contained, the number of moles of oxyethylene in the total moles of oxyalkylene is preferably 60% or more.
  • n is preferably a number such that nXm is 40 to 500.
  • Ashiru group, monovalent hydrocarbon group with carbon number 1-2 2 as Z 1 as Z 1, and a monovalent hydrocarbon group with carbon number 1-2 2 as R 2 is preferably in compound 1 It is preferable to apply those exemplified as examples.
  • Z 1 in compound 2a and compound 2b an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or a group represented by CONH—R 2 , the transparent paper It is possible to further improve the water resistance of the transparent paper, and as a result, the durability of the transparent paper against rain, snow, and the like is improved. Further, the hygroscopicity is restricted, and the stability of the transparent paper can be improved.
  • R Q is a m-valent hydrocarbon group having 1 to 22 carbon atoms or a heterocyclo m-valent alcohol residue having 6 to 12 carbon atoms, and a heterocyclic mouth having 6 to 12 carbon atoms m
  • the hetero atom in the hydric alcohol residue is preferably an oxygen atom.
  • R ° is preferably a monovalent hydrocarbon group having 1 to 22 carbon atoms.
  • the monovalent hydrocarbon group having 1 to 22 carbon atoms may be saturated or unsaturated, and may be linear or branched. Examples of such a group include the same groups as those exemplified for compound 1.
  • R. I a sorbitan residue, a linear or branched m-valent hydrocarbon group having 2 to 6 carbon atoms or an m-valent hydrocarbon group having a benzene skeleton having 6 to 18 carbon atoms, where m is 2 Particularly preferred is a number between 4 and 4.
  • the polyoxyalkylene structure is particularly preferably polyoxyethylene or a polyoxyethylene Z polyoxypropylene block copolymer.
  • the mole number of oxyethylene in the total mole number of oxyshethylene and oxypropylene is preferably at least 60%.
  • the melting point of the reactant 2 is 40 ° C. or higher, but the melting point is preferably 40 to 90 ° C., and more preferably 45 to 70 ° C. If the melting point is lower than 40 ° C., the transparent paper becomes sticky.
  • the reactant 2 is an aqueous compound, and it is preferable that the reactant 2 is a compound which gives a transparent aqueous solution when mixed with water so as to be 1% by weight. This is because, when it is strong, the recyclability of the paper becomes better.
  • the average molecular weight of the reactant 2 is preferably not more than 20, 000, and 2,000 to 5,000. , 0000 is more preferred. If the average molecular weight is more than 200, 000, application to paper tends to be difficult.
  • the compound 3 is, for example, an alkylene AO per mole of a (3-k) monoamine (primary or secondary monoamine) having R 1.
  • a (3-k) monoamine primary or secondary monoamine
  • R 1 a monoamine having R 1.
  • Okisaido was the n X k moles added, is a compound that the ends can be manufacturing by a Z 1. Note that each of the k existing n's may be the same number or different numbers.
  • Compound 3 in which Z 1 is a hydrogen atom can be obtained by adding n X k mole of an alkylene oxide of A 1 O to a monoamine, wherein Z 1 is an asinole group, a monovalent having 1 to 22 carbon atoms. a group represented by a hydrocarbon group or one CONH- R 2 compound 3, the end of the obtained compound Te this good Unishi may each Ashiru reduction, obtained by etherification or urethanization.
  • a monoamine is charged into a high-pressure reactor, the atmosphere is replaced with an inert gas, and then heated to generate active hydrogen (that is, hydrogen derived from an amino group and an imino group).
  • active hydrogen that is, hydrogen derived from an amino group and an imino group.
  • An equivalent amount of alkylene oxide is added, and then a base catalyst (for example, potassium hydroxide or sodium hydroxide) is added, and after sufficient dehydration at high temperature and reduced pressure, alkylene oxide is added alone.
  • a base catalyst for example, potassium hydroxide or sodium hydroxide
  • alkylene oxide is added alone.
  • Examples of the method include block addition or random addition.
  • the method of acylation, the method of etherification, and the method of perethaneation are the same as those in Compound 1 described above.
  • polyoxyalkylene structures to which n moles of the alkylene oxide A 1 O are added are present, and the polyoxyalkylene structure portion may be composed of one kind of oxyalkylene (for example, polyoxyalkylene).
  • oxyalkylene for example, polyoxyalkylene
  • Oxyethylene or two or more oxyalkylenes (eg, polyoxyethylene / polypropylene). And if it consists of two or more oxyalkylenes, Or a random copolymer may be formed.
  • each of a plurality of polyoxyalkylene structures may be the same or different.
  • compound 3 contains an ethylene group as A 1 , and in this case,! ! Z! ⁇ : It is preferable that the number of ethylene groups occupying is 60% or more. That is, when an oxyalkylene other than oxyethylene is contained, the number of moles of oxyethylene in the total moles of oxyalkylene is preferably 60% or more. When the number of ethylene groups in the compound 3 is 60% or more, the water solubility can be improved, the clarifying agent can be more easily removed, and the recyclability of paper can be further improved. In addition, the melting point of the compound increases, and the stickiness of the transparent paper surface can be further reduced.
  • Z 1 in compound 3 an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or a group represented by CONH-R 2 , the water resistance of the transparent paper is further improved. As a result, the durability of the transparent paper against rain and snow is improved. Further, the hygroscopicity is restricted, and the stability of the transparent paper can be improved.
  • n is preferably a number such that nXk is 40 to 500.
  • Monovalent hydrocarbon group as R 1 preferably is a monovalent hydrocarbon group having 1 2-1 8 carbon atoms, and alkoxyalkyl groups as R 1, the alkoxy moiety is an alkyl moiety of 1 to 14 carbon atoms An alkoxyalkyl group having 2 to 18 carbon atoms having 1 to 4 carbon atoms is preferable.
  • the acyl group as Z 1 is preferably an acyl group having 2 to 22 (preferably 2 to 18) carbon atoms, and the monovalent hydrocarbon group as Z 1 is preferably a 1 to 20 carbon atom (preferably The monovalent hydrocarbon groups of 1 to 18) are preferred.
  • R 2 is preferably a monovalent hydrocarbon group having 1 to 18 (preferably 6 to 18) carbon atoms.
  • Compound 3 is a compound having a temperature of 40 ° C. or higher, and preferably has a melting point of 40 to 90 ° C., and more preferably 45 to 70 ° C. If the melting point is less than 40 ° C, the transparent paper will be sticky.
  • Compound 3 is 1 weight.
  • the average molecular weight of the compound 3 is preferably not more than 200,000, more preferably from 2,000 to 15,500. If the average molecular weight exceeds 20,000,000, application to paper tends to be difficult.
  • Reactant 4 is a reaction product of a compound selected from the group consisting of polycarboxylic acids, polyisocyanates and polyglycidyl ethers with compound 4, and is an aqueous compound having a melting point of 40 ° C. or higher.
  • Compound 4 the structure as apparent from the formula (4), for example, (3- k) into individual monoamine having R 1 of a (primary or secondary monoamine) 1 Monore, A 1 0 becomes ⁇ the Ruki alkylene oxide is n X k moles added, is a compound capable of manufacturing by the ends Z 2 (method for adding an alkylene O key side is as above mentioned). Note that each of the k existing n's may be the same number or different numbers.
  • compound 4 since at least one of the k Z 2 must be hydrogen atom, compound 4, Z 2 obtained by an alkylene O key SIDE A I_ ⁇ become monoamine is n molar added Must be hydrogen (ie, a terminal hydroxyl group) or a compound obtained by acylating, etherifying, or urethane-forming a part of the terminal hydroxyl group of such a compound (acylation, etherification, or The method of urethanization is as described above).
  • the terminal (Z 2 ) needs to be a hydrogen atom. No etherification, etherification or urethanation is performed.
  • the starting monoamine is a primary monoamine such as monoalkylamine
  • at least one of the two Z 2 must be a hydrogen atom, and the other hydrogen atom is It may be used for conversion, etherification or urethanization.
  • the hydrogen atom (hydroxyl group) remaining in compound 4 is used for the reaction with polycarboxylic acid, polyisocyanate or polyglycidyl ether. That is, compound 4 reacts with the polyvalent carboxylic acid between the former OH group and the latter COOH group to form an ester bond. In addition, compound 4 reacts with the polyglycidyl ether between the former OH group and the latter glycidyl group to form a single O—CH 2 —CH (OH) single bond. Then, the compound 4 reacts with the polyisocyanate between the former OH group and the latter NCO group to form a urethane bond.
  • the reaction molar ratio of compound 4 to a compound selected from the group consisting of polycarboxylic acids, polyisocyanates, and polyglycidyl ethers is preferably 1 mol per 2 mol of the former.
  • the reactant formed by the reaction is as follows: It is a dimer having two structures derived from compound 4 in one molecule.
  • polyoxyalkylene structures to which n moles of the alkylene oxide A 1 O are added are present, and the polyoxyalkylene structure portion may be composed of one type of oxyalkylene (for example, polyoxyalkylene).
  • Propylene or may be composed of two or more oxyalkylenes (for example, polyoxylene / polypropylene).
  • two or more oxyalkylenes are used, they may form a block copolymer or a random copolymer.
  • each of a plurality of polyoxyalkylene structures may be the same or different.
  • compound 4 contains an ethylene group as A 1 , and in this case,! ! !
  • the number of ethylene groups occupied by the number is preferably 60% or more. That is, when an oxyalkylene other than oxyethylene is contained, the number of moles of the oxyethylene in the total moles of the oxyalkylene is preferably 60% or more.
  • the number of ethylene groups in the compound 4 is 60% or more, the water solubility can be improved, the clarifying agent can be more easily removed, and the recyclability of paper can be further improved.
  • the melting point of the compound increases, and the stickiness of the transparent paper surface can be further reduced.
  • the water resistance of the transparent paper is further improved by forming a part of Z 2 in compound 4 as an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or a group represented by CONH-R 2.
  • a part of Z 2 in compound 4 as an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or a group represented by CONH-R 2.
  • n is preferably a number such that nX k is 40 to 500.
  • Monovalent hydrocarbon group as R 1 preferably is a monovalent hydrocarbon group having 1 2-1 8 carbon atoms, and alkoxyalkyl groups as R 1, the alkoxy moiety is an alkyl moiety 1 to 14 carbon atoms An alkenyloxyalkyl group having 1 to 4 carbon atoms and 2 to 18 carbon atoms is preferable.
  • the acyl group as Z 2 is preferably an acyl group having 2 to 22 (preferably 2 to 18) carbon atoms, and the monovalent hydrocarbon group as Z 2 is preferably a 1 to 20 carbon atom (preferably 1 to 18). To 18) are preferred. Further, 2 2 gar 001 ⁇ 3 ⁇ 4_1 ⁇ R 2 in the case where a group represented by 2 is preferably a carbon number 1 to 1 8 (preferably 6 to 18) is a monovalent hydrocarbon group.
  • the reactant 4 is a compound having a temperature of 40 ° C. or higher, and the melting point of the reactant 4 is preferably 40 to 90 ° C., and more preferably 45 to 70 ° C. If the melting point is lower than 40 ° C, the transparent paper becomes sticky. Also, the reactant 4 becomes 1% by weight. As described above, an aqueous compound which gives a transparent aqueous solution when mixed with water is preferable. This is because, when vigorous, the recycling of transparent paper 1 "becomes better.
  • the average molecular weight of the reaction product 4 is preferably 20,000 or less, more preferably 2,000 to 15,000. However, if it exceeds 20,000, application to paper tends to be difficult.
  • Compound 5 can, for example, polyamines (hereinafter "Compound 7 J called.) Represented by the following general formula (7) to 1 mole of alkylene O key side (A 10 O, A 1 I_ ⁇ Pi A 12 0) a , S X p + t X q + u X r moles (the method of adding an alkylene oxide is as described above), and the terminal is made to be Z 1 Q , Z 11 or Z 12.
  • the definition of R 1 G , R 11 , p, q and r in compound 7 is the same as that in compound 5, and Z 1 () , Z 11 and Z 12 are the same.
  • Z 1 D , Z 11 and Z 12 are The method of acylation, etherification, or urethanization in the case where the group is a monovalent hydrocarbon group having 1 to 22 carbon atoms or 1 CONH_R 3 ° is as described above.
  • Each of p existing s, q existing t, and r existing u may be the same number or different numbers.
  • alkylene O key side (Alpha 10 Omicron, Alpha 1 ⁇ or A 12 0) is s, but t and u moles added poly O xylene polyalkylene structure is present, polyoxy alkylene structure moiety, one O It may be composed of xyalkylene (eg, polyoxyethylene) and may be composed of two or more oxyalkylenes (eg, For example, polyoxyethylene Z polyoxypropylene). When it is composed of two or more kinds of oxyalkylene, it may form a block copolymer or a random copolymer. Further, each of a plurality of polyoxyalkylene structures may be the same or different.
  • compound 5 contains an ethylene group as A 1 Q , A 11 or A 12 , and in this case, ethylene accounts for the total number of A 1 () , A 11 and A 12.
  • the number of groups is at least 60%. That is, when oxyalkylene other than oxyalkylene is contained, the number of moles of oxyethylene in the total mole of oxyalkylene is preferably 60% or more.
  • At least one of Z 1 () , Z 11 and Z 12 in the compound 5 is an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or a group represented by one CONH-R 3 °.
  • the water resistance of the transparent paper can be further improved, and as a result, the durability of the transparent paper against rain, snow, and the like becomes excellent. Further, the hygroscopicity is restricted, and the stability of the transparent paper can be improved.
  • R 1 ° and R 11 are each independently preferably a divalent hydrocarbon group having 1 to 8 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 6 carbon atoms.
  • an ethylene group or a trimethylene group is particularly preferable.
  • R 21 and R 22 are each independently a monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • Ashiru group as Z 10, Z 11 or Z 12 is preferably Ashiru group having 2 to 22 carbon atoms (preferably 2-18) monovalent hydrocarbon group as Z 10, Z 11 or Z 12 Is preferably a monovalent hydrocarbon group having 1 to 20 (preferably 1 to 18) carbon atoms.
  • s, t and u are each independently a number from 1 to 700,
  • SXp + tXq + uXr must be a number from 25 to 700.
  • sXp + tXq + uXr is preferably from 40 to 500.
  • Compound 5 is a compound having a temperature of 40 ° C. or higher, and the melting point of compound 5 is preferably from 40 to 90 ° C., and more preferably from 45 to 70 ° C. If the melting point is lower than 40 ° C, the transparent paper becomes sticky.
  • Compound 5 is preferably an aqueous compound that gives a clear aqueous solution when mixed with water so as to be 1% by weight. This is because, when it is strong, the recyclability of the transparent paper becomes better.
  • the average molecular weight of compound 5 is preferably 20,000 or less, more preferably 2,000 to 15,000. If the average molecular weight exceeds 20,000, application to paper tends to be difficult.
  • Reactant 6 is a reaction product of a compound selected from the group consisting of polycarboxylic acids, polyisocyanates and polyglycidyl ethers with compound 6, and is an aqueous compound having a melting point of 40 ° C. or higher.
  • Compound 6 can be obtained, for example, by adding an alkylene oxide (A 10
  • Z 20, Z 2 1 and Z 22 each independently represent a hydrogen atom, Ashiru group, a monovalent hydrocarbon group or a single CONH from 1 22 carbon atoms — R 3t)
  • Z 2Q , Z 21 and Z 22 are each an acyl group, a monovalent hydrocarbon group having 1 to 22 carbon atoms or one CONH—R 3 °
  • the method for acylation, etherification or urethanation of the compound is as described above. Note that each of p existing s, q existing t, and r existing u may be the same number or different numbers.
  • compound 6 at least one of Z 2 °, Z 21 and Z 22 needs to be a hydrogen atom, and thus compound 6 is different from compound 7 in that alkylene oxides (A 1 C) 0 and 11 are used . And obtained by adding an A 12 0), ⁇ 20, ⁇ 21 and Zeta 22 is hydrogen (ie, compounds terminus is a hydroxyl group), or a part of the terminal hydroxyl groups of such compounds, Ashiru reduction, It must be a compound obtained by etherification or urethanization (the method of acylation, etherification or urethanization is as described above). Thus, the hydrogen atom (hydroxyl group) remaining in compound 6 is used for the reaction with polycarboxylic acid, polysuccinate or polydaricidyl ether. In addition, the reaction molar ratio of the compound 6 and a compound selected from the group consisting of polyvalent ruponic acid, polyisocyanate and polyglycidyl ether is preferably 1 mol of the latter to 2 mol of the former.
  • alkylene oxide (Alpha 10 Omicron, 11 0 or 12 0) s, but a polyoxyalkylene structure that t and u mol adduct present, polyoxy alkylene structure moiety consist one Okishiarukiren (Eg, polyoxyethylene), or may be composed of two or more oxyalkylenes (eg, polyoxyethylene / polyoxypropylene). When it is composed of two or more kinds of oxyalkylene, it may form a block copolymer or a random copolymer. Further, each of a plurality of polyoxyalkylene structures may be the same or different.
  • Compound 6 particularly preferably contains an ethylene group as A 10 , A 11 or A 12 , and in this case, the ethylene group accounts for the total number of Alt , A 11 and A 12 . Preferably, the number is at least 60%. That is, Okishe
  • the molar number of oxyethylene occupying is 60% or more.
  • the water solubility can be improved, the clarifying agent can be more easily removed, and the recyclability of the paper can be further improved.
  • the melting point of the compound increases, and the stickiness of the transparent paper surface can be further reduced.
  • R 1Q and R 11 are each independently preferably a divalent hydrocarbon group having 1 to 8 carbon atoms, more preferably a divalent hydrocarbon group having 1 to 6 carbon atoms. And particularly preferably an ethylene group or a trimethylene group. It is preferable that R 21 and R 22 are each independently a monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • Ashiru group as Z 21 or Z 22 is preferably Ashiru group having 2 to 22 carbon atoms (preferably 2 to 18), the monovalent hydrocarbon group as Z 2 °, Z 21 or Z 22 is carbon A monovalent hydrocarbon group having a number of 1 to 20 (preferably 1 to 18) is preferable.
  • Z 2 °, Z 21 or Z 22 is a group represented by —CONH—R 3 °
  • R 30 is a monovalent hydrocarbon group having 1 to 18 (preferably 6 to 18) carbon atoms. It is preferable that there is.
  • R 10 and R 11 is ethylene group or trimethylene group, the number of p force 0-3, and particularly preferably q and r is 2.
  • s, t and u are each independently a number from 1 to 700, but sXp + tXq + uXr must be a number from 25 to 700. sXp + tXq + uXr is preferably 40 to 500.
  • Reactant 6 is a compound at 40 ° C or higher, but the melting point of Reactant 6 is 40 to 90 ° C. ° C, more preferably 45 to 70 ° C. If the melting point is lower than 40 ° C, the transparent paper will be sticky.
  • the reactant 6 is preferably an aqueous compound that gives a transparent aqueous solution when mixed with water so as to be 1% by weight. This is because, when it is strong, the recyclability of the transparent paper becomes better.
  • the average molecular weight of the reactant 6 is preferably not more than 20,000, more preferably from 2,000 to 15,500. If the average molecular weight exceeds 20,000,000, application to paper tends to be difficult.
  • the paper clarifying agent of the present invention may contain other components as long as it contains compound 1, reactant 2, compound 3, reactant 4, compound 5, or reactant 6 described above.
  • a small amount of an alcohol-based solvent or a surfactant may be contained for the purpose of lowering the viscosity or improving the permeability to paper.
  • the alcohol-based solvent examples include methanolic ethanol, ethanolanol, propynoleanolecone, ethylene glycol, and jettylendaricol.
  • a non-ionic surfactant having good permeability for example, Lauryl alcohol ethylene oxide 9 mol adduct
  • anionic surfactants with good permeability eg, dioctyl sulfosuccinate
  • Examples of the m-valent carboxylic acid used in the production of Compound 1 and Compound 2 include, for example, oxalic acid, malonic acid, succinic acid, succinic anhydride, gnoletanolic acid, adipic acid
  • Monoamines applicable to obtain compound 3 and reactant 4 include carbon atoms 1
  • monoamines having a hydrocarbon group of 2 to 22 primary amine or secondary amine
  • monoamines having an alkoxyalkyl group having 2 to 22 carbon atoms primary amine or secondary amine
  • the hydrocarbon group having 1 to 22 carbon atoms or the alkoxyalkyl group having 2 to 22 carbon atoms in the monoamine may be linear or branched.
  • Examples of the monoamine having a hydrocarbon group having 1 to 22 carbon atoms include methylamine, phenol pinoleamine, butylamine, isobutynoleamine, hexinoleamine, 2-ethynolehexylamine, octynoleamine, laurylamine, stearylamine, behenylamine, Examples thereof include leylamine, methinoleeth / reamine, dipropynoleamine, diptinoleamine, methylhexylamine, di-N-octylamine, methylstearylamine, and 4-methylaminobutanol.
  • Examples of the monoamine having an alkoxyalkyl group having 2 to 22 carbon atoms include 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, and 3-butoxypropyl. Amine, 31-decyloxypropylamine, 3-lauryloxypropylamine, 3_myristoxypropylamine and the like.
  • a polyamine (compound 7) represented by the general formula (7) is used.
  • Examples of the polyamine in which p is 0 in compound 7 include ethylenediamine; and examples of the polyamine in which 1 to 6 are: dimethylaminoethylamine, 1,3-propanediamine, methylaminopropylamine, dimethylamino Propylamine, getylaminopropylamine, diethylenetriamine, iminobispropylamine, methyliminopropylamine, triethylenetetramine and the like.
  • Compound 1, reactant 2, compound 3, reactant 4, compound 5, and reactant 6 used in the acylation reaction include acetyl chloride, propionic chloride, octanoic chloride, lauric chloride, and the like.
  • Monocarboxylic acid chlorides such as oleic acid chloride and stearic acid chloride.
  • the saturated or unsaturated alcohol used for etherification in Compound 1, Reactant 2, Compound 3, Reactant 4, Compound 5, and Reactant 6 is preferably one having 1 to 22 carbon atoms. May be linear or branched.
  • Such alcohols include, for example, methanol, ethanol, propanol, o-octano-ole, 2-ethynole-hexeno-le-a-no-cone, lauri-no-le-a-no-cone, myristino-le-a-no-re-conore, no-no-remicino-le-a-no-cone, and stearinore.
  • Anoreco beheninoleanol, alylanolecole, natural rail alcohol, docosenol and the like.
  • the glycidyl ether used in the etherification has 1 to 1 carbon atoms.
  • Glycidyl ethers of alcohols of 8 are preferred, e.g. Monoter, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether and the like.
  • a monoisocyanate having an olenoquinole group having 1 to 18 carbon atoms is used as the monoisocyanate used for the urethanization in the compound 1, the reactant 2, the compound 3, the reactant 4, the compound 5, and the reactant 6, a monoisocyanate having an olenoquinole group having 1 to 18 carbon atoms is used.
  • Preferred are, for example, methyl isocyanate, butyl isocyanate, neopentyl isocyanate, octyl isocyanate, laurylisocyanate, stearyl lysocyanate and the like.
  • Examples of the polycarboxylic acid for obtaining the reactant 2, the reactant 4, and the reactant 6 include oxalic acid, malonic acid, succinic acid, succinic anhydride, glutaric acid, adipic acid, suberic acid, and azelaine. Acid, sebacic acid, maleic acid, maleic anhydride, fumaric acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, malic acid, tartaric acid And cunic acid.
  • Examples of the polyisocyanate for obtaining the reactant 2, the reactant 4, and the reactant 6 include, for example, an aliphatic diisocyanate such as hexamethylene diisocyanate and trimethinolehexamethylene diisocyanate; Alicyclic diisocyanates such as hydrogenated xylylene disocyanate, hydrogenated xylylene disocyanate, dicyclohexyl / methandi disocyanate, norbornane disocyanate; dipheninolemetane diisocyanate, naphthalenedi isocyanate, And aromatic diisocyanates such as tolylene diisocyanate and xylylene diisocyanate.
  • an aliphatic diisocyanate such as hexamethylene diisocyanate and trimethinolehexamethylene diisocyanate
  • Alicyclic diisocyanates such as hydrogenated xylylene disocyanate, hydrogenated xylylene dis
  • hexamethylene diisocyanate, hydrogenated tolylene diisocyanate, and isophorone diisocyanate are particularly preferred because transparent paper is non-yellowing.
  • One of these polyisocyanate compounds may be used alone, or two or more thereof may be used in combination.
  • Examples of the polyglycidyl ether for obtaining Reactant 2, Reactant 4, and Reactant 6 include, for example, ethylene glycol diglycidinoleateneole and neopentinoleg. Recohol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol monoresiglycidinole ether, trimethylo monopropane polyglycidyl ether, glycerol polyglycidyl / leetenore, pentaerythritol polyglycidyl ether, etc. Is mentioned.
  • the method for producing a transparent paper according to the present invention is characterized by including an attaching step of attaching the above-described paper clarifying agent of the present invention to paper, wherein the attaching step comprises: It is possible to adopt a method in which the resin is heated and melted and adhered to the paper, and a method in which an aqueous solution of the paper clarifying agent is adhered (applied) to the paper.
  • paper to which the paper clarifying agent is adhered it is preferable to use paper made mainly of vegetable pulp composed of cellulosic fibers in view of the mechanism of the transparency of the present invention.
  • the paper clarifying agent of the present invention is preferably applied to at least one side of paper.
  • Conventionally known coating methods can be applied, for example, bar coater, doctor coat, blade coat, air knife coat, squeeze coat, reverse coat coating
  • the paper clarifying agent it is preferable to apply the paper clarifying agent at a weight such that the effective component is 20 to 100% of the basis weight of the paper.
  • oxidized starch, starch derivatives, polyvinyl alcohol, vinyl acetate and maleic acid may be used.
  • a water-soluble resin such as methylcellulose or acrylamide resin, or a commercially available varnish may be applied.
  • the melting point was measured according to JIS K0064 (1992), a visual method.
  • the clarifying agents for paper of Examples and Comparative Examples were applied to the surface of a test paper having an opacity of 68% and a basis weight of 50 gZm 2 , and applied with a single coater.
  • the paper clarifying agent is solid, heat and melt it to the temperature described in each Example and Comparative Example and apply it to the surface of the test paper.
  • the application was performed so that the active ingredient such as an aqueous compound in the paper clarifying agent was 35 g / m 2 (70% based on test paper).
  • the coated paper was dried at 105 ° C for 60 seconds and cooled at room temperature to obtain a transparent paper.
  • the transparency, stickiness of the surface, and paper recyclability were evaluated by the following methods (1), (2) and (3), respectively.
  • the opacity (%) of the transparent paper was measured using REFLECTOMETER EMOLED TC-ED (Tokyo Denshoku Co., Ltd.) in accordance with JIS P 8138 (1 976). The smaller the value, the better the transparency.
  • Dissolution rate (weight before immersion ⁇ weight after immersion) / total weight of active ingredient ⁇ 100
  • the recyclability of transparent paper was evaluated based on the elution rate of the active ingredient. The higher the dissolution rate, the better the recyclability of the paper.
  • dissolution rate is 90. /. More than 95 ° /. Less than
  • a 5 L high-pressure reactor was charged with 186 g of radial alcohol and 3.7 g of lithium hydroxide, dehydrated under reduced pressure at 100 to 120 ° C for 30 minutes, and then ethylene oxide 3520 at 120 to 150. g was introduced while maintaining the reaction pressure at 4 kg / cm 2 or less. After the introduction, in 1 2 O ⁇ 1 50 ° C, after the reaction pressure was allowed to react almost 0 kg / cm to about 30 minutes until 2, it cooled, acetic acid in 80 ° C or below by the addition of about 4 g After neutralization, an adduct of 80 mol of lauryl alcohol ethylene oxide was obtained. This pressed pulp was a white solid at room temperature and had a melting point of 50 ° C.
  • a 500 mL four-necked flask was equipped with a dehydrator, a thermometer, and a nitrogen inlet tube.
  • the reaction was carried out at 150 to 200 ° C for about 3 hours until the acid value became 1 nigKOHZg or less.
  • the mixture was cooled to ° C and reacted for about 3 hours to obtain lauric acid monoester of polyethylenedaricol.
  • the melting point of this monoester was 54 ° C.
  • Transparent paper was produced using this polyethylene glycol laurate monoester as a paper clarifying agent.
  • Hexamethylene diisocyanate (8.4 g) was added dropwise over about 1 hour. After dropping, sample on the way, and react at 100 to 110 ° C for about 5 hours with an infrared spectrophotometer (IR-810, JASCO Corporation) until the absorption of the isocyanate group disappears. Was. The melting point of the reaction was 51 ° C.
  • the obtained reaction product (35 g) was heated and melted, and water (55 g) was gradually added and mixed therein.Then, the mixture was cooled to 40 ° C or lower, and ethanol (10 g) was added and mixed until uniform. Was. Then, a transparent paper was prepared using the obtained solution as a paper clarifying agent. (Example 5)
  • P EG 2000 polyethylene glycol (manufactured by Sanyo Chemical Industries, Ltd.)), molecular weight approx.
  • PEG4000 polyethylene glycol (Sanyo Chemical Industries, Ltd., molecular weight 300)
  • PEG 6 000 Polyethylene Dalicol (Sanyo Chemical Industries, Ltd., molecular weight approx. 83)
  • Pull mouth nick F_68 (Asahi Denka Kogyo Co., Ltd., molecular weight approx. 8350) Melt 30 g by heating, gradually add 60 g of water and mix, then cool to below 40 ° C Then, 10 g of ethanol was added and mixed until uniform. Then, a transparent paper was produced by using the obtained solution as a paper clearing agent.
  • Sunmol N-300 (manufactured by Nikka Chemical Co., Ltd., 30 mol adduct of noelphenol ethylene oxide, melting point: 43 ° C) was used as a paper clarifying agent, and was heated and melted at 100 ° C. To produce a transparent paper.
  • a 5 L high-pressure reactor was charged with 104 g of neopentinoledaricorne and 3.6 g of potassium hydroxide, dehydrated at 130 to 140 ° C for 30 minutes under reduced pressure, and then cooled to 13 °.
  • 350 g of ethylene oxide was introduced while maintaining the reaction pressure at 4 kg / cm 2 or less.
  • 1 50 ° C after the reaction pressure was allowed to react almost 0 kg / cni about 3 0 minutes until 2, cooled and then sum the medium of acetic acid at below 8 0 ° C was added about 4 g
  • 80 mol of neopentyl glycol ethylene oxide adduct was obtained.
  • the adduct was a white solid at room temperature and had a melting point of 52 ° C. This adduct was used as a paper clarifying agent, and was heated and melted at 100 ° C. to produce a transparent paper.
  • a 5 L high-pressure reactor was charged with 92 g of glycerin and 4.lg of potassium hydroxide, dehydrated under reduced pressure at 130 to 140 for 30 minutes, and then ethylene oxide at 130 to 150 ° C. 60 g were introduced while maintaining the reaction pressure at 4 kg / cm 2 or less. After introduction, 1 5 0 ° C, after the reaction pressure was allowed to react substantially 0 k GZcm about 3 0 minutes until 2, cooled, medium acetic acid at 80 ° C below about 4. In addition 5 g Then, 90 mol of Dari serine ethylene oxide adduct was obtained. The adduct was a white solid at room temperature and had a melting point of about 48 ° C. This adduct was used as a paper clarifying agent, and was heated and melted at 100 ° C. to produce a transparent paper.
  • a 5-L high-pressure reactor was charged with 700 g of BPA_16 (a product of Nichika Chemical Co., Ltd., 16 moles of ethylenoxide of bisphenol A) and 3.5 g of potassium hydroxide. After dehydration under reduced pressure at 130-140 ° C for 30 minutes, 277 g of ethylenoxide was introduced at 130-150 ° C while maintaining the reaction pressure at 4 kg / cm 2 or less. After the introduction, in 1 5 0 ° C, after the reaction pressure was almost react 0 k gZ cm to about 3 0 minutes until 2, cooled, the acetic acid from about 3.
  • BPA_16 a product of Nichika Chemical Co., Ltd., 16 moles of ethylenoxide of bisphenol A
  • a 50 OmL four-necked flask was equipped with a dehydrator, thermometer, and nitrogen inlet tube.
  • the reaction was carried out at 200 to 220 ° C for about 5 hours until the acid value became 0.5 ragK0H / g or less.
  • An ethylene glycol adduct of adipic acid was obtained.
  • the melting point of this adduct was 54 ° C. This adduct was used as a paper clarifying agent, and was heated and melted at 100 ° C. to produce a transparent paper.
  • a 50 OmL four-necked flask was equipped with a dehydrator, a thermometer, and a nitrogen inlet tube, and 400 g of PEG4000 (manufactured by Sanyo Chemical Co., Ltd., average molecular weight 300,000), conoic acid 11.8 g and 0.5 g of paratoluenesulfonic acid, raise the temperature while introducing nitrogen gas, and react at 200 to 220 ° C for about 5 hours until the acid value becomes 0.5 mgK0H / g or less.
  • the melting point of this adduct was 59 ° C. This adduct is used as a paper clarifying agent, and is heated and melted at 100 ° C. A transparent paper was made.
  • a 50 OmL four-necked flask was equipped with a dehydrator, thermometer, and nitrogen inlet tube.
  • 360 g of PEG2000 (manufactured by Sanyo Chemical Co., Ltd., average molecular weight 2000), 360 g of trimellitic anhydride, and 11.6 g of paramellitic anhydride were added to the flask.
  • Toluenesulfonic acid (0.5 g) was charged, the temperature was raised while introducing nitrogen gas, and the reaction was carried out at 200 to 220 ° C for about 5 hours until the acid value became 0.5 mgK0H / g or less.
  • An ethylene oxide adduct was obtained.
  • the melting point of this adduct was 53 ° C. This adduct was used as a paper clarifying agent, and was heated and melted at 100 ° C to produce a transparent paper.
  • a 50 OmL four-necked flask was equipped with a vacuum dehydrator, a manometer, a thermometer, and a nitrogen inlet tube, into which PEG 2000 (manufactured by Sanyo Chemical Co., Ltd., average molecular weight 20000) 360 g, bis (2-hi) 17.8 g of terephthalate and 0.1 g of zinc acetate were charged, the temperature was increased while introducing nitrogen gas, and the reaction was carried out at 220 to 250 ° C under reduced pressure (50 to 10 mmHg) for about 4 hours. An ethylene oxide adduct of the acid was obtained. The melting point of this adduct was 50 ° C. This adduct was used as a paper clearing agent, and was heated and melted at 100 ° C. to produce a transparent paper.
  • PEG 2000 manufactured by Sanyo Chemical Co., Ltd., average molecular weight 20000
  • a 50 OmL four-necked flask was equipped with a dehydrator, a thermometer, and a nitrogen inlet tube, into which 320 g of stearyl alcohol ethylene oxide 28 mol adduct, succinic acid 12.6 g, and paratoluenesulfonic acid 0 were added. 5 g, raise the temperature while introducing nitrogen gas, and react at 200-220 ° C for about 5 hours until the acid value becomes 0.5 mgKOH / g or less, to obtain stearyl alcohol ethylene oxide adduct. A succinic acid ester was obtained. The melting point of this compound was 46 ° C. This compound was used as a paper clarifying agent, and was heated and melted at 100 ° C. to produce a transparent paper. (Example 19)
  • Adecapul mouth nick TR-70 7 (Asahi Denka Co., Ltd., ethylenediamine propylene oxide and ethylene oxide block adduct, average molecular weight 12,000, melting point 49 ° C) The mixture was heated and melted at 100 ° C to produce a transparent paper.
  • a dehydrator, thermometer, and nitrogen inlet tube were attached to a 500 mL four-necked flask.
  • Compound, average molecular weight 12,100, melting point 49 ° C) 300 g, lauric acid 10 g, and paratoluenesulfonic acid 0.31 g, and heated while introducing nitrogen gas.
  • the reaction was carried out at 220 to 240 ° C. until the acid value became 1 mg KOHZ g or less, to obtain diradiuric acid esters of propylene oxide of ethylenediamine and a block adduct of ethylene oxide.
  • the melting point of this compound was 48 ° C. This compound was used as a paper clarifying agent, and was heated and melted at 100 ° C. to produce a transparent paper.
  • a 5 L high-pressure reactor was charged with 313 g of stearylamine ethylene oxide 2 mol adduct and 3.7 g of sodium hydroxide, and after sufficiently purging with nitrogen, was heated and melted.
  • 211 g of ethylene oxide was introduced at a reaction pressure of 4 kgZcm 2 or less.
  • the reaction was carried out at 150 to 180 ° C. for about 30 minutes until the reaction pressure became approximately 0 kg / cm 2 .
  • the reaction mixture was cooled and subjected to deoxidation under reduced pressure for 30 minutes. Further, at 80 ° C.
  • Example 22 A 50 OmL four-necked flask was equipped with a dehydrator, a thermometer, and a nitrogen inlet tube, and 242.5 g of a 50 mol ethylene oxide adduct of stearylamine obtained in Example 3 was placed therein. And 20 g of lauric acid and 0.24 g of paratoluenesulfonic acid, and the temperature was increased while introducing nitrogen gas to obtain an acid value of 1111 ⁇ The reaction was carried out at 230 to 250 ° C. for about 5 hours until a monoradiuric acid ester of ethylene oxide 50 mozole adduct of stearylamine was obtained. The melting point of this compound was 47 ° C. This compound was used as a paper clarifying agent, and was heated and melted at 100 ° C. to produce a transparent paper.
  • a 50 OmL four-necked flask was equipped with a dehydrator, a thermometer, and a nitrogen inlet tube, and 485 g of the caroyl with 50 mol of ethylene oxide of stearylamine obtained in Example 21 was charged therein.
  • the temperature was raised while introducing nitrogen gas, the pressure was reduced at 100 to 120 ° C, and dehydration was performed for about 1 hour.
  • 16.8 g of hexamethylene diisocyanate was added dropwise. Sampling is carried out during the dropping, and 80-80 until the absorption of the isocyanate group disappears with an infrared spectrophotometer (IR-810, B-spectroscopy).
  • the reaction was carried out at 100 for 5 hours.
  • the melting point of the obtained compound was 50 ° C.
  • This compound was used as a paper clarifying agent, and was heated and melted at 10 ° C. to produce a transparent paper.
  • a 300 mL four-necked flask was equipped with a dehydrator, a thermometer, and a nitrogen inlet tube.
  • Adekapur Mouth Nick TR-707 (produced by Asahi Denka Co., Ltd., ethylenediamine propylene oxide and ethylene) 240 g of an oxide block adduct, average molecular weight of 12,000) was charged, the temperature was increased while introducing nitrogen gas, the pressure was reduced at 100 to 120 ° C, and dehydration was performed for about 1 hour. After cooling to 70 ° C., 1.7 g of hexamethylene diisocyanate was added dropwise.
  • Transparent paper was prepared by using paraffin wax 115 ° F (Nippon Seisaku Co., Ltd., melting point 45 ° C) as a paper clarifying agent, which was heated and melted at 10 ° C.
  • Transparent paper was produced by using 130 ° F (Noraffine wax, Mobil Oil Co., Ltd., melting point 58 ° C.) as a paper clarifying agent and heating and melting at 100 ° C.
  • Kuraray Povar PVA-l10 (Kuraray Co., Ltd., polybutyl alcohol, degree of polymerization 1000, solid at 40 ° C or more) l OOg and 900g of water are mixed, and 90 ⁇ 100 ° C, 3 ⁇ After stirring and dissolving for 4 hours, the mixture was cooled to room temperature to obtain a 10% by weight aqueous solution of polybutyl alcohol. This aqueous solution was used as a paper clarifying agent to prepare a transparent paper.
  • a 40% by weight aqueous solution of sodium polyacrylate (molecular weight 10,000, solid at 40 ° C. or higher) was prepared, and a transparent paper was prepared using this aqueous solution as a paper clarifying agent.
  • Table 1 below shows the evaluation results of the transparent papers obtained in the above Examples and Comparative Examples.
  • the transparent paper obtained using the paper clarifying agent of the example of the present invention has excellent transparency, has no stickiness on the surface, and has a high elution rate of the active ingredient. for It was found that the clarifying agent was easily removed, and the recyclability of the paper was good. On the other hand, the transparency of the transparent papers obtained in Comparative Examples 1 and 2 was slightly inferior to that of the Examples and there was no stickiness on the surface, but the elution rate of the active ingredient was 20% or less, and the recyclability was low. Was inferior. Further, in Comparative Examples 3 and 4, an aqueous compound solid at 40 ° C. was used, but since the chemical structure was different from that of the present invention, the transparency was very poor.
  • the present invention it is possible to obtain a transparent paper having excellent transparency, no stickiness on the surface of the transparent paper, easy removal of the clarifying agent, and excellent paper recyclability. It is possible to provide a possible paper clarifier. In addition, it is possible to provide a method for producing transparent paper using such a paper clarifying agent.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

L'invention concerne un clarificateur pour papiers qui comprend un composé eau compatible, représenté par la formule générale (1) suivante et dont le point de fusion excède au moins 40°C: R0-(X1-(A-O)¿n-Z?1)m, dans laquelle R0 représente un groupe hydrocarboné C¿1-22? ayant une valence de m ou un résidu de valence m d'un alcool hétérocyclique C6-12; X?1¿ représente O- ou COO-; A représente C¿2-4? alkylène; Z?1¿ représente hydrogène, acyle, un groupe hydrocarboné monovalent C¿1-22?, ou CONH-R?2¿; m représente un nombre de 1 à 10; et n un nombre satisfaisant à la relation 25 ≤ n x m ≤ 700; pour autant que R2 soit un groupe hydrocarboné monovalent C¿1-22? et que, lorsque m est égal à 2, R?0¿ puisse représenter une liaison simple.
PCT/JP2002/004174 2001-04-25 2002-04-25 Clarificateur de papier et procede de production de papier transparent WO2002088467A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP2001-128414 2001-04-25
JP2001128414A JP4713008B2 (ja) 2001-04-25 2001-04-25 紙用透明化剤
JP2002113896A JP4162421B2 (ja) 2002-04-16 2002-04-16 紙用透明化剤及び透明紙の製造方法
JP2002-113896 2002-04-16
JP2002116624A JP4298217B2 (ja) 2002-04-18 2002-04-18 紙用透明化剤及び透明紙の製造方法
JP2002-116624 2002-04-18

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WO2002088467A1 true WO2002088467A1 (fr) 2002-11-07

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS40577B1 (fr) * 1963-01-31 1965-01-13
JPS5450612A (en) * 1977-09-30 1979-04-20 Gen Corp Production of transparent paper
GB2122230A (en) * 1982-04-30 1984-01-11 Ricoh Kk Transparentized intermediate original sheets

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS40577B1 (fr) * 1963-01-31 1965-01-13
JPS5450612A (en) * 1977-09-30 1979-04-20 Gen Corp Production of transparent paper
GB2122230A (en) * 1982-04-30 1984-01-11 Ricoh Kk Transparentized intermediate original sheets

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