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WO2011070800A1 - Feuille de base en papier antiadhésif - Google Patents

Feuille de base en papier antiadhésif Download PDF

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Publication number
WO2011070800A1
WO2011070800A1 PCT/JP2010/052786 JP2010052786W WO2011070800A1 WO 2011070800 A1 WO2011070800 A1 WO 2011070800A1 JP 2010052786 W JP2010052786 W JP 2010052786W WO 2011070800 A1 WO2011070800 A1 WO 2011070800A1
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WIPO (PCT)
Prior art keywords
poa
polymerization
release paper
group
pva
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.)
Ceased
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PCT/JP2010/052786
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English (en)
Japanese (ja)
Inventor
真輔 新居
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Kuraray Co Ltd
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Kuraray Co Ltd
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Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to JP2011545101A priority Critical patent/JP5524240B2/ja
Publication of WO2011070800A1 publication Critical patent/WO2011070800A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
    • D21H27/001—Release paper
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a release paper base paper having excellent surface barrier properties, oil resistance, and water resistance.
  • the release paper which is coated with a release layer coating containing a silicone resin with water repellency on the surface to give release performance to the surface, is a substrate for obtaining adhesive labels, adhesive tapes, and industrial adhesive papers. In addition, it is used as a release paper.
  • paper has many voids between pulp fibers, which are the main components of the paper, and is highly permeable and air permeable, when paint is applied directly to the paper surface, the paint is between the fibers. Penetration occurs, and a coating film cannot be formed on the paper surface, and a release paper having sufficient release performance cannot be obtained.
  • a method of coating an aqueous PVA solution on the paper surface using the excellent film forming ability and oil resistance of polyvinyl alcohol (hereinafter sometimes abbreviated as PVA) is generally used.
  • PVA polyvinyl alcohol
  • ordinary PVA has excellent barrier properties against the coating material for the release layer and the solvent contained therein, it has poor water resistance, and there is a problem that polyvinyl alcohol is eluted and blocked by humidification during processing of the adhesive layer. .
  • Patent Document 1 For the purpose of improving the water resistance of PVA, a release paper base paper using a modified PVA containing an ⁇ -olefin unit having 4 or less carbon atoms has been reported, and the water resistance and barrier properties have been improved as a release paper base paper. Although there is an example (Patent Document 1), further performance improvement has been demanded.
  • An object of the present invention is to provide a base paper for release paper having excellent barrier properties and water resistance against a solvent in an oily or water dispersible varnish.
  • An object of the present invention is a release paper base paper obtained by coating a base material with a coating agent containing a polyoxyalkylene-modified vinyl alcohol polymer (hereinafter sometimes abbreviated as POA-modified PVA).
  • a coating agent containing a polyoxyalkylene-modified vinyl alcohol polymer hereinafter sometimes abbreviated as POA-modified PVA.
  • POA group a polyoxyalkylene group represented by the following general formula (I) (hereinafter sometimes abbreviated as POA group) in the side chain, has a viscosity average polymerization degree P of 500 to 5000, and a saponification degree of 20
  • This is achieved by providing a release paper base having a polyoxyalkylene group modification amount S (hereinafter sometimes abbreviated as POA group modification amount S) of 0.1 to 10 mol%. Is done.
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • m and n represent the number of repeating units of each oxyalkylene unit, and 0 ⁇ m ⁇ 10 and 3 ⁇ n ⁇ 20.
  • the release paper base paper of the present invention exhibits high water resistance and barrier properties by using POA-modified PVA.
  • the POA-modified PVA contained in the coating agent that is a raw material for the release paper base paper of the present invention has a POA group represented by the following general formula (I) in the side chain.
  • R1 represents a hydrogen atom or a methyl group
  • R2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • m and n represent the number of repeating units of each oxyalkylene unit, and 0 ⁇ m ⁇ 10 and 3 ⁇ n ⁇ 20.
  • unit 1 a unit having the number of repeating units m is referred to as unit 1
  • unit 2 a unit having the number of repeating units n is referred to as unit 2.
  • the arrangement of the unit 1 and the unit 2 may be random or block.
  • the repeating unit number m of the unit 1 of the POA group represented by the general formula (I) needs to satisfy 0 ⁇ m ⁇ 10, more preferably 0 ⁇ m ⁇ 5, and particularly preferably 0 ⁇ m ⁇ 2. Further, the number n of repeating units of unit 2 needs to satisfy 3 ⁇ n ⁇ 20, preferably 5 ⁇ n ⁇ 18, and particularly preferably 8 ⁇ n ⁇ 15. When n is less than 3, the interaction between POA groups does not appear, and the viscosity of the POA-modified PVA aqueous solution may be low. When n is more than 20, the hydrophobicity of the POA group becomes high, and the POA-modified PVA Water solubility may decrease.
  • the POA-modified PVA contained in the coating agent that is the raw material of the release paper base paper of the present invention only needs to contain the POA group represented by the above general formula (I) in the side chain, and the POA-modified PVA is produced.
  • the method is not particularly limited, but the POA-modified vinyl ester copolymer obtained by copolymerizing an unsaturated monomer having a POA group represented by the general formula (I) with a vinyl ester monomer is obtained.
  • a saponification method is preferred.
  • the above copolymerization is preferably performed in an alcohol solvent or without a solvent.
  • the unsaturated monomer having a POA group represented by the general formula (I) is preferably an unsaturated monomer represented by the following general formula (II).
  • R1, R2, m, and n are the same as those in the general formula (I).
  • R3 represents a hydrogen atom or a —COOM group, where M represents a hydrogen atom, an alkali metal or an ammonium group.
  • R4 represents a hydrogen atom, a methyl group or a —CH 2 —COOM group, where M is as defined above.
  • X represents —O—, —CH 2 —O—, —CO—, — (CH 2 ) k —, —CO—O— or —CO—NR 5 —.
  • R5 represents a hydrogen atom or a saturated alkyl group having 1 to 4 carbon atoms
  • k represents the number of repeating units of a methylene unit, and 1 ⁇ k ⁇ 15.
  • R2 of the unsaturated monomer represented by the general formula (II) a hydrogen atom, a methyl group or a butyl group is preferable, and a hydrogen atom or a methyl group is more preferable. Furthermore, it is particularly preferable that R1 of the unsaturated monomer represented by the general formula (II) is a hydrogen atom or a methyl group, R2 is a hydrogen atom or a methyl group, and R3 is a hydrogen atom.
  • R1 in the general formula (II) is a hydrogen atom or a methyl group
  • R2 is a hydrogen atom
  • R3 is a hydrogen atom
  • the unsaturated monomer represented by the general formula (II) is specifically polyoxyethylene.
  • polyoxyethylene polyoxybutylene monoacrylic acid amide, polyoxyethylene polyoxybutylene monomethacrylic acid amide, polyoxyethylene polyoxybutylene monovinyl ether are preferably used, polyoxyethylene polyoxybutylene monomethacrylic acid amide, Polyoxyethylene polyoxybutylene monovinyl ether is particularly preferably used.
  • the unsaturated monomer represented by the general formula (II) is specifically R1 in the general formula (II) is a hydrogen atom or methyl
  • R2 being a hydrogen atom and R3 being a hydrogen atom include those in which the terminal OH group of the unsaturated monomer exemplified above is substituted with an alkoxy group having 1 to 8 carbon atoms.
  • unsaturated monomers in which the OH group at the terminal of polyoxyethylene polyoxybutylene monomethacrylamide or polyoxyethylene polyoxybutylene monovinyl ether is substituted with a methoxy group are preferably used.
  • An unsaturated monomer in which the OH group at the terminal of butylene monomethacrylamide is substituted with a methoxy group is particularly preferably used.
  • the temperature employed when copolymerizing the unsaturated monomer having a POA group represented by the general formula (I) and the vinyl ester monomer is preferably 0 to 200 ° C, more preferably 30 to 140 ° C. preferable.
  • the copolymerization temperature is lower than 0 ° C., it is difficult to obtain a sufficient polymerization rate.
  • polymerizes is higher than 200 degreeC, it is difficult to obtain POA modified PVA which has the POA modified amount prescribed
  • the heat generated by the polymerization is balanced with the heat released from the surface of the reactor.
  • Examples thereof include a method and a method of controlling by an external jacket using an appropriate heat medium, but the latter method is preferable from the viewpoint of safety.
  • Polymerization methods used for copolymerization of unsaturated monomers having a POA group represented by the general formula (I) and vinyl ester monomers include batch polymerization, semi-batch polymerization, continuous polymerization, Any of continuous polymerization may be used.
  • the polymerization method any known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method can be used.
  • a bulk polymerization method or a solution polymerization method in which polymerization is performed in the absence of a solvent or an alcohol solvent is preferably employed, and an emulsion polymerization method is employed for the purpose of producing a copolymer having a high degree of polymerization.
  • the alcohol solvent include methyl alcohol, ethyl alcohol, propyl alcohol, and the like, but are not limited thereto. These solvents can be used in combination of two or more.
  • azo initiators As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like are appropriately selected according to the polymerization method.
  • the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile) and the like
  • peroxide initiators include perisopropyl compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, ⁇ -cumylperoxyneodecanate, and t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethyl
  • the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator.
  • the redox initiator include a combination of the above-described peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, Rongalite and the like.
  • vinyl ester monomers examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, Examples include vinyl stearate, vinyl oleate, vinyl benzoate, etc. Among them, vinyl acetate is most preferable.
  • the unsaturated monomer having a POA group represented by the general formula (I) and the vinyl ester monomer are copolymerized
  • other monomers may be copolymerized within a range not to impair the gist of the present invention.
  • monomers that can be used include ⁇ -olefins such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and its salts; methyl acrylate, ethyl acrylate, n-propyl acrylate, and i-propyl acrylate.
  • Acrylic acid esters such as n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate and octadecyl acrylate; methacrylic acid and salts thereof; methyl methacrylate, methacryl Methacrylic acid such as ethyl acetate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate Esters; N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acrylamidepropyld
  • the present invention is used for the purpose of adjusting the degree of polymerization of the copolymer obtained in the copolymerization of the unsaturated monomer having a POA group represented by the general formula (I) and the vinyl ester monomer.
  • Copolymerization may be carried out in the presence of a chain transfer agent as long as the gist of the invention is not impaired.
  • Chain transfer agents include aldehydes such as acetaldehyde and propionaldehyde; ketones such as acetone and methyl ethyl ketone; mercaptans such as 2-hydroxyethanethiol; halogenated hydrocarbons such as trichloroethylene and perchloroethylene; sodium phosphinate 1 Examples thereof include phosphinic acid salts such as hydrates, among which aldehydes and ketones are preferably used.
  • the addition amount of the chain transfer agent is determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target vinyl ester polymer, but is generally 0.1% relative to the vinyl ester monomer. ⁇ 10% by weight is desirable.
  • an alcoholysis decomposition reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as P-toluenesulfonic acid can be applied.
  • a hydrolysis reaction can be applied.
  • the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene; These can be used alone or in combination of two or more. Among them, it is convenient and preferable to perform the saponification reaction using methanol or a methanol / methyl acetate mixed solution as a solvent and sodium hydroxide as a catalyst.
  • the POA-modified PVA contained in the coating agent that is the raw material of the release paper base paper of the present invention needs to have a POA group modification amount S of 0.1 to 10 mol%.
  • the POA group modification amount S exceeds 10 mol%, the proportion of hydrophobic groups contained in one molecule of the POA group modified PVA increases, and the water solubility of the PVA may decrease.
  • the POA group modification amount S is less than 0.1 mol%, the water solubility of the POA modified PVA is excellent, but the number of POA groups contained in the PVA is small, and physical properties based on the POA modification are not expressed. There is a case.
  • the POA group modification amount S is represented by the molar fraction of the POA group with respect to the main chain methylene group of PVA.
  • the lower limit of the POA group modification amount S is 0.1 mol% or more, preferably 0.2 mol% or more, and more preferably 0.3 mol% or more.
  • the upper limit of the POA group modification amount S is preferably less than 2.0 mol%, more preferably 1.5 mol% or less.
  • the POA group modification amount S of the POA-modified PVA can be determined from proton NMR of the POA-modified vinyl ester that is a precursor of the POA-modified PVA. Specifically, after reprecipitation and purification of the POA-modified vinyl ester with n-hexane / acetone three or more times, the sample is dried at 50 ° C. under reduced pressure for 2 days to obtain a sample of POA-modified vinyl ester for analysis. Create The sample is dissolved in CDCl 3 and measured at room temperature using 500 MHz proton NMR (JEOL GX-500).
  • n the number of repeating units of unit 2.
  • S (mol%) ⁇ (number of protons of ⁇ / 3n) / (number of protons of ⁇ + (number of protons of ⁇ / 3n)) ⁇ ⁇ 100
  • the viscosity average polymerization degree P of the POA-modified PVA is measured according to JIS-K6726. That is, after re-saponifying and purifying the PVA, it is obtained by the following equation from the intrinsic viscosity [ ⁇ ] measured in water at 30 ° C.
  • the degree of polymerization of POA-modified PVA contained in the coating agent that is the raw material of the release paper base paper of the present invention is 500 to 5000, preferably 500 to 3000.
  • the degree of polymerization exceeds 5000, the productivity of the PVA is lowered and is not practical.
  • the degree of polymerization is less than 500, the barrier properties of the resulting release paper may not be expressed.
  • the saponification degree of the POA-modified PVA needs to be 20 to 99.99 mol%, preferably 40 to 99.9 mol%, more preferably 80 to 99.9 mol%, and 95 to 99.9 mol%. More preferred is 98-99.9 mol%.
  • the degree of saponification is less than 20 mol%, the water solubility of the POA-modified PVA is lowered and it is difficult to prepare an aqueous solution of PVA.
  • the degree of saponification exceeds 99.99 mol%, the POA-modified PVA It is not practical because production becomes difficult.
  • the saponification degree of the POA-modified PVA is a value that can be measured according to JIS-K6726.
  • the content of the POA group represented by the general formula (I) is preferably 50 parts by weight or less, more preferably 30 parts by weight or less, and particularly preferably 15 parts by weight or less.
  • the lower limit of the content is preferably 2.5 parts by weight or more.
  • the content of the POA group represented by the general formula (I) is represented by the weight part (weight fraction) of the POA group represented by the general formula (I) with respect to 100 parts by weight of the main chain of PVA, and the POA group This is a value calculated using the amount of modification S, the number m of repeating units of unit 1, the number of repeating units n of unit 2, and the saponification degree of POA-modified PVA. Even if the above-mentioned POA group modification amount S is equivalent, the POA group content in the POA-modified PVA increases as the degree of saponification increases or as m or n increases.
  • the viscosity of a 4% by weight aqueous solution of POA-modified PVA contained in the coating agent that is the raw material for the release paper base paper of the present invention was measured with a B-type viscometer under the condition of a rotor rotational speed of 6 rpm, the viscosity ⁇ 1 at 20 ° C.
  • the ratio ⁇ 2 / ⁇ 1 of the viscosity ⁇ 2 at 40 ° C. is preferably 0.8 or more.
  • the viscosity ratio ⁇ 2 / ⁇ 1 is more preferably 1.0 or more, further preferably 1.5 or more, and particularly preferably 2.0 or more. When the viscosity ratio ⁇ 2 / ⁇ 1 is less than 0.8, the interaction between POA groups is small, and physical properties associated with POA groups may not be expressed.
  • the POA-modified PVA contained in the coating agent that is the raw material of the release paper base paper of the present invention has a viscosity of a 4% by weight aqueous solution of unmodified PVA having a similar degree of polymerization measured under the conditions of 20 ° C. and a rotor rotational speed of 6 rpm.
  • the viscosity ratio ⁇ 1 / ⁇ 3 is preferably greater than 1.2, more preferably greater than 1.5, even more preferably greater than 2.0, and greater than 5.0.
  • unmodified PVA having a similar degree of polymerization refers to unmodified PVA having a degree of polymerization in the range of 0.95 to 1.05 times the degree of polymerization of POA-modified PVA.
  • the coating agent that is the raw material of the release paper base paper of the present invention is obtained by dissolving the above POA-modified PVA in water or a mixed solution of water and an organic solvent.
  • organic solvents include alcohol solvents such as methanol and ethanol; ester solvents such as methyl acetate and ethyl acetate; diethyl ether, 1,4-dioxane, methyl cellosolve, cellosolve, butyl cellosolve, MTBE (methyl tertiary butyl ether) Ether solvents such as butyl carbitol; ketone solvents such as acetone and diethyl ketone; glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol and triethylene glycol; diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl Glycol ether solvents such as ether and 3-methoxy-3-methyl-1-butanol; ethylene glycol
  • the mixing ratio of water and organic solvent is preferably in the range of 100/0 to 50/50 (weight ratio), more preferably the coating agent is an aqueous solution.
  • the viscosity of the coating agent is often about 10 to 3000 cps at 50 ° C.
  • various polymers water-soluble polymer, polymer emulsion, latex, etc.
  • fillers surfactants (nonionic, Anionic), a lubricant, an antifoaming agent, a dispersant, a wetting agent, a pH adjusting agent, an ultraviolet absorber, and the like can be appropriately blended depending on the use or performance.
  • water-soluble polymer examples include starch and derivatives thereof, cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, and ethylcellulose, arabic rubber, polyvinyl alcohol, and poly (meth) acrylic acid alkali metal salts (soda salts, etc.) ), (Meth) acrylic acid- (meth) acrylic acid ester copolymer alkali metal salt (soda salt, etc.), polyvinylpyrrolidone, (meth) acrylamide / (meth) acrylic acid ester copolymer, (meth) acrylamide / (Meth) acrylic acid ester / (meth) acrylic acid terpolymer, alkali metal salt (soda salt, etc.) of styrene / maleic anhydride copolymer, alkali metal salt of isobutylene / maleic anhydride copolymer (soda) Salt), Isobuty
  • polymer emulsion examples include emulsions of polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylic ester, vinyl chloride / vinyl acetate copolymer, polybutyl methacrylate, ethylene / vinyl acetate copolymer, and the like.
  • latex examples include latexes such as styrene / butadiene copolymer latex and styrene / butadiene / acrylic copolymer.
  • filler kaolin, clay, calcium carbonate, calcined clay, titanium oxide, diatomaceous earth, silica, colloidal silica, aluminum oxide, aluminum hydroxide, synthetic aluminum silicate, synthetic magnesium silicate, polystyrene fine particles, polyvinyl acetate series Examples thereof include fine particles, urea-formalin resin fine particles, and wheat flour.
  • a water-resistant agent such as glyoxal, urea resin, melamine resin, polyvalent metal salt, water-soluble polyamide resin, etc. can be added to the coating agent as necessary.
  • the concentration of the coating agent containing POA-modified PVA and other additives as required is not particularly limited, and is used for coating amount (increase in dry weight of paper generated by coating) and coating. Although it is arbitrarily selected according to the apparatus, operating conditions, etc., it is usually 1 to 15% by weight.
  • the base material of the release paper base paper of the present invention chemical pulp such as hardwood kraft pulp, softwood kraft pulp, mechanical pulp such as GP, RGP, TMP, etc. are used as raw materials.
  • high quality paper, medium quality paper, and alkaline paper produced by a round net paper machine can be used.
  • the base paper may contain organic and inorganic pigments and paper-making aids such as paper strength enhancers, sizing agents, yield improvers and the like.
  • the basis weight is preferably selected from the range of 10 to 100 g / m 2 .
  • the release paper base paper of the present invention is obtained by applying the above coating agent to a substrate and drying.
  • the coating equipment include a 2-roll size press, a gate roll size press, a metering size press, an air knife coater, a bar coater, a roll coater, and a blade coater.
  • the coating amount can be arbitrarily selected according to the properties of the paper, but it is particularly preferably about 0.05 to 3.0 g / m 2 per one side of normal paper.
  • Drying after coating can be performed by, for example, hot air, infrared rays, a heating cylinder, or a combination of these, and the dried release paper base can be further improved in barrier properties by humidity conditioning and calendaring. Can do.
  • As the humidity control condition a condition in which the moisture content in the paper is 5 to 20% by weight is desirable.
  • the roll temperature is preferably from room temperature to 200 ° C. and the roll linear pressure from 20 to 350 kg / cm.
  • the release paper base paper thus obtained has an excellent sealing effect on the top coating agent.
  • the top coating agent solvent-based silicone used for the release layer, non-solvent type (emulsion-type, oligomer-type) silicone, etc., solvent-based pressure-sensitive adhesive used for the top-coat layer of the release layer, emulsion type An adhesive etc. are mentioned.
  • the air permeability of the release paper base paper of the present invention is preferably 10,000 seconds or more, more preferably 30,000 seconds or more, and even more preferably 50,000 seconds or more. When the air permeability is 1000 seconds or less, the sealing effect on the topcoat coating agent of the release paper base paper is not sufficient, which may be uneconomical.
  • the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. While the delay solution was added dropwise so that the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution was constant, polymerization was performed at 60 ° C. for 3 hours, and then the polymerization was stopped by cooling. The total amount of comonomer solution added until the polymerization was stopped was 75 ml. The solid content concentration when the polymerization was stopped was 24.4%. Subsequently, unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30 ° C.
  • AIBN 2,2′-azobisisobutyronitrile
  • POA-modified polyvinyl acetate POA-modified polyvinyl acetate
  • an alkaline solution 10% methanol solution of sodium hydroxide
  • saponification was carried out (POA modified PVAc concentration of saponified solution 20%, molar ratio of sodium hydroxide to vinyl acetate unit in POA modified PVAc 0.1).
  • a gel-like product was formed in about 1 minute after the addition of the alkaline solution.
  • Production Examples 2 to 28 Charge amount of vinyl acetate and methanol, type of unsaturated monomer having POA group used during polymerization (Table 2), polymerization conditions such as addition amount, concentration of POA-modified PVAc during saponification, hydroxylation to vinyl acetate unit Various POA-modified PVA (PVA2 to 28) were produced in the same manner as in Production Example 1 except that the saponification conditions such as the molar ratio of sodium were changed as shown in Tables 1 and 2.
  • Production Example 29 (Production of PVA29) A 250 L pressure reactor equipped with a stirrer, nitrogen inlet, ethylene inlet, initiator addition port and delay solution addition port was charged with 106.1 kg of vinyl acetate and 43.9 kg of methanol and heated to 60 ° C. Thereafter, the system was purged with nitrogen by nitrogen bubbling for 30 minutes. Next, ethylene was introduced so that the pressure in the reaction vessel was 1.4 kg / cm 2 . A 2,8'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (AMV) solution as an initiator was dissolved in methanol to prepare a 2.8 g / L solution, and nitrogen gas was bubbled to form nitrogen. Replaced.
  • AMV 2,8'-azobis (4-methoxy-2,4-dimethylvaleronitrile)
  • Et-modified PVAc ethylene-modified polyvinyl acetate
  • Et-modified PVAc methanol solution adjusted to a concentration of 30% by adding methanol to the resulting solution (100 g of Et-modified PVAc in solution)
  • 46.5 g based on vinyl acetate unit in Et-modified PVAc.
  • Saponification was carried out by adding an alkaline solution (10% methanol solution of NaOH). About 1 minute after addition of the alkaline solution, the gelled system was pulverized with a pulverizer, allowed to stand at 60 ° C.
  • Et-modified PVA29 Et-modified PVA (PVA29).
  • the polymerization degree of PVA29 was 1500, the saponification degree was 98.5 mol%, and the ethylene modification amount was 3.0 mol%.
  • Production Example 30 (Production of PVA30) 700 g of vinyl acetate and 300 g of methanol were charged into a 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and an initiator addition port, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and polymerization was performed at 60 ° C. for 3 hours. Then, the polymerization was stopped by cooling. The solid content concentration when the polymerization was stopped was 17.0%.
  • AIBN 2,2′-azobisisobutyronitrile
  • Production Examples 31 to 35 (Production of PVA 31 to 35) Various methods were used in the same manner as in Production Example 30 except that the saponification conditions such as the amounts of vinyl acetate and methanol, the concentration of PVAc during saponification, and the molar ratio of sodium hydroxide to vinyl acetate units were changed as shown in Table 1. Of unmodified PVA (PVA 31-35).
  • Tables 1 and 2 show the production conditions of PVA 1 to 35.
  • the insoluble matter calculated according to the above formula was determined according to the following criteria.
  • C Insoluble matter 0.1% or more, less than 0.5%
  • D Insoluble matter 0.5 % Or more, less than 1.0%
  • E Insoluble matter 1.0% or more
  • ⁇ Preparation of release paper base paper> On a semi-glassine paper with a basis weight of 80 g / m 2 and an air permeability of 140 seconds, a PVA aqueous solution with a concentration of 4% was applied by hand using MayerBar at a coating amount of 0.1 g / m 2 at 110 ° C. After drying using a hot air dryer for 1 minute, the humidity was adjusted at 20 ° C. and 65% RH for 72 hours, and a super calender treatment was performed once under the conditions of 150 ° C., 250 kg / cm, and 10 m / min. The obtained release paper base paper was subjected to an air permeability test, a barrier property test, and a water resistance test by the following methods.
  • the above results are shown in Table 3.
  • the POA-modified PVA contained in the coating agent that is the raw material of the release paper base paper is excellent in solubility and has a higher viscosity than the unmodified PVA having the same degree of polymerization. Moreover, it has the feature that aqueous solution viscosity at 40 degreeC is high compared with aqueous solution viscosity at 20 degreeC.
  • the release paper base paper of this invention is excellent in barrier property and water resistance, and it turns out that it is very useful. This is because the POA unit on the surface of the coating layer coated with POA-modified PVA has a configuration in which the PVA unit is present inside, and the coating layer surface becomes hydrophobic, so that the above water resistance is expressed. It is done. On the other hand, the oil resistance is considered to be due to the properties of the PVA unit existing inside.
  • the release paper base paper of the present invention is excellent in surface barrier properties, oil resistance, and water resistance by using POA-modified PVA, and is generated when a release layer is applied. This is effective in improving problems such as penetration of the release agent into the base paper to be used and troubles in peeling failure caused by elution of the barrier layer into water, which becomes a problem when using a water-dispersible silicone resin and a water-dispersible adhesive.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une feuille de base en papier antiadhésif préparée par enduction, sur un substrat, d'un agent de revêtement qui contient un polymère d'alcool vinylique, qui présente sur une chaîne latérale, un groupe polyoxyalkylène représenté par la formule (I). Le polymère d'alcool vinylique a un degré de polymérisation à viscosité moyenne (P) de 500 à 5000, un degré de saponification de 20% à 99,99% en mole, et une quantité de modification de groupe polyoxyalkylène (S) de 0,1% à 10% en mole. Ainsi, il est possible de produire une feuille de base en papier antiadhésif qui dispose de propriétés barrière, ainsi que d'une résistance aux huiles et à l'eau. (Dans la formule (I), R1 représente un atome d'hydrogène ou un groupe méthyle ; R2 représente un atome d'hydrogène ou un groupe alkyle ayant de 1 à 8 atomes de carbone ; et m et n représentent chacun le nombre de motifs oxyalkylène récurrents et satisfait respectivement à 0=m=10 et 3=n=20.)
PCT/JP2010/052786 2009-12-09 2010-02-23 Feuille de base en papier antiadhésif Ceased WO2011070800A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013015185A1 (fr) 2011-07-22 2013-01-31 株式会社クラレ Polymère d'alcool vinylique modifié par polyoxyalkylène et son utilisation

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7058260B2 (ja) * 2017-03-30 2022-04-21 株式会社クラレ 剥離紙原紙及びその製造方法、並びに剥離紙
CN110662870B (zh) * 2017-03-30 2023-01-17 株式会社可乐丽 剥离纸原纸和其制造方法、以及剥离纸

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07179714A (ja) * 1993-12-21 1995-07-18 Arakawa Chem Ind Co Ltd 剥離紙用アンダーコート剤
JPH1121788A (ja) * 1997-07-03 1999-01-26 Kuraray Co Ltd 紙用コーティング剤
JPH11323795A (ja) * 1998-05-15 1999-11-26 Nippon Synthetic Chem Ind Co Ltd:The 剥離紙
JP2001295199A (ja) * 2000-04-11 2001-10-26 Kuraray Co Ltd 剥離紙原紙
JP2006274479A (ja) * 2005-03-29 2006-10-12 Mitsubishi Paper Mills Ltd 剥離紙用原紙
JP2007009348A (ja) * 2005-06-28 2007-01-18 Hokuetsu Paper Mills Ltd 工程剥離紙原紙及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07179714A (ja) * 1993-12-21 1995-07-18 Arakawa Chem Ind Co Ltd 剥離紙用アンダーコート剤
JPH1121788A (ja) * 1997-07-03 1999-01-26 Kuraray Co Ltd 紙用コーティング剤
JPH11323795A (ja) * 1998-05-15 1999-11-26 Nippon Synthetic Chem Ind Co Ltd:The 剥離紙
JP2001295199A (ja) * 2000-04-11 2001-10-26 Kuraray Co Ltd 剥離紙原紙
JP2006274479A (ja) * 2005-03-29 2006-10-12 Mitsubishi Paper Mills Ltd 剥離紙用原紙
JP2007009348A (ja) * 2005-06-28 2007-01-18 Hokuetsu Paper Mills Ltd 工程剥離紙原紙及びその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013015185A1 (fr) 2011-07-22 2013-01-31 株式会社クラレ Polymère d'alcool vinylique modifié par polyoxyalkylène et son utilisation
US9181373B2 (en) 2011-07-22 2015-11-10 Kuraray Co., Ltd. Polyoxyalkylene modified vinyl alcohol-based polymer and use thereof
EP2735577A4 (fr) * 2011-07-22 2015-11-11 Kuraray Co Polymère d'alcool vinylique modifié par polyoxyalkylène et son utilisation

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