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WO2014112586A1 - Composition contenant un polymère de type alcool vinylique modifié par polyoxyalkylène - Google Patents

Composition contenant un polymère de type alcool vinylique modifié par polyoxyalkylène Download PDF

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Publication number
WO2014112586A1
WO2014112586A1 PCT/JP2014/050808 JP2014050808W WO2014112586A1 WO 2014112586 A1 WO2014112586 A1 WO 2014112586A1 JP 2014050808 W JP2014050808 W JP 2014050808W WO 2014112586 A1 WO2014112586 A1 WO 2014112586A1
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group
formula
poa
represented
block
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Japanese (ja)
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雅子 川越
徳地　一記
仲前　昌人
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Kuraray Co Ltd
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Kuraray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—Polyalkylene oxides

Definitions

  • the present invention relates to a composition containing a vinyl alcohol polymer containing a monomer unit having a polyoxyalkylene group.
  • a vinyl alcohol polymer (hereinafter sometimes abbreviated as “PVA”) is a few crystalline water-soluble polymers, and has excellent film-forming properties, interface properties, and strength properties. For this reason, PVA is widely used as a raw material for thickeners, paper coating agents, adhesives, fiber processing agents, binders, emulsion stabilizers, films, fibers and the like. Moreover, in order to improve the specific performance of PVA, development of modified PVA by controlling crystallinity, introducing functional groups, and the like has been performed. Furthermore, a PVA-boric acid crosslinking solution in which boric acid or the like is added to PVA to cause a crosslinking reaction is used for the purpose of controlling shape retention performance or improving the strength of the PVA matrix.
  • the content of the POA group and the POA group It has been proposed to improve the temperature-sensitive thickening by adjusting the number of repeating units of the oxyalkylene group (see JP 2008-291120 A and JP 10-338714 A).
  • PVA having such a POA group exhibits temperature-sensitive thickening, the change in viscosity due to the temperature is insufficient, and it is difficult for temperature-sensitive thickening to occur at low concentrations, or the viscosity does not increase even at low temperatures. There are inconveniences such as high handling and poor handling. Under such circumstances, it is required to improve the handling property at low temperature and the temperature-sensitive thickening.
  • JP 2008-291120 A Japanese Patent Laid-Open No. 10-338714
  • the present invention has been made based on the above-mentioned circumstances, and aims to provide a composition that can exhibit excellent temperature-sensitive thickening that has a low viscosity at low temperatures and is excellent in handleability, and that rapidly thickens as the temperature rises. To do.
  • a vinyl alcohol polymer containing a monomer unit having a polyoxyalkylene group (hereinafter sometimes abbreviated as “POA-modified PVA”), and a surfactant;
  • the polyoxyalkylene group includes a block represented by the following formula (1) (hereinafter also referred to as “block (1)”),
  • block (1) The structural unit of the block is 50 mol% or more based on the polyoxyalkylene group,
  • the content of the monomer unit is 0.05 mol% or more and 10 mol% or less with respect to the monomer unit of the vinyl alcohol polymer, and the viscosity average polymerization degree of the vinyl alcohol polymer is 150 or more and 5,000.
  • the saponification degree is 40 mol% or more and 99.99 mol% or less
  • the surfactant is a composition represented by the following formula (I).
  • one of R 1 and R 2 is a methyl group or an ethyl group, and the other is a hydrogen atom.
  • M represents the number of repeating units and is an integer of 10 to 40.
  • the plurality of R 1 and R 2 may be the same or different.
  • R 3 is an alkylene group having 3 to 5 carbon atoms.
  • R 4 is a single bond or an alkylene group having 1 to 5 carbon atoms.
  • X 1 is a hydrogen atom or an organic group.
  • X 2 is a hydrophilic group, x is an integer of 1 to 100. When x is 2 or more, a plurality of R 3 each independently satisfy the above definition.
  • the aqueous solution of the composition contains a POA-modified PVA having a polyoxyalkylene group containing a block having the above specific structure and a surfactant having the above specific structure, so that the viscosity is low and the handling property is increased at a low temperature. Then, an excellent temperature-sensitive thickening that sharply thickens can be exhibited.
  • the POA-modified PVA can have a hydrophobic interaction with the surfactant having the specific structure by including the block having the specific structure.
  • the hydrophobicity of this surfactant is considered to change depending on the temperature.
  • the hydrophobic interaction between the POA groups is small at low temperatures, and the surfactant does not affect the hydrophobic interaction between the POA groups.
  • the composition has a low viscosity and excellent handleability at low temperatures.
  • a stronger intermolecular crosslinking structure is formed by the interaction between the POA groups due to the intervention of the surfactant. As a result, the composition rapidly thickens as the temperature increases.
  • the solubility of the composition in water, the temperature-sensitive viscosity increase, and the like are further improved. Can be made. Thus, it is thought that the said composition exhibits the above-mentioned outstanding temperature-sensitive viscosity increase by having the said structure.
  • the hydrophilic group of X 2 is a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or a group represented by the following formula (II).
  • y is an integer of 1 or more and 200 or less.
  • hydrophilic group of the X 2 With such a specific hydrophilic group, the interaction of POA groups and the surfactant described above is considered to be strong, as a result, the composition is excellent due to an increase in the temperature-sensitive viscous .
  • the organic group of X 1 is an alkyl group having 1 to 29 carbon atoms or a hydrophilic group.
  • Hydrophilic group of the above X 1 is a group represented by the following formula (III).
  • z is an integer of 1 or more and 200 or less.
  • the polyoxyalkylene group preferably further includes a block represented by the following formula (2) (hereinafter also referred to as “block (2)”).
  • block (2) a block represented by the following formula (2) (hereinafter also referred to as “block (2)”).
  • n represents the number of repeating units and is an integer of 1 to 50.)
  • the monomer unit preferably has the polyoxyalkylene group in the side chain.
  • the above-described interaction is considered to be further strengthened, and as a result, the temperature-sensitive thickening of the composition is further improved.
  • the block represented by the above formula (1) is located on the main chain side from the block represented by the above formula (2). It is considered that the above-described interaction is further strengthened by having each of the blocks at the specific position, and as a result, the temperature-sensitive thickening of the composition is further improved.
  • the block represented by the above formula (1) and the block represented by the above formula (2) are directly bonded.
  • these blocks are located adjacent to each other, it is considered that the above-described interaction is further strengthened, and as a result, the temperature-sensitive thickening of the composition is further improved.
  • the POA-modified PVA is preferably obtained by saponifying a copolymer of an unsaturated monomer represented by the following formula (3) and a vinyl ester monomer.
  • Y is a group that includes the block represented by Formula (1) and may include the block represented by Formula (2).
  • R 5 represents a hydrogen atom or An alkyl group having 1 to 8 carbon atoms
  • R 6 is a hydrogen atom or a methyl group
  • X is —O—, —CH 2 —O—, —CO—, — (CH 2 ) k —, —COO. - or -CO-NR 7 - and it .
  • R 7 is .k a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, is an integer of 1-15).
  • the POA-modified PVA contained in the composition is obtained by saponifying the copolymer of the specific monomer, adjustment of the saponification degree of the POA-modified PVA is facilitated, and the temperature sensitivity is increased. The viscosity and the like can be further increased.
  • the mass ratio of the surfactant to the POA-modified PVA is preferably 3/100 or more and 70/100 or less.
  • the composition is excellent in handling property at low temperature and temperature-sensitive thickening, it is suitably used as a coating agent such as a paper coating agent and a glass fiber coating agent.
  • the composition is excellent in handleability at low temperatures and temperature-sensitive thickening, it is suitably used as a thickening agent for various emulsion adhesives.
  • the composition of the present invention has a low viscosity at a low temperature and excellent handleability, and can exhibit an excellent temperature-sensitive thickening that rapidly increases as the temperature rises. Therefore, the composition is suitably used as a coating agent, a thickener and the like.
  • composition has a POA group containing a block represented by the formula (1) described in detail below, and the content of the monomer unit having this POA group (hereinafter also referred to as “POA group modification rate”). ), PVA having a specific range of saponification degree and viscosity average polymerization degree (hereinafter also referred to as “POA-modified PVA”) and a surfactant, the viscosity is low at low temperatures and excellent in handleability. Excellent temperature-sensitive thickening can be achieved.
  • POA group modification rate PVA having a specific range of saponification degree and viscosity average polymerization degree
  • surfactant a surfactant
  • the POA-modified PVA can have a hydrophobic interaction with the surfactant having the specific structure by including the block having the specific structure.
  • the hydrophobicity of this surfactant is considered to change depending on the temperature. Since the POA-modified PVA has a block having the above specific structure, the hydrophobic interaction between the POA groups is small at low temperatures, and the surfactant does not affect the hydrophobic interaction between the POA groups. As a result, the composition has a low viscosity and excellent handleability at low temperatures.
  • a stronger intermolecular crosslinking structure is formed by the interaction between the POA groups due to the intervention of the surfactant.
  • the composition rapidly thickens as the temperature increases. Further, by setting the content of the monomer unit and the viscosity average polymerization degree and saponification degree of the POA-modified PVA within the specific ranges, the solubility of the composition in water, the temperature-sensitive viscosity increase, and the like are further improved. Can be made. Thus, it is thought that the said composition exhibits the above-mentioned outstanding temperature-sensitive viscosity increase by having the said structure.
  • the composition usually further contains water.
  • the composition may be one in which the POA-modified PVA, the surfactant and water are simultaneously dissolved, or a composition obtained by adding a surfactant to a POA-modified PVA aqueous solution.
  • the composition can also include a water-containing solvent.
  • the water-containing solvent is composed of water and a solvent other than water.
  • the composition may contain an optional component in addition to the above components as long as the effects of the present invention are not impaired. Hereinafter, these components will be described in detail.
  • the POA-modified PVA contains a monomer unit having a polyoxyalkylene group containing a block represented by the above formula (1) (hereinafter also referred to as “block (1)”).
  • the content ratio of the structural unit of the block (1) to the polyoxyalkylene group that is, the ratio of the structural unit of the block (1) to the total structural units of the polyoxyalkylene group needs to be 50 mol% or more. 50 mol% or more and 99 mol% or less is preferable, and 60 mol% or more and 95 mol% or less is more preferable.
  • the “block” refers to a portion composed of a chain structure of predetermined structural units.
  • one of R 1 and R 2 is a methyl group or an ethyl group, and the other is a hydrogen atom.
  • m represents the number of repeating units and is an integer of 10 or more and 40 or less.
  • a plurality of R 1 and R 2 may be the same or different.
  • Examples of the block (1) include a polyoxypropylene block in which the number of repeating units of oxypropylene units is m, a polyoxybutylene block in which the number of repeating units of oxybutylene units is m, and the like.
  • the number m of repeating units of the oxyalkylene unit in the block (1) needs to be an integer of 10 to 40, preferably 15 to 38, and more preferably 20 to 35. When m is less than 10, the temperature-sensitive thickening due to the interaction between the POA group and the surfactant is not sufficiently exhibited.
  • R 1 and R 2 in the above formula (1) is a methyl group or an ethyl group, and the other is a hydrogen atom.
  • R 1 is a methyl group and R 2 is a hydrogen atom because the POA-modified PVA is easy to produce.
  • the polyoxyalkylene group preferably further includes a block represented by the above formula (2) (hereinafter also referred to as “block (2)”).
  • block (2) a block represented by the above formula (2)
  • the monomer unit when the monomer unit further includes the block (2) in addition to the block (1), the temperature-sensitive thickening due to the interaction between the POA group and the surfactant is improved.
  • n represents the number of repeating units and is an integer of 1 to 50.
  • Block (2) is a (poly) oxyethylene block in which the number of repeating units of oxyethylene units is n.
  • the number n of repeating units of oxyethylene units in the block (2) is preferably 3 or more and 40 or less, and more preferably 5 or more and 10 or less. When n exceeds 40, the interaction between POA groups decreases, and the temperature-sensitive thickening may not be sufficiently exhibited.
  • the polyoxyalkylene group may further include a block (a) different from the block (1) and the block (2).
  • the said composition can also improve temperature-sensitive thickening by further including a block (a).
  • Examples of the block (a) include a polyoxypentylene block, a polyoxyhexylene block, a polyoxystyrene block, a polyalkylene block, and a polyoxyethylene block having 51 to 70 repeating units.
  • the polyoxyalkylene group may be contained in any of the main chain, the side chain, and the terminal of the POA-modified PVA. From the viewpoint of enhancing the above-mentioned interaction and the viewpoint of ease of synthesis, the side chain or the terminal may be included. It is preferable that it is contained in.
  • the “main chain” refers to the longest chain among the chains formed by bonding a plurality of atoms constituting the POA-modified PVA.
  • “Side chain” refers to a chain other than the main chain in the POA-modified PVA.
  • the block (1) is on the main chain side and the opposite side of the block (2). Although it may be located at any position, it is preferably located at the main chain side. Further, in this case, it is preferable that the block (1) and the block (2) are directly coupled.
  • the POA-modified PVA is a copolymer containing a monomer unit containing a POA group and a vinyl alcohol unit (—CH 2 —CHOH—), and may further contain other monomer units.
  • the method for producing the POA-modified PVA contained in the composition is not particularly limited, but the POA-modified vinyl ester system obtained by copolymerizing an unsaturated monomer containing a POA group and a vinyl ester monomer is obtained. A method of saponifying the polymer is preferred.
  • the unsaturated monomer containing a POA group is preferably an unsaturated monomer represented by the following formula (3).
  • Y is a group that includes a block represented by Formula (1) and may include a block represented by Formula (2).
  • R 5 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • R 6 is a hydrogen atom or a methyl group.
  • X is —O—, —CH 2 —O—, —CO—, — (CH 2 ) k —, —COO— or —CO—NR 7 —.
  • R 7 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • k is an integer of 1 to 15.
  • Examples of the alkyl group having 1 to 8 carbon atoms represented by R 5 include a methyl group, an ethyl group, a propyl group, and a butyl group.
  • R 5 is preferably a hydrogen atom, a methyl group or a butyl group, more preferably a hydrogen atom or a methyl group.
  • X when X is asymmetric, that is, —CH 2 —O—, —COO—, or —CO—NR 7 —, the direction of X may be any.
  • X -O -, - CH 2 -O -, - CO-NR 7 - are preferred, -CO-NR 7 -, more preferably, -CO-NH- is more preferred.
  • R 7 is preferably a hydrogen atom.
  • the direction of the group represented by Y (the arrangement of the block (1), the block (2), etc.) is as described above.
  • unsaturated monomers represented by the above formula (3) unsaturated monomers represented by the following formulas (3-1) to (3-3) are more preferable, and the following formula (3-1) The unsaturated monomer represented by is more preferable.
  • R 1 , R 2 and m are the same as in the above formula (1).
  • n is the same as in the above formula (2).
  • R 5 , R 6 and X are the same as in the above formula (3).
  • B indicates that both adjacent units are formed by block copolymerization.
  • R 5 in the above formula (3) is a hydrogen atom
  • R 6 is a hydrogen atom or a methyl group
  • examples include polyoxyalkylene mono (meth) acrylamide, polyoxyalkylene mono (meth) allyl ether, polyoxyalkylene monovinyl ether, polyoxyalkylene mono (meth) acrylate and the like.
  • R 1 in the block (1) is a methyl group and R 2 is a hydrogen atom
  • polyoxypropylene (poly) oxyethylene monoacrylamide polyoxypropylene (poly) oxyethylene monomethacrylamide
  • polyoxy Propylene (poly) oxyethylene monoallyl ether polyoxypropylene (poly) oxyethylene monomethallyl ether
  • polyoxypropylene (poly) oxyethylene monovinyl ether polyoxypropylene (poly) oxyethylene monoacrylate
  • polyoxypropylene (poly ) Oxyethylene monomethacrylate etc.
  • R 1 is an ethyl group and R 2 is a hydrogen atom
  • polyoxybutylene (poly) oxyethylene monoacrylamide polyoxybutylene (poly) oxyethylene monomethacrylamide
  • polyoxybutylene (poly) oxyethylene monoallyl ether examples include polyoxybutylene (poly) oxyethylene monomethallyl ether, polyoxybutylene (poly) oxyethylene monovinyl ether, polyoxybutylene (poly) oxyethylene monoacrylate, polyoxybutylene (poly) oxyethylene monomethacrylate, and the like.
  • polyoxypropylene (poly) oxyethylene monoacrylamide, polyoxypropylene (poly) oxyethylene monomethacrylamide, polyoxypropylene (poly) oxyethylene monovinyl ether, polyoxypropylene (poly) oxyethylene monoallyl ether are Preferably used.
  • the unsaturated monomer when R 5 in the above formula (3) is an alkyl group having 1 to 8 carbon atoms
  • the unsaturated monomer exemplified when R 5 is a hydrogen atom specifically, the unsaturated monomer exemplified when R 5 is a hydrogen atom.
  • the terminal hydroxyl group is substituted with an alkoxy group having 1 to 8 carbon atoms.
  • the terminal hydroxyl group of polyoxypropylene (poly) oxyethylene monomethacrylamide, polyoxypropylene (poly) oxyethylene monoallyl ether, polyoxypropylene (poly) oxyethylene monovinyl ether is replaced with a methoxy group or an ethoxy group
  • the unsaturated monomer is preferably used.
  • the temperature at which the unsaturated monomer represented by the above formula (3) is copolymerized with the vinyl ester monomer is not particularly limited, but is preferably 0 ° C or higher and 200 ° C or lower, and 30 ° C or higher and 140 ° C or lower. Is more 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 group modification rate prescribed
  • a method for controlling the temperature employed in the copolymerization to 0 ° C. or more and 200 ° C. or less, for example, by controlling the polymerization rate the heat generated by the polymerization is balanced with the heat released from the surface of the reactor. And a method of controlling by an external jacket using an appropriate heat medium. The latter method is preferable from the viewpoint of safety.
  • the polymerization method employed for the copolymerization of the unsaturated monomer represented by the above formula (3) and the vinyl ester monomer is batch polymerization, semi-batch polymerization, continuous polymerization, or semi-continuous polymerization. Either is acceptable.
  • As the polymerization method an arbitrary method can be adopted from known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these, a bulk polymerization method or a solution polymerization method in which polymerization is performed in the absence of a solvent or in the presence of an alcohol solvent is preferable.
  • an emulsion polymerization method is employed.
  • the alcohol solvent used in the bulk polymerization method or the solution polymerization method for example, methanol, ethanol, n-propanol or the like can be used. Two or more of these solvents may be used in combination.
  • azo initiators As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like may be 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-tri
  • 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 used for copolymerization include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, and lauric acid. Examples thereof include vinyl, vinyl palmitate, vinyl stearate, vinyl oleate, vinyl benzoate and the like. Of these, vinyl acetate is most preferred.
  • monomers such as ethylene, propylene, n-butene, and isobutylene; acrylic acid and salts thereof; acrylic acid esters; methacrylic acid and salts thereof; methacrylic acid esters; acrylamide; N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acrylamidepropyldimethylamine and its salt or quaternary salt, N-methylolacrylamide and its derivative, etc.
  • ⁇ -olefins such as ethylene, propylene, n-butene, and isobutylene
  • acrylic acid and salts thereof acrylic acid esters
  • methacrylic acid and salts thereof methacrylic acid esters
  • acrylamide N-methylacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, diacetoneacrylamide, acrylamidepropanesulfonic acid and its salt, acrylamidepropy
  • a monomer giving an ⁇ -olefin unit may be copolymerized within a range not impairing the effect of the present invention.
  • the content of the ⁇ -olefin unit is preferably 1 mol% or more and 20 mol% or less.
  • the present invention is used for the purpose of adjusting the degree of polymerization of the resulting POA-modified vinyl ester polymer upon copolymerization of the unsaturated monomer represented by the above formula (3) and the vinyl ester monomer.
  • Copolymerization may be carried out in the presence of a chain transfer agent as long as the effects of the invention are 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 And phosphinic acid salts such as hydrates. Of these, aldehydes and ketones are preferred.
  • the addition amount of the chain transfer agent may be determined according to the chain transfer constant of the added chain transfer agent and the degree of polymerization of the target POA-modified vinyl ester polymer. Usually, 0.1 mass% or more and 10 mass% or less are preferable with respect to a vinyl ester-type monomer.
  • the saponification reaction of the POA-modified vinyl ester polymer may be an alcoholysis decomposition reaction using a conventionally known basic catalyst such as sodium hydroxide, potassium hydroxide, sodium methoxide, or an acidic catalyst such as p-toluenesulfonic acid. Hydrolysis reactions 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 may 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 group modification rate of the POA-modified PVA must be 0.05 mol% or more and 10 mol% or less, preferably 0.1 mol% or more and 5 mol% or less, preferably 0.1 mol% or more and 2 mol%. The following is more preferable, and 0.15 mol% or more and 1.5 mol% or less is more preferable.
  • the POA group modification rate exceeds 10 mol%, the proportion of POA groups contained in one molecule of the POA-modified PVA increases, so the water solubility of the POA-modified PVA decreases and the temperature-sensitive viscosity increases.
  • the POA group modification rate is less than 0.05 mol%, the water solubility of the POA modified PVA is excellent, but since the proportion of POA groups contained in one molecule of the POA modified PVA is low, the POA group and the surfactant The temperature-sensitive thickening due to the interaction is reduced.
  • the POA group modification rate is the ratio (mol%) of the number of moles of monomer units having POA groups including the block (1) to the number of moles of all monomer units constituting the POA-modified PVA.
  • the POA group modification rate may be determined from POA-modified PVA or may be determined from the precursor POA-modified vinyl ester copolymer, which can be determined by proton NMR.
  • the POA group modification rate can be calculated by the following method. That is, for example, when obtaining from a precursor POA-modified vinyl ester polymer (POA-modified polyvinyl acetate), specifically, first, a POA-modified vinyl ester polymer using a mixed solvent of n-hexane / acetone. After the reprecipitation purification is sufficiently performed three times or more, drying is performed under reduced pressure at 50 ° C.
  • the POA group modification rate can be calculated using the following formula.
  • m represents the number of repeating units of oxypropylene units.
  • POA group modification rate (mol%) [(Area of peak ⁇ / 3 m) / ⁇ Area of peak ⁇ + (Area of peak ⁇ / 3 m) ⁇ ] ⁇ 100
  • the POA group modification rate can be easily determined by appropriately changing the calculation target peak or calculation formula.
  • the viscosity average polymerization degree (P) of the POA-modified PVA used in the present invention (hereinafter sometimes abbreviated as “polymerization degree”) is measured according to JIS K6726. That is, after re-saponifying and purifying the above PVA, it is obtained from the intrinsic viscosity [ ⁇ ] (unit: deciliter / g) measured in water at 30 ° C. by the following formula.
  • the apparent viscosity average degree of polymerization of the whole PVA after mixing is made into the viscosity average degree of polymerization in that case.
  • Degree of polymerization ([ ⁇ ] ⁇ 10 3 /8.29) (1 / 0.62)
  • the degree of polymerization of the POA-modified PVA needs to be 150 or more and 5,000 or less, preferably 150 or more and 4,000 or less, more preferably 200 or more and 3,500 or less, and further preferably 200 or more and 3,000 or less.
  • the degree of polymerization exceeds 5,000, the productivity of the POA-modified PVA is lowered, which is not practical.
  • the saponification degree of the POA-modified PVA needs to be 40 mol% or more and 99.99 mol% or less, preferably 50 mol% or more and 99.9 mol% or less, and more preferably 60 mol% or more and 99 mol% or less.
  • the saponification degree of the POA-modified PVA is a value that can be measured according to JIS-K6726.
  • the surfactant contained in the composition is a compound represented by the following formula (I).
  • R 3 is an alkylene group having 3 to 5 carbon atoms.
  • R 4 is a single bond or an alkylene group having 1 to 5 carbon atoms.
  • X 1 is a hydrogen atom or an organic group.
  • X 2 is a hydrophilic group.
  • x is an integer of 1 to 100. When x is 2 or more, a plurality of R 3 each independently satisfy the above definition.
  • the hydrophilic group of X 2 is a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, or a group represented by the following formula (II).
  • the counter cation in the carboxyl group salt or the sulfonic acid group salt include alkali metal cations such as sodium and potassium; alkaline earth metal cations such as calcium and barium; ammonium ions and the like.
  • the hydrophilic group of the X 2 With such a specific hydrophilic group, the interaction of POA groups and the surfactant described above is considered to be strong, as a result, the composition is excellent due to an increase in the temperature-sensitive viscous .
  • X 2 is preferably a sulfonic acid or a salt thereof, or a group represented by the following formula (II), and more preferably a group represented by the following formula (II).
  • y is an integer of 1 to 200.
  • Y is preferably an integer of 2 or more, 100 or less, more preferably an integer of 2 or more and 40 or less, and further preferably an integer of 3 or more and 20 or less.
  • the organic group of X 1 is an alkyl group having 1 to 29 carbon atoms or a hydrophilic group.
  • the alkyl group having 1 to 29 carbon atoms of X 1 is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 10 carbon atoms.
  • Hydrophilic group of the above X 1 is a group represented by the following formula (III).
  • z is an integer of 1 or more and 200 or less.
  • Z is preferably an integer of 2 or more, 100 or less, more preferably an integer of 2 or more and 40 or less, and further preferably an integer of 3 or more and 20 or less.
  • X 1 is a hydrogen atom, a hydrophilic group represented by the above formula (III), or an alkyl group having 1 to 29 carbon atoms. It is considered that the above-mentioned interaction becomes stronger when X 1 is a hydrogen atom or the specific group, and the composition is more excellent in temperature-sensitive thickening.
  • Examples of the alkylene group having 3 to 5 carbon atoms represented by R 3 include a propanediyl group, a butanediyl group, and a pentanediyl group. Of these, a propanediyl group and a butanediyl group are preferable, and a 1,2-propanediyl group and a 1,4-butanediyl group are more preferable from the viewpoint that the surfactant has appropriate hydrophobicity.
  • Examples of the alkylene group having 1 to 5 carbon atoms represented by R 4 include a methylene group, an ethanediyl group, and a propanediyl group.
  • R 4 is preferably a single bond.
  • X is preferably an integer of 2 to 60, more preferably an integer of 2 to 50, and still more preferably an integer of 3 to 30.
  • the surfactant is not particularly limited as long as it is a compound having a structure represented by the above formula (I).
  • Diblock copolymers or random copolymers such as polyethylene glycol-polypropylene glycol, polyethylene glycol-polytetramethylene glycol, polyethylene glycol-polybutylene glycol, polyethylene glycol-polypentylene glycol; Triblock copolymers such as polyethylene glycol-polypropylene glycol-polyethylene glycol, polyethylene glycol-polytetramethylene glycol-polyethylene glycol, polyethylene glycol-polybutylene glycol-polyethylene glycol, polyethylene glycol-polypentylene glycol-polyethylene glycol; Polypropylene glycol-sulfate sodium salt, polytetramethylene glycol-sulfate sodium salt, polybutylene glycol-sulfate sodium salt, polypentylene glycol-sulfate sodium salt; Examples include polyethylene glycol-poly
  • a diblock copolymer of polyethylene glycol-polypropylene glycol, polyethylene glycol-polypropylene glycol-polyethylene glycol A triblock copolymer is preferable, and a polyethylene glycol-polypropylene glycol-polyethylene glycol triblock copolymer is more preferable.
  • the mass ratio of the surfactant contained in the composition to the POA-modified PVA is preferably from 3/100 to 70/100, and from 5/100 to 50. / 100 or less is more preferable, and 10/100 or more and 25/100 or less is more preferable.
  • ⁇ Solvent> It does not specifically limit as said solvent which the said composition may contain, Water, an organic solvent, etc. are mentioned. Among these, at least a part of the solvent is water, that is, a water-containing solvent is preferable.
  • the content of water in the solvent is preferably 10% by mass or more, more preferably 40% by mass or more, and further preferably 70% by mass or more.
  • organic solvent for example, alcohol solvents, such as methanol and ethanol; Ester solvents such as methyl acetate and ethyl acetate; Ether solvents such as diethyl ether, 1,4-dioxane, methyl cellosolve, cellosolve, butyl cellosolve, methyl-t-butyl ether, butyl carbitol; Ketone solvents such as acetone and diethyl ketone; Glycol solvents such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol; Glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol; Examples thereof include glycol ester solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether a
  • the ratio ⁇ 2 / ⁇ 1 between the viscosity ⁇ 1 at 20 ° C. and the viscosity ⁇ 2 at 50 ° C. Is preferably 2 or more, more preferably 5 or more, still more preferably 10 or more, and particularly preferably 100 or more. Further, the viscosity ratio ⁇ 2 / ⁇ 1 is preferably 2,000 or less, and more preferably 1,000 or less.
  • the composition includes various plasticizers, antifoaming agents, ultraviolet absorbers, fillers, pH adjusters, water resistance, as long as the effects of the present invention are not impaired. It may contain additives such as an agent and a fluorescent brightening agent.
  • composition is not limited to the above-described POA-modified PVA, but other various water-soluble polymers such as various types of PVA, starch, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose. May be contained.
  • the composition can be prepared, for example, by mixing the POA-modified PVA, the surfactant, water, and optional components at a predetermined ratio.
  • a method of mixing these components is not particularly limited, and POA-modified PVA may be added to a mixture of a surfactant and water, or a surfactant may be added to a POA-modified PVA solution.
  • As the solution temperature at the time of the heating for example, 80 ° C. or more and 95 ° C. or less is adopted.
  • composition is excellent in handleability because the increase in viscosity at low temperatures is suppressed even when the concentration of POA-modified PVA is high, and the viscosity increases rapidly at high temperatures and exhibits excellent temperature-sensitive thickening. In applications where temperature fluctuation is assumed, it can be suitably used as a viscosity modifier. Therefore, the composition comprises a coating agent such as a paper coating agent and a glass fiber coating agent; a thickener such as various emulsion adhesives; a viscosity modifier, a temperature-sensitive binder, a gelling agent, and a temperature-sensitive adhesive. It can be suitably used as an agent or the like.
  • sizing agent for example, internally added sizing agent; fiber processing agent; dye; metal or glass surface coating agent; coating agent such as anti-fogging agent; adhesive such as wood, paper, aluminum foil, plastic; non-woven binder; fibrous binder; Binders for building materials such as gypsum board and fiberboard; Additives for urea resin adhesives; Additives for cement and mortar; Hot melt adhesives; Various adhesives such as pressure sensitive adhesives; Ethylene, vinyl acetate, vinyl chloride Dispersants for emulsion polymerization of various ethylenically unsaturated monomers such as: Stabilizers for pigment dispersion such as paints and adhesives; Various ethylenic properties such as vinyl chloride, vinylidene chloride, styrene, (meth) acrylic acid, vinyl acetate Dispersion stabilizer for suspension polymerization of unsaturated monomers; molded products such as fibers, films, sheets, pipes, tubes, water-soluble fibers, and temporary
  • parts and% represent parts by mass and mass%, respectively.
  • Viscosity average degree of polymerization and degree of saponification The viscosity average polymerization degree and saponification degree of PVA were determined by the method described in JIS-K6726.
  • the POA group modification rate of PVA was determined by the method using proton NMR described above.
  • the proton NMR was measured using JEOL GX-500 (500 MHz).
  • the arrangement of the oxypropylene unit and the oxyethylene unit is a block shape, and the block of the oxypropylene unit is located on the X side with respect to the block of the oxyethylene unit.) 3.7 g is charged and nitrogen bubbling is performed. Then, the system was purged with nitrogen for 30 minutes. Moreover, the solution which made the density
  • AIBN 2,2′-azobisisobutyronitrile
  • alkaline solution (10% methanol solution of sodium hydroxide) was added to 386 g of POA-modified PVAc methanol solution prepared by adding methanol to this solution (100.0 g of POA-modified PVAc in the solution).
  • POA modified PVAc concentration in saponified solution 25%, molar ratio of sodium hydroxide to vinyl acetate units in POA modified PVAc 0.03 After adding the alkaline solution, a gel-like material was formed in about 1 minute. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to allow saponification to proceed, and then 500 g of methyl acetate was added to remain. The alkali was neutralized.
  • PVA1 had a viscosity average polymerization degree of 3,000, a saponification degree of 98 mol%, and a POA group modification rate of 0.2 mol%.
  • Table 1 shows the production conditions
  • Table 4 shows the measurement results of the degree of polymerization, the degree of saponification, and the POA group modification rate.
  • POA-modified PVAc POA-modified vinyl ester polymer
  • an alkali solution 10% methanol solution of sodium hydroxide
  • a methanol solution of POA-modified PVAc prepared by adding methanol thereto 120.0 g of POA-modified PVAc in the solution.
  • Saponification was carried out (POA modified PVAc concentration in saponified solution 25%, molar ratio of sodium hydroxide to vinyl acetate units in POA modified PVAc 0.03). After adding the alkaline solution, a gel-like material was formed in about 1 minute.
  • PVA14 had a viscosity average polymerization degree of 2,400, a saponification degree of 98 mol%, and a POA group modification rate of 0.2 mol%.
  • Table 1 shows the production conditions
  • Table 4 shows the measurement results of the degree of polymerization, the degree of saponification, and the POA group modification rate.
  • the oxypropylene unit and the oxyethylene unit are each arranged in a block shape, and the positions of the polyoxyethylene block and the polyoxypropylene block are as described in the above formula. .
  • saponification was carried out (the concentration of unmodified PVAc in the saponified solution was 25 mass%, the molar ratio of sodium hydroxide to the vinyl acetate unit in the unmodified PVAc was 0.03).
  • a gel-like material was formed in about 1 minute after the addition of the alkaline solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to proceed with saponification, and then 500 g of methyl acetate was added to remove the remaining alkali. Neutralized.
  • the obtained composition was subjected to solubility evaluation and solution evaluation (viscosity at 20 ° C. and viscosity at 50 ° C., and a viscosity ratio between the viscosity at 20 ° C. and the viscosity at 50 ° C.) according to the following methods.
  • solubility evaluation and solution evaluation viscosity at 20 ° C. and viscosity at 50 ° C., and a viscosity ratio between the viscosity at 20 ° C. and the viscosity at 50 ° C.
  • Example 2 to 25 and Comparative Examples 1 to 15 Each composition was prepared in the same manner as in Example 1 except that the types of PVA and surfactant used, and the mass ratio of the surfactant and PVA were as shown in Table 4.
  • Table 3 shows the types of surfactants used.
  • surfactants A to E are surfactants represented by the formula (I).
  • Viscosity evaluation (Viscosity at 20 ° C. and viscosity at 50 ° C.) Using a BL-type viscometer, the viscosity (mPa ⁇ s) of each composition prepared above was measured under the conditions of a rotor rotation speed of 6 rpm, 20 ° C. and 50 ° C., and the viscosity at 20 ° C. was ⁇ 1 at 50 ° C. the viscosity was ⁇ 2.
  • thermosensitive thickening The viscosity ratio ( ⁇ 2 / ⁇ 1 ) between ⁇ 1 and ⁇ 2 measured as described above was calculated, and the temperature-sensitive thickening was evaluated according to the following criteria. In addition, when the following evaluation is A to C, it can be said that the temperature-sensitive thickening is excellent.
  • Example 1 in which the degree of polymerization of POA-modified PVA, the POA group modification rate, the degree of saponification, the structure of the monomer units contained, the type of surfactant, and the mass ratio of the surfactant to the POA-modified PVA were specified. 2, 5 to 8, 10 to 13, 17 to 19 and 24 have been found to exhibit particularly excellent temperature-sensitive thickening (the solubility evaluation is A or more, and the temperature-sensitive thickening). Is greater than or equal to B).
  • the composition of the present invention has a low viscosity at a low temperature and excellent handleability, and can exhibit an excellent temperature-sensitive thickening that rapidly increases as the temperature rises. Therefore, the composition is suitably used as a coating agent, a thickener and the like.

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Abstract

La présente invention a pour objet une composition qui peut présenter des propriétés épaississantes thermosensibles tellement excellentes que la composition a une faible viscosité à une plus basse température et est par conséquent facile à manipuler et est rapidement épaissie lorsque la température de la composition est augmentée. La composition selon la présente invention comprend un polymère de type alcool vinylique qui contient un motif monomère comprenant un groupe polyoxyalkylène et un tensioactif, le groupe polyoxyalkylène contenant une séquence représentée par la formule (1), la quantité d'un motif constitutif de la séquence étant supérieure ou égale à 50 % en mole par rapport à la quantité du groupe polyoxyalkylène, la quantité du motif monomère étant de 0,05 à 10 % en mole inclus par rapport à la teneur du motif monomère du polymère de type alcool vinylique, le polymère de type alcool vinylique ayant un degré de polymérisation moyen en viscosité de 150 à 5000 inclus et un degré de saponification de 40 à 99,99 % en mole inclus et le tensioactif étant un composé représenté par la formule (I).
PCT/JP2014/050808 2013-01-18 2014-01-17 Composition contenant un polymère de type alcool vinylique modifié par polyoxyalkylène Ceased WO2014112586A1 (fr)

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Cited By (1)

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CN112004881A (zh) * 2018-04-27 2020-11-27 株式会社可乐丽 聚乙烯醇膜和使用其而得的偏振膜的制备方法

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JP2001354452A (ja) * 2000-06-07 2001-12-25 Nippon Synthetic Chem Ind Co Ltd:The ガラス繊維用処理剤
WO2002085634A1 (fr) * 2001-04-18 2002-10-31 Asahi Kasei Kabushiki Kaisha Emulsion et liquide de revetement et support d'enregistrement utilisant cette emulsion
JP2008524393A (ja) * 2004-12-21 2008-07-10 バクスター・インターナショナル・インコーポレイテッド ポリアルコキシスルホネート表面改変因子
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WO2012124746A1 (fr) * 2011-03-17 2012-09-20 株式会社クラレ Solution de polymère d'alcool vinylique modifié et son procédé de production
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
WO2013054834A1 (fr) * 2011-10-14 2013-04-18 株式会社クラレ Solution de polymère d'alcool vinylique modifié par alkyle
WO2013125678A1 (fr) * 2012-02-24 2013-08-29 株式会社クラレ Épaississant

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JP2001253993A (ja) * 2000-03-10 2001-09-18 Nippon Synthetic Chem Ind Co Ltd:The ポリビニルアルコール系フィルム及びその製造方法
JP2001354452A (ja) * 2000-06-07 2001-12-25 Nippon Synthetic Chem Ind Co Ltd:The ガラス繊維用処理剤
WO2002085634A1 (fr) * 2001-04-18 2002-10-31 Asahi Kasei Kabushiki Kaisha Emulsion et liquide de revetement et support d'enregistrement utilisant cette emulsion
JP2008524393A (ja) * 2004-12-21 2008-07-10 バクスター・インターナショナル・インコーポレイテッド ポリアルコキシスルホネート表面改変因子
WO2011040377A1 (fr) * 2009-09-29 2011-04-07 株式会社クラレ Epaississant qui contient un polymère d'alcool vinylique
JP2011126931A (ja) * 2009-12-15 2011-06-30 Kuraray Co Ltd 分散液および感熱記録材料
WO2012124746A1 (fr) * 2011-03-17 2012-09-20 株式会社クラレ Solution de polymère d'alcool vinylique modifié et son procédé de production
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
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112004881A (zh) * 2018-04-27 2020-11-27 株式会社可乐丽 聚乙烯醇膜和使用其而得的偏振膜的制备方法
CN112004881B (zh) * 2018-04-27 2023-03-10 株式会社可乐丽 聚乙烯醇膜和使用其而得的偏振膜的制备方法

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