WO2019225731A1 - 樹脂材料、水溶液及び接着剤 - Google Patents
樹脂材料、水溶液及び接着剤 Download PDFInfo
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- WO2019225731A1 WO2019225731A1 PCT/JP2019/020609 JP2019020609W WO2019225731A1 WO 2019225731 A1 WO2019225731 A1 WO 2019225731A1 JP 2019020609 W JP2019020609 W JP 2019020609W WO 2019225731 A1 WO2019225731 A1 WO 2019225731A1
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- 125000004185 ester group Chemical group 0.000 description 1
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- 125000001033 ether group Chemical group 0.000 description 1
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- 239000000665 guar gum Substances 0.000 description 1
- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 239000004816 latex Substances 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
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- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- ADTJPOBHAXXXFS-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]prop-2-enamide Chemical compound CN(C)CCCNC(=O)C=C ADTJPOBHAXXXFS-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
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- 235000013808 oxidized starch Nutrition 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
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- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
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- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
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- 235000019698 starch Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of 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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/12—Hydrolysis
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- C09J129/00—Adhesives 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
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- 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
- C08K5/01—Hydrocarbons
Definitions
- the present invention relates to a resin material mainly composed of an ethylene-modified vinyl alcohol polymer, which is excellent in hue, water solubility and viscosity stability of an aqueous solution.
- the present invention also relates to an aqueous solution and an adhesive containing the resin material.
- Polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”) is known as a water-soluble synthetic polymer, and a raw material of vinylon which is a synthetic fiber, a paper processing agent, a fiber processing agent, an adhesive, an emulsification Widely used in applications such as stabilizers for polymerization and suspension polymerization, inorganic binders, films and the like.
- Patent Document 1 discloses that the ethylene unit content is 2 to 19 mol%, the polymerization degree is 200 to 2000, the saponification degree is 80 to 99.99 mol%, and the total content of the carboxyl group and the lactone ring.
- An ethylene-vinyl alcohol copolymer of 0.02 to 0.4 mol% has been proposed.
- Patent Document 2 describes an adhesive using an ethylene-modified vinyl alcohol polymer.
- the high-speed coatability of the adhesive is not sufficiently satisfactory industrially.
- the present invention has been made based on the above-described circumstances, and is excellent in hue, water solubility and viscosity stability of an aqueous solution, and a resin material mainly composed of an ethylene-modified vinyl alcohol polymer, and the resin material It is an object to provide an aqueous solution containing an adhesive and an adhesive.
- the above-mentioned problem is that an ethylene-modified vinyl alcohol polymer having a specific amount of propyl group at one end, and a specific amount of sodium acetate, the ethylene unit content, viscosity average polymerization degree and saponification degree are in a specific range. It is solved by providing a resin material containing.
- the present invention includes the following inventions.
- the ethylene unit content is 1 mol% or more and less than 15 mol%
- the viscosity average polymerization degree is 200 or more and less than 3000
- the saponification degree is 80 mol% or more and less than 99.9 mol%
- the resin material according to [1] wherein the resin material has a solubility of 90% or more when 90 parts by mass of water is stirred at 90 ° C.
- the compound having a conjugated double bond and having a molecular weight of 1000 or less has a conjugated double bond between aliphatic double bonds and / or a conjugated double bond between an aliphatic double bond and an aromatic ring.
- the resin material comprising a compound.
- the compound having a conjugated double bond and having a molecular weight of 1,000 or less includes a compound having a conjugated double bond between aliphatic double bonds, and a compound having a conjugated double bond between the aliphatic double bonds.
- the resin material according to [6] which is at least one selected from the group consisting of a conjugated diene compound, a conjugated triene compound, and a conjugated polyene compound.
- the resin material according to [7], wherein the compound having a conjugated double bond between aliphatic double bonds is a conjugated diene compound.
- the resin material according to any one of [5] to [8], wherein the compound having a conjugated double bond and having a molecular weight of 1000 or less includes a compound having a conjugated double bond of an aliphatic double bond and an aromatic ring. .
- the present invention it is possible to provide a resin material mainly composed of an ethylene-modified vinyl alcohol polymer, which is excellent in hue, water solubility and viscosity stability of an aqueous solution, and an aqueous solution thereof. Furthermore, according to this invention, the adhesive agent which contains the said aqueous solution and is excellent in high-speed coating property can be provided.
- Example it is the schematic of 3 rolls used for evaluation of an adhesive agent.
- the resin material of the present invention has an ethylene unit content of 1 mol% or more and less than 15 mol%, a viscosity average polymerization degree of 200 or more and less than 3000, and a saponification degree of 80 mol% or more and less than 99.9 mol%.
- an ethylene-modified vinyl alcohol polymer having a propyl group at one end of 0.0005 mol% to 0.10 mol% hereinafter sometimes abbreviated as “ethylene-modified PVA”
- content of the said sodium acetate is 0.05 mass% or more and less than 2 mass%, It is characterized by the above-mentioned.
- the resin material of the present invention contains ethylene-modified PVA as a main component.
- the “main component” means that the content in the resin material is 50% by mass or more.
- the resin material of the present invention preferably contains 70% by mass or more of ethylene-modified PVA, more preferably 80% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, 98 mass% or more is the most preferable.
- the resin material excellent in the viscosity stability of the aqueous solution can be obtained because the ethylene-modified PVA which is the main component of the resin material has a specific amount of propyl group at one end. The reason is not necessarily clear, but the propyl group in the ethylene-modified PVA can control the association state of the ethylene-modified PVA chain in the aqueous solution in which the resin material is dissolved. As a result, a resin material having excellent viscosity stability of the aqueous solution can be obtained.
- the “hue” of the resin material is a particle having a particle size of less than 100 ⁇ m and more than 1000 ⁇ m using a sieve (aperture: 100 ⁇ m, 1000 ⁇ m) from the powdered resin material, as described in Examples below. It means a yellow index (YI) measured and calculated according to JIS Z 8722: 2009 and JIS K 7373: 2006 using a color meter (SM-T-H1 manufactured by Suga Test Instruments) after removal.
- YI yellow index
- the ethylene-modified PVA used in the present invention has an ethylene unit content of 1 mol% or more and less than 15 mol%, preferably 1 mol% or more and less than 10 mol%, preferably 1 mol% or more and less than 8 mol%. Is more preferable, and 1 mol% or more and less than 5 mol% is more preferable.
- the ethylene unit content is less than 1 mol%, the viscosity stability of the aqueous solution decreases, and when it is 15 mol% or more, the water solubility decreases.
- the measuring method of the content rate of an ethylene unit is as having described in the Example mentioned later.
- the ethylene-modified PVA used in the present invention has a viscosity average polymerization degree of 200 or more and less than 3000, preferably 400 or more and less than 2800, and more preferably 450 or more and less than 2500. If the viscosity average polymerization degree is less than 200, the production is difficult and the hue becomes insufficient, and if it is 3000 or more, the viscosity stability of the aqueous solution becomes insufficient.
- the viscosity average degree of polymerization is a value obtained by measurement according to JIS K 6726: 1994. Specifically, when the saponification degree is less than 99.5 mol%, the intrinsic viscosity [ ⁇ ] (liter / liter) measured in water at 30 ° C.
- the saponification degree of the ethylene-modified PVA used in the present invention is 80 mol% or more and less than 99.9 mol%, preferably 90 mol% or more and less than 99.9 mol%.
- the degree of saponification is less than 80 mol%, the solubility in water decreases.
- Ethylene-modified PVA having a saponification degree of 99.9 mol% or more is difficult to produce.
- the saponification degree is a value obtained by measurement according to JIS K 6726: 1994.
- the ethylene-modified PVA used in the present invention has a propyl group at one end of 0.0005 mol% or more and 0.10 mol% or less. From the viewpoint of superior viscosity stability of an aqueous solution, 0.001 mol% or more and 0 or less. Less than 0.08 mol% is preferable, and 0.005 mol% or more and less than 0.05 mol% is more preferable.
- the propyl group content is less than 0.0005 mol%, the hue and viscosity stability of the aqueous solution are insufficient.
- the propyl group content exceeds 0.10 mol% the viscosity stability of the aqueous solution becomes insufficient.
- an alkyl group having a smaller number of carbon atoms than a propyl group is difficult to introduce into ethylene-modified PVA or has an insufficient hue.
- the viscosity stability of the aqueous solution becomes insufficient.
- the content of the propyl group in the ethylene-modified PVA can be determined from 1 H-NMR of an ethylene-modified vinyl ester polymer that is a precursor or re-acetylated product of ethylene-modified PVA, for example. After reprecipitation purification of the vinyl ester polymer of the sample using a mixed solution of n-hexane and acetone three times or more, it is dried under reduced pressure at 80 ° C. for 3 days to produce an ethylene-modified vinyl ester polymer for analysis. . An ethylene-modified vinyl ester polymer for analysis is dissolved in DMSO-d 6 and 1 H-NMR (500 MHz) is measured at 80 ° C.
- the 1,2-glycol bond amount of the ethylene-modified PVA used in the present invention is preferably 1.2 mol% or more and less than 2.0 mol%, more preferably 1.4 mol% or more and less than 1.9 mol%.
- the 1,2-glycol bond amount is 1.2 mol% or more, the productivity is excellent and industrially advantageous, and the viscosity stability of the aqueous solution is excellent.
- the 1,2-glycol bond amount is less than 2.0 mol%, the productivity is excellent and industrially advantageous, and the yellowing can be further suppressed by the hue.
- the method for measuring the amount of 1,2-glycol bonds is as described in the examples described later.
- the content of sodium acetate in the resin material of the present invention is 0.05% by mass or more and less than 2% by mass, and 0.1 mass% or more and 1. Less than 5% by mass is preferable, and 0.15% by mass or more and less than 1.0% by mass is more preferable. If it is less than 0.05% by mass, the viscosity stability of the aqueous solution is lowered, and if it is 2% by mass or more, the hue deteriorates.
- the content of sodium acetate was determined according to the dissolution conductivity method described in JIS K 6726: 1994.
- content of sodium acetate means the content rate of sodium acetate with respect to the total mass of ethylene modified PVA and sodium acetate.
- the resin material of the present invention preferably further contains a compound having a conjugated double bond and a molecular weight of 1000 or less from the viewpoint of improving high-speed coating properties and water-resistant adhesion.
- the mechanism for improving the high-speed coating property is not clear, but the conjugated double bond site interacts with the ethylene unit of ethylene-modified PVA in a polar solvent, so that the intermolecular interaction between ethylene-modified PVA is moderately inhibited. It is estimated that it is caused by
- a compound having a conjugated double bond and a molecular weight of 1,000 or less is a compound having a conjugated double bond between aliphatic double bonds or a compound having a conjugated double bond between an aliphatic double bond and an aromatic ring. is there.
- the former is preferable from the viewpoint that the effect of improving high-speed coating properties and water-resistant adhesion is higher.
- the molecular weight is preferably 800 or less, and more preferably 500 or less.
- a compound having a conjugated double bond and a molecular weight of 1000 or less may be used alone or in combination of two or more.
- a compound having a conjugated double bond between aliphatic double bonds has a structure in which carbon-carbon double bonds and carbon-carbon single bonds are alternately connected, It is a compound having a conjugated double bond, the number of which is 2 or more.
- Examples thereof include conjugated polyene compounds having a conjugated structure that are alternately connected.
- a conjugated diene compound is preferable from the viewpoint that the effect of improving high-speed coating properties and water-resistant adhesion is higher.
- the compound having a conjugated double bond used in the present invention and having a molecular weight of 1,000 or less may have a plurality of conjugated double bonds independently in one molecule. Also included are compounds having three of these.
- the compound having a conjugated double bond and a molecular weight of 1000 or less may have a functional group other than the conjugated double bond.
- other functional groups include carboxy groups and salts thereof, hydroxyl groups, ester groups, carbonyl groups, ether groups, amino groups, dialkylamino groups, imino groups, amide groups, cyano groups, diazo groups, nitro groups, mercapto groups, Examples include sulfone groups, sulfoxide groups, sulfide groups, thiol groups, sulfonic acid groups and salts thereof, phosphoric acid groups and salts thereof, polar groups such as halogen atoms, and nonpolar groups such as phenyl groups.
- polar groups are preferable, and carboxy groups and salts thereof, and hydroxyl groups are more preferable as other functional groups.
- the other functional group may be directly bonded to the carbon atom in the conjugated double bond, or may be bonded to a position away from the conjugated double bond. Multiple bonds in other functional groups may be in a position capable of conjugating with the conjugated double bond, for example, 1-phenyl-1,3-butadiene having a phenyl group, sorbic acid having a carboxy group, etc. Used as a compound having a double bond and a molecular weight of 1000 or less. A compound having a conjugated double bond and having a molecular weight of 1000 or less may have a nonconjugated double bond or a nonconjugated triple bond.
- a compound having a conjugated double bond and a molecular weight of 1000 or less specifically, 2,3-dimethyl-1,3-butadiene, 4-methyl-1,3-pentadiene, 1-phenyl-1,3-butadiene, Compounds having a conjugated double bond between aliphatic double bonds such as sorbic acid and myrcene; 2,4-diphenyl-4-methyl-1-pentene, ⁇ -methylstyrene polymer, 1,3-diphenyl-1- Examples thereof include compounds having a conjugated double bond of an aliphatic double bond such as butene and an aromatic ring.
- the content of the compound having a conjugated double bond and a molecular weight of 1000 or less is preferably 0.000001 to 0.01 parts by mass with respect to 100 parts by mass of ethylene-modified PVA.
- the content is more preferably 0.000002 parts by mass or more, and further preferably 0.000003 parts by mass or more.
- the content is more preferably 0.0075 parts by mass or less, further preferably 0.005 parts by mass or less, and particularly preferably 0.0025 parts by mass or less.
- the method for adding a compound having a conjugated double bond and a molecular weight of 1000 or less is not particularly limited.
- the resin material of the present invention preferably has a solubility of 90% or more, more preferably 95% or more when 90 parts by mass of water is stirred at 90 ° C. and 300 rpm for 5 parts with respect to 10 parts by mass of the resin material. .
- solubility is less than 90%, the viscosity stability of the aqueous solution tends to decrease.
- the powder made of the resin material of the present invention preferably has a yellow index (hereinafter sometimes abbreviated as “YI”) of 13.0 or less, more preferably 11.0 or less, and even more preferably 10.0 or less. 9.0 or less is particularly preferable.
- YI in the present specification is a value measured and calculated according to JIS Z 8722: 2009 and JIS K 7373: 2006.
- a preferred method for producing the resin material of the present invention is an ethylene-modified PVA having a polymerization step of reacting ethylene and vinyl acetate to obtain an ethylene-modified vinyl ester polymer, and a saponification step of saponifying the ethylene-modified vinyl ester polymer.
- ethylene and vinyl acetate are reacted in the presence of a propyl group-containing initiator and a chain transfer agent, and the water content of the saponification raw material solution to be subjected to the saponification step is set to a specific amount, and saponification is performed.
- a catalyst having a sodium atom is used as a catalyst for the process.
- an initiator having a propyl group and a chain transfer agent are used in combination in the polymerization step, a specific amount of propyl group can be efficiently introduced into one end of the resulting ethylene-modified PVA, and the water content of the saponification raw material solution is set to a specific amount, And the content of sodium acetate in the resin material obtained can be controlled by using the catalyst which has a sodium atom.
- the ethylene-modified PVA can be produced by polymerizing ethylene and vinyl acetate by a conventionally known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, or a dispersion polymerization method.
- a solution polymerization method in which polymerization is performed together with a lower alcohol is preferable.
- C3 or less alcohols, such as methanol, ethanol, propanol, isopropanol are preferable, and methanol is more preferable.
- any of a batch method, a semi-batch method and a continuous method can be adopted.
- ⁇ -olefins such as propylene, n-butene and isobutylene
- acrylic acid and salts thereof methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid n-propyl, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
- acrylic acid esters such as (meth) acrylic acid dodecyl and (meth) acrylic acid octadecyl
- (meth) acrylamide N-olefins
- the method for introducing a propyl group is not particularly limited, but a method in which ethylene and vinyl acetate are reacted in the presence of an initiator having a propyl group and a chain transfer agent in the polymerization step is preferable.
- an initiator having a propyl group and the chain transfer agent having a propyl group an ethylene-modified PVA having a specific amount of propyl group introduced at one end can be efficiently produced.
- Examples of the initiator having a propyl group include n-propyl peroxydicarbonate and 1,1'-propane-1-nitrile.
- the amount of the initiator having a propyl group is preferably 0.000125% by mass or more and 0.25% by mass or less, and 0.0003% by mass or more and 0% by mass with respect to vinyl acetate in order to obtain a desired propyl group content. .2% by mass or less is more preferable, and 0.0005% by mass or more and 0.15% by mass or less is more preferable.
- Examples of the chain transfer agent having a propyl group include propanethiol and propylaldehyde.
- the concentration in the system of the chain transfer agent having a propyl group is preferably 0.0001% by mass or more and 0.005% by mass or less, and 0.0002% by mass with respect to vinyl acetate in order to obtain a desired propyl group content.
- the content is more preferably 0.004% by mass or less, and further preferably 0.0003% by mass or more and 0.003% by mass or less.
- the polymerization temperature is not particularly limited and is preferably 0 to 180 ° C, more preferably 20 to 160 ° C, and further preferably 30 to 150 ° C.
- vacuum boiling polymerization where the solvent is boiled under reduced pressure
- normal pressure non-boiling polymerization where the solvent is not boiled under normal pressure
- polymerizing above the boiling point of the solvent used in the polymerization step either pressure non-boiling polymerization in which the solvent is not boiled under pressure or pressure boiling polymerization in which the polymerization is performed while boiling the solvent under pressure Can also be selected.
- the ethylene pressure in the polymerization reactor in the polymerization step is not limited, but is preferably 0.01 to 0.9 MPa, more preferably 0.05 to 0.7 MPa, and further preferably 0.1 to 0.65 MPa.
- the polymerization rate of vinyl acetate at the outlet of the polymerization reactor is not particularly limited, but is preferably 10 to 90%, more preferably 15 to 85%.
- the removal process which removes the vinyl acetate which remains in the polymerization liquid containing the obtained ethylene modified vinyl ester polymer after a superposition
- the method for removing the remaining vinyl acetate is not particularly limited, but (i) a method for removing by heating, (ii) a method for removing methanol by adding methanol continuously while heating, (iii) continuously removing methanol vapor.
- Examples thereof include a method of blowing into the polymerization solution, and (iv) a method of continuously blowing methanol vapor into the polymerization solution while heating.
- the removal may be performed while continuously adding a polymerization solution containing an ethylene-modified vinyl ester polymer to the reactor in which the removal step is performed, or the removal may be performed after batch charging.
- the average residence time of the polymerization liquid containing the ethylene-modified vinyl ester polymer is preferably 1 hour or more and 5 hours or less.
- the average residence time is less than 1 hour, removal of residual vinyl acetate tends to be insufficient, and the hue of the resulting ethylene-modified PVA tends to deteriorate.
- the average residence time exceeds 5 hours, heat is applied excessively, and the hue of the resulting ethylene-modified PVA tends to deteriorate.
- the temperature at which the removing device is heated is not particularly limited.
- the temperature in the removal step is usually from 10 to 120 ° C., and preferably from 50 to 90 ° C., which is the temperature near the boiling point of methanol or vinyl acetate.
- the amount of vinyl acetate remaining in the polymerization solution containing the ethylene-modified vinyl ester polymer after the removing step that is, the content ratio of vinyl acetate to the total mass of the ethylene-modified vinyl ester polymer and vinyl acetate is 1.0% by mass. Is preferably less than 0.5% by mass. If the amount of the remaining vinyl acetate exceeds 1.0% by mass, the hue of the resin material obtained tends to deteriorate.
- a saponification raw material solution can be prepared by adding a small amount of water to the polymerization solution containing the ethylene-modified vinyl ester polymer obtained in the polymerization step and, if necessary, the subsequent removal step.
- the amount of water added may be adjusted so that the water content of the resulting saponification raw material solution (hereinafter sometimes abbreviated as “system water content”) is 0.1% by mass or more and 3.0% by mass or less. Preferably, 0.3 mass% or more and 2.5 mass% or less are more preferable.
- alcoholysis or hydrolysis reaction using a catalyst having sodium atoms in the saponification raw material solution can be applied.
- the catalyst having a sodium atom include sodium hydroxide and sodium methoxide.
- the solvent used in the saponification step 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.
- One kind can be used alone, or two or more kinds can be used in combination.
- the amount of the catalyst used is preferably 0.001 or more and 0.5 or less, more preferably 0.002 or more and 0.4 or less, and more preferably 0.004 or more and 0.000 or less in terms of a molar ratio to vinyl acetate units in the ethylene-modified vinyl ester polymer. 3 or less is more preferable.
- a washing step may be provided as necessary after the saponification step.
- the solvent used for washing include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate.
- the conditions for the washing step are not particularly limited, but washing is preferably performed at a temperature of 20 ° C. to the boiling point of the solvent for about 30 minutes to 10 hours.
- An aqueous solution containing the resin material is a preferred embodiment of the present invention.
- the aqueous solution is used for various applications such as adhesives, dispersion stabilizers, coating agents, binders, paper processing agents, viscosity modifiers, raw materials for molded articles such as films, and resin materials for post-reactions.
- the adhesive agent containing the said aqueous solution is a more suitable embodiment of this invention as it mentions later.
- the content of components (solid content) other than water and organic solvent in the aqueous solution is preferably 1 to 50% by mass.
- the content is more preferably 3% by mass or more, and further preferably 5% by mass or more.
- the content is more preferably 45% by mass or less, and further preferably 40% by mass or less.
- the aqueous solution further contains an inorganic filler.
- an inorganic filler what is used for the adhesive agent mentioned later is mentioned.
- the content of the inorganic filler is preferably 20 to 500 parts by mass with respect to 100 parts by mass of the ethylene-modified PVA.
- the content is more preferably 50 parts by mass or more.
- the content is more preferably 300 parts by mass or less.
- an alcohol such as methanol, ethylene glycol or glycerin, or a water-soluble organic such as cellosolve is used.
- a solvent may be included.
- the content of the organic solvent is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, and still more preferably 10 parts by mass or less with respect to 100 parts by mass of water.
- the adhesive containing the aqueous solution is a preferred embodiment of the present invention.
- the adhesive preferably further contains an inorganic filler from the viewpoint of improving the fluidity and adhesive strength of the adhesive.
- the inorganic filler is not particularly limited, and can be appropriately selected according to the adherend, coating machine, required performance, and the like.
- examples of the inorganic filler include clays such as kaolinite, halloysite, pyroferrite, and sericite, heavy, light, or surface-treated calcium carbonate, aluminum hydroxide, aluminum oxide, gypsum, talc, titanium oxide, and the like. Can be mentioned. Of these, clay is preferable.
- These inorganic fillers can be used individually by 1 type or in combination of 2 or more types.
- the average particle diameter of the inorganic filler is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 5 ⁇ m or less from the viewpoint that a uniform slurry solution can be obtained without the inorganic filler aggregating or sedimenting in the aqueous solution.
- the average particle size of the inorganic filler can be measured with a laser diffraction particle size distribution analyzer SALD-2300 manufactured by Shimadzu Corporation.
- the content of the inorganic filler is preferably 20 to 500 parts by mass with respect to 100 parts by mass of ethylene-modified PVA.
- the content is more preferably 50 parts by mass or more.
- the content of the inorganic filler exceeds 500 parts by mass, the fluidity of the adhesive tends to deteriorate, the inorganic filler tends to settle in the aqueous solution, and the adhesive strength tends to decrease.
- the content is more preferably 300 parts by mass or less.
- the adhesive may contain an additive other than a resin material mainly composed of ethylene-modified PVA, an inorganic filler, and water.
- additives include, for example, metal salts of phosphoric acid compounds such as sodium polyphosphate and sodium hexametaphosphate and inorganic dispersants such as water glass; polyacrylic acid and its salts; sodium alginate; ⁇ -olefin-maleic anhydride
- Anionic polymer compounds such as copolymers and their metal salts; nonionic surfactants such as ethylene oxide adducts of higher alcohols and copolymers of ethylene oxide and propylene oxide.
- flavor etc. can also be added as another additive as needed.
- a water-soluble boron compound such as boric acid; borax; boric acid esters of polyhydric alcohols such as glycerin and ethylene glycol can be added.
- natural pastes such as starch, casein, gelatin, guar gum, gum arabic and sodium alginate
- processed natural pastes such as CMC, oxidized starch and methylcellulose
- various rubber latexes such as rubber emulsion.
- a known PVA may be used in combination as another additive.
- the total content of other additives is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 25 parts by mass or less, and particularly preferably 10 parts by mass or less with respect to 100 parts by mass of ethylene-modified PVA.
- the method for producing the adhesive is not particularly limited, and can be obtained, for example, by dissolving a resin material mainly composed of the ethylene-modified PVA in water. Specifically, the resin material, if necessary, a compound having a conjugated double bond and a molecular weight of 1000 or less and an inorganic filler are added to water, and then the resin material is dissolved.
- a batch method or a continuous method can be adopted.
- an inorganic filler or other additives (i) a resin material, a compound having a conjugated double bond and a molecular weight of 1000 or less, and an inorganic filler are mixed in advance.
- the obtained mixture may be added to water, or (ii) a resin material, a compound having a conjugated double bond and a molecular weight of 1000 or less, and an inorganic filler may be sequentially added to water.
- a resin material When adding each component to water, it is preferable to stir the water.
- the resin material is dissolved by heating a slurry obtained by adding a resin material, and optionally a compound having a conjugated double bond and a molecular weight of 1000 or less and an inorganic filler to water.
- an arbitrary heating method such as a heating method in which steam is directly blown or an indirect heating method using a jacket type reactor can be employed.
- the viscosity of the adhesive of the present invention may be adjusted according to the application, but the viscosity measured with a B-type viscometer (30 rpm, 20 ° C.) is usually 100 to 8000 mPa ⁇ s.
- the adhesive of the present invention is less susceptible to jumping and foam entrapment, can be cast evenly, and has less stringing, so it has excellent high-speed coating properties. Therefore, it can be suitably used for a known application in which PVA has been conventionally used as an adhesive.
- the adhesive is suitably used as an adhesive for paper such as paperboard, cardboard, paper tube, bag, wallpaper, and the like.
- a method of applying the adhesive to a substrate is a preferred embodiment of the adhesive.
- the resin material of the present invention is used for various applications. Examples thereof are given below, but the invention is not limited to them.
- Dispersant use dispersion stabilizer for pigments contained in paints, adhesives, etc., dispersion stabilizer for suspension polymerization of various vinyl compounds such as vinyl chloride, vinylidene chloride, styrene, (meth) acrylate, vinyl acetate and the like Dispersing aid
- Coating agent Paper coating agent, sizing agent, textile processing agent, leather finish agent, paint, antifogging agent, metal corrosion inhibitor, galvanizing brightener, antistatic agent
- adhesion Applications Adhesives, adhesives, rewet adhesives, various binders, additives for cement and mortar
- Emulsifier applications Emulsifiers for emulsion polymerization, post-emulsifiers such as bitumen (5)
- Flocculant applications Suspension in water And dissolved flocculants, metal flocculants (6)
- the ethylene unit content of the ethylene-modified PVA was determined from 1 H-NMR of an ethylene-modified vinyl ester polymer that is a precursor or re-acetylated product of ethylene-modified PVA. Specifically, reprecipitation purification of the ethylene-modified vinyl ester polymers of the samples of Examples and Comparative Examples was performed three times or more using a mixed solution of n-hexane and acetone, and then dried under reduced pressure at 80 ° C. for 3 days. Thus, an ethylene-modified vinyl ester polymer for analysis is prepared.
- ethylene-modified PVA The amount of 1,2-glycol bond contained in ethylene-modified PVA was determined from the 1 H-NMR peak. Specifically, ethylene-modified PVA is saponified to a saponification degree of 99.9 mol% or more, thoroughly washed with methanol, and then dried under reduced pressure at 90 ° C. for 2 days, dissolved in DMSO-d 6 and dissolved in trifluoroacetic acid. A sample with a few drops added was measured at 80 ° C. using 1 H-NMR of 500 MHz.
- the peak derived from the methine proton of the vinyl alcohol unit is 3.2 to 4.0 ppm (integrated value A), and the peak derived from one methine proton of the 1,2-glycol bond is around 3.15 to 3.35 ppm (integrated value).
- the content of the propyl group at one end of the ethylene-modified PVA was determined from 1 H-NMR of an ethylene-modified vinyl ester polymer which is a precursor or re-acetylated product of ethylene-modified PVA. After reprecipitation purification of the ethylene-modified vinyl ester polymer of the sample three times or more using a mixed solution of n-hexane and acetone, it was dried under reduced pressure at 80 ° C. for 3 days to obtain an ethylene-modified vinyl ester polymer for analysis. Produced.
- Viscosity stability of aqueous solution of resin material 100 g of a 10% aqueous solution of a resin material prepared under the above conditions is allowed to stand at 5 ° C., and the viscosity c when the liquid temperature reaches 5 ° C. is determined and compared with the viscosity d when left at 5 ° C. for 48 hours.
- the viscosity stability of the aqueous solution was determined from the ratio (viscosity ratio) d / c. A larger d / c value indicates a greater increase in viscosity when left at 5 ° C., which means that the viscosity stability is worse.
- the viscosity (mPa ⁇ s) is a value measured using a B-type viscometer BLII (manufactured by Toki Sangyo Co., Ltd.) under the conditions of a rotor speed of 60 rpm and a temperature of 20 ° C.
- Inorganic filler 1 Kaolinite clay “ASP 200” (average particle size 0.4 ⁇ m) manufactured by BASF Inorganic filler 2; Kaolinite-based clay “Huber 900” (average particle size 0.6 ⁇ m) manufactured by Humber (JM Huber) Inorganic filler 3; Heavy calcium carbonate “Whiteon P-30” (average particle size 1.75 ⁇ m) manufactured by Shiraishi Kogyo Co., Ltd.
- Example 1 Manufacture of resin material (1)
- a continuous polymerization tank equipped with a reflux condenser, a raw material supply line, a reaction liquid take-out line, a thermometer, a nitrogen inlet, an ethylene inlet, and a stirring blade was used.
- a continuous polymerization tank was continuously fed with 671 L / hr of vinyl acetate, 148 L / hr of methanol, and 1.0 L / hr of a 1% methanol solution of n-propylperoxydicarbonate as an initiator using a metering pump. .
- the amount of n-propyl peroxydicarbonate added was 0.00132% by mass / vinyl acetate.
- the ethylene pressure in the continuous polymerization tank was adjusted to 0.23 MPa.
- the polymerization liquid was continuously taken out from the continuous polymerization tank so that the liquid level in the continuous polymerization tank was constant.
- the polymerization rate at the outlet of the continuous polymerization tank was adjusted to 26%.
- propanethiol as a chain transfer agent was 0.00042% by mass / concentration in the system of vinyl acetate (concentration with respect to 100 when the residual vinyl acetate in the continuously extracted polymerization solution was 100).
- the residence time in the continuous polymerization tank was 5 hours.
- the temperature at the outlet of the continuous polymerization tank was 60 ° C.
- the polymerization solution is recovered from the continuous polymerization tank, and the remaining vinyl acetate (hereinafter sometimes abbreviated as “VAc”) is removed by introducing methanol vapor into the polymerization solution while heating to 75 ° C. in a warm water bath. Then, a methanol solution (32% PVAc concentration) of an ethylene-modified vinyl ester polymer (hereinafter sometimes abbreviated as “PVAc”) was obtained. The average residence time in the removal step was 2 hours, and the vinyl acetate remaining in the methanol solution of the obtained ethylene-modified vinyl ester polymer was 0.1%.
- VAc vinyl acetate
- the saponification reaction is carried out for 1 hour using sodium hydroxide at a molar ratio of 0.012 with respect to the ethylene-modified vinyl ester polymer as a saponification catalyst at a water content of 0.5% for use in the saponification step at 40 ° C. It was.
- the obtained polymer was immersed in methanol and washed. Next, the solvent was removed by centrifugation, followed by drying.
- the ethylene unit content was 2 mol%, the viscosity average polymerization degree was 1700, the saponification degree was 98.5 mol%, and 1,2-glycol Resin material whose main component is ethylene-modified PVA having a bond content of 1.6 mol%, a propyl group content at one end of 0.0061 mol%, and a sodium acetate content of 0.42% (1) was obtained.
- Comparative Example 1 since the degree of saponification of ethylene-modified PVA, which is the main component of the resin material (13), is too low, it was insoluble in water, and the solubility and viscosity stability of the aqueous solution could not be evaluated.
- Comparative Example 2 since the ethylene-modified PVA, which is the main component of the resin material (14), does not contain an ethylene unit, gelation occurs when left at 5 ° C. for 48 hours, and the viscosity stability of a 10% aqueous solution is very high. It was bad.
- Comparative Example 3 the viscosity stability of the aqueous solution was poor because the propyl group content of ethylene-modified PVA, which is the main component of the resin material (15), was too high.
- Comparative Example 4 since the viscosity-average polymerization degree of ethylene-modified PVA, which is the main component of the resin material (16), is too high, the solubility is poor, and gelation occurs when left at 5 ° C. for 48 hours. Sex was also very bad.
- Comparative Example 5 since the ethylene-modified PVA that is the main component of the resin material (17) does not contain a propyl group at one end, the hue (YI) and the viscosity stability of the aqueous solution were poor.
- Comparative Example 6 since the ethylene-modified PVA, which is the main component of the resin material (18), has a dodecyl group instead of a propyl group at one end, it gelled when left at 5 ° C.
- Example 13 The obtained resin material (1) powder (32 parts) and inorganic filler 1 (68 parts) were thoroughly dry blended, and then poured into stirring water (331 parts, 20 ° C.). Further, 2,4-diphenyl-4-methyl-1-pentene (DPMP) as a compound having a conjugated double bond and a molecular weight of 1000 or less was added to 0.004 parts by mass with respect to 100 parts by mass of the resin material (1). The mixture was poured into water, heated to 95 ° C., kept warm for 2 hours, and the resin material (1) was dissolved to obtain an adhesive. The obtained adhesive had a solid content concentration of 23.2%, and a viscosity at 20 ° C. and 30 rpm was 1210 mPa ⁇ s. The high-speed coatability of the obtained adhesive was evaluated according to the method described above. The results are shown in Table 3.
- DPMP 2,4-diphenyl-4-methyl-1-pentene
- Examples 14 to 16, Comparative Examples 10 to 12 Example 13 except that the type of resin material to be used, the type of inorganic filler, the type and content of a compound having a conjugated double bond and a molecular weight of 1000 or less, and the solid content concentration were changed as shown in Table 3.
- the adhesive was prepared and evaluated in the same manner as described above. The results are shown in Table 3.
- Comparative Example 10 since the ethylene-modified PVA, which is the main component of the resin material (14), does not contain ethylene units, adhesive droplets jump out from between the rolls (jumping) and are not uniformly transferred to the rolls. In addition, the adhesive solution foam was severely bitten and the high-speed coating property was insufficient. In Comparative Example 11, since the viscosity average polymerization degree of ethylene-modified PVA, which is the main component of the resin material (16), is too high, it was not uniformly transferred to the roll, and a lot of stringing of the adhesive occurred. It was confirmed that the high-speed coating property was insufficient.
- the resin material of the present invention is excellent in hue, water solubility, and viscosity stability of an aqueous solution. Therefore, the industrial usefulness of the present invention is extremely high.
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Abstract
Description
[1]エチレン単位の含有率が1モル%以上15モル%未満であり、粘度平均重合度が200以上3000未満であり、けん化度が80モル%以上99.9モル%未満であり、片末端にプロピル基を0.0005モル%以上0.10モル%以下有するエチレン変性ビニルアルコール系重合体と、酢酸ナトリウムとを含有し、前記酢酸ナトリウムの含有量が0.05質量%以上2質量%未満である、樹脂材料。
[2]樹脂材料10質量部に対して水90質量部を、90℃下、300rpmで5時間撹拌した際の樹脂材料の溶解度が90%以上である、[1]の樹脂材料。
[3]エチレン変性ビニルアルコール系重合体の1,2-グリコール結合量が1.2モル%以上2.0モル%未満である、[1]又は[2]の樹脂材料。
[4]エチレン変性ビニルアルコール系重合体のエチレン単位の含有率が1モル%以上5モル%未満である、[1]~[3]のいずれかの樹脂材料。
[5]共役二重結合を有する分子量1000以下の化合物をさらに含有し、前記化合物の含有量が、エチレン変性ビニルアルコール系重合体100質量部に対して0.000001~0.01質量部である、[1]~[4]のいずれかの樹脂材料。
[6]前記共役二重結合を有する分子量1000以下の化合物が、脂肪族二重結合同士の共役二重結合を有する化合物及び/又は脂肪族二重結合と芳香環との共役二重結合を有する化合物を含む、[5]の樹脂材料。
[7]前記共役二重結合を有する分子量1000以下の化合物が、脂肪族二重結合同士の共役二重結合を有する化合物を含み、前記脂肪族二重結合同士の共役二重結合を有する化合物が、共役ジエン化合物、共役トリエン化合物及び共役ポリエン化合物からなる群から選ばれる少なくとも1種である、[6]の樹脂材料。
[8]前記脂肪族二重結合同士の共役二重結合を有する化合物が、共役ジエン化合物である、[7]の樹脂材料。
[9]前記共役二重結合を有する分子量1000以下の化合物が、脂肪族二重結合と芳香環との共役二重結合を有する化合物を含む、[5]~[8]のいずれかの樹脂材料。
[10]前記共役二重結合を有する分子量1000以下の化合物の分子量が、500以下である、[1]~[9]のいずれかの樹脂材料。
[11]前記エチレン変性ビニルアルコール系重合体が、片末端にプロピル基を0.001モル%以上0.08モル%未満有する、[1]~[10]のいずれかの樹脂材料。
[12]前記酢酸ナトリウムの含有量が0.1質量%以上1.5質量%未満である、[1]~[11]のいずれかの樹脂材料。
[13]イエローインデックスが13.0以下である、[1]~[12]のいずれかの樹脂材料からなる粉末。
[14][1]~[12]のいずれかの樹脂材料を含有する、水溶液。
[15][14]の水溶液を用いてなる、接着剤。
本発明の樹脂材料は、エチレン単位の含有率が1モル%以上15モル%未満であり、粘度平均重合度が200以上3000未満であり、けん化度が80モル%以上99.9モル%未満であり、片末端にプロピル基を0.0005モル%以上0.10モル%以下有するエチレン変性ビニルアルコール系重合体(以下、「エチレン変性PVA」と略記することがある)と、酢酸ナトリウムとを含有し、前記酢酸ナトリウムの含有量が0.05質量%以上2質量%未満であることを特徴とする。本発明の樹脂材料は、エチレン変性PVAを主成分として含有する。本明細書において、「主成分」とは、樹脂材料中の含有率が50質量%以上であることを意味する。本発明の樹脂材料は、エチレン変性PVAを70質量%以上含むことが好ましく、80質量%以上含むことがより好ましく、90質量%以上含むことがさらに好ましく、95質量%以上含むことが特に好ましく、98質量%以上が最も好ましい。
本発明に用いるエチレン変性PVAは、エチレン単位の含有率が1モル%以上15モル%未満であることが重要であり、1モル%以上10モル%未満が好ましく、1モル%以上8モル%未満がより好ましく、1モル%以上5モル%未満がさらに好ましい。エチレン単位の含有率が1モル%未満では水溶液の粘度安定性が低下し、15モル%以上では水溶性が低下する。エチレン単位の含有率の測定方法は、後記する実施例に記載のとおりである。
P=([η]×104/8.29)(1/0.62)
プロピル基の含有率(モル%)=100×(S/3)/R
本発明の樹脂材料における酢酸ナトリウムの含有量は0.05質量%以上2質量%未満であることが重要であり、色相と水溶液の粘度安定性により優れる点から、0.1質量%以上1.5質量%未満が好ましく、0.15質量%以上1.0質量%未満がより好ましい。0.05質量%未満であると水溶液の粘度安定性が低下し、2質量%以上であると色相が悪化する。酢酸ナトリウムの含有量はJIS K 6726:1994に記載の溶解電導度法に従って求めた。なお、酢酸ナトリウムの含有量とは、エチレン変性PVA及び酢酸ナトリウムの合計質量に対する酢酸ナトリウムの含有割合を意味する。
本発明の樹脂材料は、高速塗工性や耐水接着性の向上の観点から、共役二重結合を有する分子量1000以下の化合物をさらに含有することが好適である。高速塗工性が向上するメカニズムは定かではないが、極性溶媒中において共役二重結合部位がエチレン変性PVAのエチレン単位と相互作用することで、エチレン変性PVA同士の分子間相互作用を適度に阻害することに起因すると推定される。
本発明の樹脂材料の好適な製造方法は、エチレンと酢酸ビニルを反応させてエチレン変性ビニルエステル重合体を得る重合工程、及び該エチレン変性ビニルエステル重合体をけん化するけん化工程を有する、エチレン変性PVAの製造方法において、前記重合工程においてプロピル基を有する開始剤及び連鎖移動剤の存在下でエチレンと酢酸ビニルを反応させて、さらに前記けん化工程に供するけん化原料溶液の含水率を特定量とし、けん化工程の触媒としてナトリウム原子を有する触媒を用いる方法である。重合工程においてプロピル基を有する開始剤及び連鎖移動剤を併用すると、得られるエチレン変性PVAの片末端に特定量のプロピル基を効率的に導入でき、さらにけん化原料溶液の含水率を特定量とし、かつ、ナトリウム原子を有する触媒を用いることで、得られる樹脂材料中の酢酸ナトリウムの含有量を制御できる。
エチレン変性PVAは、エチレンと酢酸ビニルを塊状重合法、溶液重合法、懸濁重合法、乳化重合法、分散重合法等の従来公知の方法で重合して製造できる。本発明の効果を高める点では、低級アルコールとともに重合する溶液重合法が好ましい。低級アルコールに特に限定はないが、メタノール、エタノール、プロパノール、イソプロパノール等の炭素数3以下のアルコールが好ましく、メタノールがより好ましい。重合操作は、回分法、半回分法及び連続法のいずれの重合方式も採用できる。
重合工程後に、得られたエチレン変性ビニルエステル重合体を含有する重合液中に残存する酢酸ビニルを除去する除去工程を有することが好ましい。このような除去工程を有することで着色の一因である酢酸ビニルをより多く除去できるため、結果として、得られる樹脂材料の色相がより一層向上する。残存する酢酸ビニルを除去する方法は特に限定されないが、(i)加熱により除去する方法、(ii)加熱をしながらメタノールを連続的に加えて除去する方法、(iii)メタノール蒸気を連続的に重合液に吹き込む方法、(iv)加熱をしながらメタノール蒸気を連続的に重合液に吹き込む方法等が挙げられる。除去工程を実施する反応器中に、エチレン変性ビニルエステル重合体を含有する重合液を連続的に添加しながら除去を行ってもよいし、一括で仕込んだ後に除去を行ってもよい。
重合工程、及び必要に応じてその後の除去工程で得られた、エチレン変性ビニルエステル重合体を含有する重合液に、さらに少量の水を添加することでけん化原料溶液を調製できる。水の添加量は、得られるけん化原料溶液の含水率(以下、「系含水率」と略記することがある)が0.1質量%以上3.0質量%以下となるように調整することが好ましく、0.3質量%以上2.5質量%以下がより好ましい。けん化原料溶液の系含水率を上記範囲とすることで、得られる樹脂材料における酢酸ナトリウムの含有量を容易に調整できる。
けん化工程後に必要に応じて洗浄工程を設けてもよい。洗浄に用いる溶媒としては、メタノール、エタノール等のアルコール類;酢酸メチル、酢酸エチル等のエステル類が挙げられる。洗浄工程の条件は特に限定されないが、20℃~溶媒の沸点の温度で、30分~10時間程度洗浄することが好ましい。
前記樹脂材料を含有する水溶液が、本発明の好適な実施態様である。当該水溶液は、接着剤、分散安定剤、被覆剤、バインダー、紙加工剤、粘度調整剤、フィルム等の成形物原料、後反応用樹脂原料など様々な用途に用いられる。中でも、当該水溶液を含有する接着剤が、後述するとおり、本発明のより好適な実施態様である。
前記水溶液を含有する接着剤は、本発明の好適な実施態様である。当該接着剤は、接着剤の流動性及び接着力の向上の点から、さらに無機充填剤を含有することが好ましい。無機充填剤は特に限定されるものではなく、被着体、塗工機、要求性能などに応じて適宜選択できる。無機充填剤として、例えば、カオリナイト、ハロイサイト、パイロフェライト及びセリサイトなどのクレー、重質、軽質、又は表面処理された炭酸カルシウム、水酸化アルミニウム、酸化アルミニウム、石膏類、タルク、酸化チタン等が挙げられる。中でもクレーが好ましい。これらの無機充填剤は1種を単独で、又は2種以上を組合せて使用できる。無機充填剤が水溶液中で凝集したり沈降したりすることなく均一なスラリー溶液が得られる点から、無機充填剤の平均粒径は10μm以下が好ましく、8μm以下がより好ましく、5μm以下がさらに好ましい。無機充填剤の平均粒径は株式会社島津製作所製のレーザ回折式粒子径分布測定装置SALD-2300で測定できる。
本発明の樹脂材料は種々の用途に使用される。以下にその例を挙げるがこれに限定されるものではない。
(1)分散剤用途:塗料、接着剤等に含まれる顔料の分散安定剤、塩化ビニル、塩化ビニリデン、スチレン、(メタ)アクリレート、酢酸ビニル等の各種ビニル化合物の懸濁重合用分散安定剤及び分散助剤
(2)被覆剤用途:紙のコーティング剤、サイズ剤、繊維加工剤、皮革仕上剤、塗料、防曇剤、金属腐食防止剤、亜鉛メッキ用光沢剤、帯電防止剤
(3)接着剤用途:接着剤、粘着剤、再湿接着剤、各種バインダー、セメントやモルタル用添加剤
(4)乳化剤用途:乳化重合用乳化剤、ビチュメン等の後乳化剤
(5)凝集剤用途:水中懸濁物及び溶存物の凝集剤、金属凝集剤
(6)紙加工用途:紙力増強剤、耐油性・耐溶剤性付与剤、平滑性向上剤、表面光沢改良助剤、目止剤、バリア剤、耐光性付与剤、耐水化剤、染料・顕色剤分散剤、接着力改良剤、バインダー
(7)農業用途:農薬用バインダー、農薬用展着剤、農業用被覆剤、土壌改良剤、エロージョン防止剤、農薬用分散剤
(8)医療・化粧品用途:造粒バインダー、コーティング剤、乳化剤、貼付剤、結合剤、フィルム製剤基材、皮膜形成剤
(9)粘度調整剤用途:増粘剤、レオロジー調整剤
(10)フィルム用途:水溶性フィルム、偏光フィルム、バリアフィルム、繊維製品包装用フィルム、種子養生シート、植生シート、シードテープ、吸湿性フィルム
(11)成形品用途:繊維、パイプ、チューブ、防漏膜、ケミカルレース用水溶性繊維、スポンジ
(12)ゲル用途:医薬用ゲル、工業用ゲル
(13)後反応用途:低分子有機化合物、高分子有機化合物、無機化合物との後反応用途
エチレン変性PVAのエチレン単位の含有率は、エチレン変性PVAの前駆体又は再酢化物であるエチレン変性ビニルエステル重合体の1H-NMRから求めた。具体的には、実施例及び比較例の試料のエチレン変性ビニルエステル重合体の再沈精製をn-ヘキサンとアセトンの混合溶液を用いて3回以上行った後、80℃で3日間減圧乾燥して分析用のエチレン変性ビニルエステル重合体を作製する。分析用のエチレン変性ビニルエステル重合体をDMSO-d6に溶解し、80℃で1H-NMR(500MHz)を測定した。酢酸ビニルの主鎖メチンプロトンに由来するピーク(積分値P:4.7~5.2ppm)とエチレン及び酢酸ビニルの主鎖メチレンプロトンに由来するピーク(積分値Q:1.0~1.6ppm)を用い次式によりエチレン単位の含有率を算出した。
エチレン単位の含有率(モル%)=100×((Q-2P)/4)/P
エチレン変性PVAの粘度平均重合度はJIS K 6726:1994に準じて測定した。具体的には、けん化度が99.5モル%未満の場合には、けん化度99.5モル%以上になるまでけん化したエチレン変性PVAについて、水中、30℃で測定した極限粘度[η](リットル/g)を用いて下記式により粘度平均重合度(P)を求めた。
P=([η]×104/8.29)(1/0.62)
エチレン変性PVAのけん化度は、JIS K 6726:1994に準じて測定した。
エチレン変性PVAに含まれる1,2-グリコール結合量は1H-NMRのピークから求めた。具体的には、エチレン変性PVAをけん化度99.9モル%以上にけん化後、十分にメタノール洗浄を行い、次いで90℃で2日間減圧乾燥したPVAをDMSO-d6に溶解し、トリフルオロ酢酸を数滴加えた試料を500MHzの1H-NMRを用いて80℃で測定した。ビニルアルコール単位のメチンプロトン由来のピークは3.2~4.0ppm(積分値A)に、1,2-グリコール結合の1つのメチンプロトン由来のピークは3.15~3.35ppm付近(積分値B)に帰属され、次式で1,2-グリコール結合量を算出した。
1,2-グリコール結合量(モル%)=B/A×100
エチレン変性PVAの片末端のプロピル基の含有率は、エチレン変性PVAの前駆体又は再酢化物であるエチレン変性ビニルエステル重合体の1H-NMRから求めた。試料のエチレン変性ビニルエステル重合体の再沈精製をn-ヘキサンとアセトンの混合溶液を用いて3回以上行った後、80℃で3日間減圧乾燥して分析用のエチレン変性ビニルエステル重合体を作製した。分析用のエチレン変性ビニルエステル重合体をDMSO-d6に溶解し、80℃で1H-NMR(500MHz)を測定した。酢酸ビニルの主鎖メチンプロトンに由来するピーク(積分値R:4.7~5.2ppm)とプロピル基のメチルプロトンに由来するピーク(積分値S:0.7~1.0ppm)を用い次式によりプロピル基の含有率を算出した。
プロピル基の含有率(モル%)=100×(S/3)/R
エチレン変性PVAを主成分とする樹脂材料における酢酸ナトリウムの含有量は、JIS K 6726:1994に記載の溶解電導度法に従って求めた。
樹脂材料10gに対して水90g、すなわち樹脂材料の10%水溶液100gを、90℃下、300rpmで5時間撹拌した後、200メッシュ(JIS標準篩のメッシュ換算では、目開き75μm;前記篩の目開きは、JIS Z 8801-1-2006の公称目開きWに準拠)の金網で全量ろ過し(ろ過前の金網の質量をa(g)とする)、金網ごと105℃で3時間乾燥した(乾燥後の金網と金網上に残存した物質の合計質量をb(g)とする)。下記式を用いて樹脂材料の溶解度(%)を求めた。
溶解度(%)=100-100×{(b-a)/10}
上記の条件で調製した樹脂材料の10%水溶液100gを5℃下で放置し、液温が5℃となった時点の粘度cを求め、5℃下で48時間放置した際の粘度dと比較し、それらの比(粘度比)d/cより、水溶液の粘度安定性を求めた。d/cの値が大きいほど、5℃下で放置した場合の粘度上昇が大きいことを示し、粘度安定性が悪いことを意味する。なお、粘度(mPa・s)はロータ回転数60rpm、温度20℃の条件で、B型粘度計BLII(東機産業株式会社製)を用いて測定した値である。
樹脂材料の色相は、粉末のイエローインデックス(YI)により求めた。篩(目開き:100μm、1000μm)を用いて100μm未満及び1000μmを超える粒子を除去した後、カラーメーター(スガ試験機製SM-T-H1)を用いて測定した。なお、YIはJIS Z 8722:2009及びJIS K 7373:2006に準じて測定、計算された値である。
無機充填剤1;BASF社製カオリナイト系クレー「ASP 200」(平均粒径0.4μm)
無機充填剤2;ヒューバー(J.M.Huber)社製カオリナイト系クレー「Huber 900」(平均粒径0.6μm)
無機充填剤3;白石工業社製重質炭酸カルシウム「ホワイトンP-30」(平均粒径1.75μm)
3本ロールを用いて以下の実施例及び比較例により得られた接着剤を評価した。このとき使用した3本ロールを図1に示す。各ロールの表面温度を30℃に調整した。ロール[II]とロール[III]の間に調製した接着剤[IV]を加えて、ロール[I]の表面速度を100m/分となるように回転することにより、次の各項目を評価した。
(1)ジャンピング:ロール[I]とロール[II]の間から接着剤の液滴が飛び出すかどうかを目視にて下記の基準で判定した。
A;全く液滴が飛び出さなかった
B;少数の液滴が飛び出した
C;多数の液滴が飛び出した
(2)ロール転写:ロール[I]へ接着剤が均一にのるかどうかを目視で判定した。
A;均一
B;不均一
(3)発泡:3本ロールを5分間回転させた。ロールを回転させる前の接着剤[IV]100mlの質量に対する、ロールを回転させた後の接着剤[IV]100mlの質量の比(回転後の質量/回転前の質量)から接着剤[IV]の泡のかみ込みを評価した。
(4)糸曳き:ロール[I]とロール[II]の間の接着剤の糸曳き性を目視にて以下の基準で判定した。
A;糸曳きの発生が確認されなかった
B;糸曳きが発生しているのが確認された
[樹脂材料(1)の製造]
還流冷却器、原料供給ライン、反応液取出ライン、温度計、窒素導入口、エチレン導入口及び撹拌翼を備えた連続重合槽を用いた。連続重合槽に酢酸ビニルを671L/hr、メタノールを148L/hr、開始剤としてn-プロピルパーオキシジカーボネートの1%メタノール溶液を1.0L/hr、それぞれ定量ポンプを用いて連続的に供給した。n-プロピルパーオキシジカーボネートの添加量は0.00132質量%/酢酸ビニルであった。連続重合槽内のエチレン圧力が0.23MPaになるように調整した。連続重合槽内の液面が一定になるように連続重合槽から重合液を連続的に取り出した。連続重合槽の出口での重合率が26%になるように調整した。この時、連鎖移動剤としてプロパンチオールを0.00042質量%/酢酸ビニルの系内濃度(連続的に抜き取る重合液中の残存酢酸ビニルを100とした際のそれに対する濃度)となるように連続的に添加した。連続重合槽の滞留時間は5時間であった。連続重合槽の出口の温度は60℃であった。連続重合槽より重合液を回収し、温水浴で75℃に加熱しながら重合液にメタノール蒸気を導入することで残存する酢酸ビニル(以下、「VAc」と略記することがある)の除去を行い、エチレン変性ビニルエステル重合体(以下、「PVAc」と略記することがある)のメタノール溶液(PVAcの濃度32%)を得た。除去工程での平均滞留時間は2時間、得られたエチレン変性ビニルエステル重合体のメタノール溶液中に残存する酢酸ビニルは0.1%であった。次いで40℃下、けん化工程に供する系含水率を0.5%、けん化触媒としてエチレン変性ビニルエステル重合体に対してモル比0.012の割合で水酸化ナトリウムを用い、1時間けん化反応を行った。得られた重合体をメタノールに浸漬し洗浄を行った。次いで溶媒を遠心分離で除去したのち乾燥を行い、エチレン単位の含有率が2モル%であり、粘度平均重合度が1700であり、けん化度が98.5モル%であり、1,2-グリコール結合量が1.6モル%であり、片末端でのプロピル基の含有率が0.0061モル%であるエチレン変性PVAを主成分とし、酢酸ナトリウムの含有量が0.42%である樹脂材料(1)を得た。
[樹脂材料(2)~(21)の製造]
使用するエチレン圧力、酢酸ビニルの使用量、メタノールの使用量、開始剤の種類及び使用量、連鎖移動剤の種類及び使用量、重合温度、重合率等の重合条件、残存酢酸ビニルモノマー除去工程における平均滞留時間、水浴温度等の条件、けん化時のPVAcの濃度、エチレン変性ビニルエステル重合体に対する水酸化ナトリウムのモル比、系含水率等のけん化条件を表1に示す通りに変更した以外は、実施例1における樹脂材料(1)の製造と同様にして樹脂材料(2)~(21)を製造した。製造結果を表2に示す。さらに、得られた樹脂材料(2)~(21)について、実施例1と同様に溶解度、水溶液の粘度安定性及び色相(YI)を評価した。結果を表2に示す。
実施例13
得られた樹脂材料(1)の粉末(32部)と無機充填剤1(68部)を充分にドライブレンドした後、撹拌している水(331部、20℃)に投入した。さらに、共役二重結合を有する分子量1000以下の化合物として2,4-ジフェニル-4-メチル-1-ペンテン(DPMP)を、樹脂材料(1)100質量部に対して、0.004質量部となるように水に投入し、95℃まで加熱し、2時間保温して樹脂材料(1)を溶解して接着剤を得た。得られた接着剤の固形分濃度は23.2%であり、20℃、30rpmでの粘度は1210mPa・sであった。得られた接着剤の高速塗工性を上述の方法に従って評価した。結果を表3に示す。
使用する樹脂材料の種類、無機充填剤の種類、共役二重結合を有する分子量1000以下の化合物の種類及びその含有量、並びに固形分濃度を表3に示すように変更した以外は、実施例13と同様にして接着剤の作製及び評価を行った。結果を表3に示す。
Claims (15)
- エチレン単位の含有率が1モル%以上15モル%未満であり、粘度平均重合度が200以上3000未満であり、けん化度が80モル%以上99.9モル%未満であり、片末端にプロピル基を0.0005モル%以上0.10モル%以下有するエチレン変性ビニルアルコール系重合体と、酢酸ナトリウムとを含有し、前記酢酸ナトリウムの含有量が0.05質量%以上2質量%未満である、樹脂材料。
- 樹脂材料10質量部に対して水90質量部を、90℃下、300rpmで5時間撹拌した際の樹脂材料の溶解度が90%以上である、請求項1に記載の樹脂材料。
- エチレン変性ビニルアルコール系重合体の1,2-グリコール結合量が1.2モル%以上2.0モル%未満である、請求項1又は2に記載の樹脂材料。
- エチレン変性ビニルアルコール系重合体のエチレン単位の含有率が1モル%以上5モル%未満である、請求項1~3のいずれかに記載の樹脂材料。
- 共役二重結合を有する分子量1000以下の化合物をさらに含有し、前記化合物の含有量が、エチレン変性ビニルアルコール系重合体100質量部に対して0.000001~0.01質量部である、請求項1~4のいずれかに記載の樹脂材料。
- 前記共役二重結合を有する分子量1000以下の化合物が、脂肪族二重結合同士の共役二重結合を有する化合物及び/又は脂肪族二重結合と芳香環との共役二重結合を有する化合物を含む、請求項5に記載の樹脂材料。
- 前記共役二重結合を有する分子量1000以下の化合物が、脂肪族二重結合同士の共役二重結合を有する化合物を含み、前記脂肪族二重結合同士の共役二重結合を有する化合物が、共役ジエン化合物、共役トリエン化合物及び共役ポリエン化合物からなる群から選ばれる少なくとも1種である、請求項6に記載の樹脂材料。
- 前記脂肪族二重結合同士の共役二重結合を有する化合物が、共役ジエン化合物である、請求項7に記載の樹脂材料。
- 前記共役二重結合を有する分子量1000以下の化合物が、脂肪族二重結合と芳香環との共役二重結合を有する化合物を含む、請求項5~8のいずれかに記載の樹脂材料。
- 前記共役二重結合を有する分子量1000以下の化合物の分子量が、500以下である、請求項1~9のいずれかに記載の樹脂材料。
- 前記エチレン変性ビニルアルコール系重合体が、片末端にプロピル基を0.001モル%以上0.08モル%未満有する、請求項1~10のいずれかに記載の樹脂材料。
- 前記酢酸ナトリウムの含有量が0.1質量%以上1.5質量%未満である、請求項1~11のいずれかに記載の樹脂材料。
- イエローインデックスが13.0以下である、請求項1~12のいずれかに記載の樹脂材料からなる粉末。
- 請求項1~12のいずれかに記載の樹脂材料を含有する、水溶液。
- 請求項14に記載の水溶液を用いてなる、接着剤。
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