WO2012043455A1 - 熱成形用ポリビニルアセタール樹脂 - Google Patents
熱成形用ポリビニルアセタール樹脂 Download PDFInfo
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- WO2012043455A1 WO2012043455A1 PCT/JP2011/071847 JP2011071847W WO2012043455A1 WO 2012043455 A1 WO2012043455 A1 WO 2012043455A1 JP 2011071847 W JP2011071847 W JP 2011071847W WO 2012043455 A1 WO2012043455 A1 WO 2012043455A1
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- polyvinyl acetal
- acetal resin
- thermoforming
- resin
- aldehyde
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- 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
- C08F8/28—Condensation with aldehydes or ketones
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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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- 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
- C08F116/00—Homopolymers 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
- C08F116/02—Homopolymers 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
- C08F116/04—Acyclic compounds
- C08F116/06—Polyvinyl alcohol ; Vinyl alcohol
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- 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
- C08F16/00—Homopolymers and 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
- C08F16/38—Homopolymers and 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 acetal or ketal radical
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- 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
- C08F216/38—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 acetal or ketal radical
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- 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
- C08F8/48—Isomerisation; Cyclisation
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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
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
Definitions
- the present invention relates to a polyvinyl acetal resin for thermoforming capable of providing a molded article having excellent stability during thermoforming and excellent heat resistance. More specifically, it is also suitable for use in molding applications that require high thermal stability, such as mixing with other resins and performing melt molding at high temperatures, or when more stable molding and quality are required.
- the present invention relates to a thermoforming polyvinyl acetal resin.
- the polyvinyl acetal resin is produced by acetalizing a polyvinyl alcohol resin with an aldehyde, and has been conventionally used in a wide range of fields such as an intermediate film for automobile windshields and safety glass, various binders, and adhesives.
- polyvinyl acetal resin has insufficient thermal stability, and when used for thermoforming, it may cause generation of decomposition gas, generation of cross-linked gel, etc. due to thermal decomposition or thermal degradation.
- decomposition and deterioration are likely to occur, causing coloring of molded products and deterioration of physical properties, etc., making it difficult to perform molding stably for a long time In some cases, it may be difficult to obtain a product of the required quality.
- Patent Documents 1 to 3 disclose interlayer films for laminated glass made of polyvinyl acetal resin and various plasticizers.
- Patent Document 4 discloses an interlayer film for laminated glass in which poly ( ⁇ -caprolactone) is blended with a polyvinyl acetal resin instead of a plasticizer.
- poly ( ⁇ -caprolactone) has a low melting point and low heat resistance, so the range of use is limited. In addition, the surface hardness of the molded product may decrease.
- Factors that affect the thermal stability of the polyvinyl acetal resin include the degree of polymerization of the polyvinyl alcohol resin as a raw material, the degree of saponification, the modified species and the amount of modification, the acetal species and the degree of acetalization of the polyvinyl acetal resin, and further in the resin Residual metal residues, unreacted aldehydes, by-products, and the like are considered. These factors are intertwined in a complicated manner, and it is considered that thermal deterioration such as decomposition, cross-linking gelation, and coloring occurs. However, with respect to these factors, it is not clearly understood by what mechanism the thermal degradation proceeds, and a polyvinyl acetal resin having sufficient thermal stability could not be obtained.
- Patent Document 5 an alkyl acetalized polyvinyl alcohol resin having a metal ion concentration of 100 ppm or less is disclosed as a binder resin for ink, but thermoforming even when this resin is used for thermoforming. There was a problem that the sex was not enough.
- the present invention provides a thermoforming polyvinyl acetal resin that can provide a molded article having excellent thermal stability and heat resistance without impairing the characteristics of the conventional polyvinyl acetal resin. It is to provide.
- the present inventors have found that the degree of polymerization and saponification of the polyvinyl alcohol resin to be used, and the degree of acetalization during the production of the polyvinyl acetal resin, also remain. It has been found that a polyvinyl acetal resin excellent in thermal stability can be obtained by controlling the content of alkali metal or alkaline earth metal to be in a specific range. Furthermore, it has been found that by controlling the structure of the aldehyde used in acetalization, it is possible to provide a molded product having excellent heat resistance. The present invention has been further studied and completed based on these findings.
- the present invention is obtained by acetalizing a polyvinyl alcohol resin having a viscosity average polymerization degree of 500 to 2000 and a saponification degree of 99.5 mol% or more with aldehyde, and the total of vinyl alcohol units acetalized with aldehyde is It is a polyvinyl acetal resin for thermoforming having a content of alkali metal or alkaline earth metal of 0.1 to 50 ppm at 65 to 88 mol% with respect to all repeating units.
- the molar ratio of vinyl alcohol unit acetalized with an aldehyde having 4 or more carbon atoms / vinyl alcohol unit acetalized with an aldehyde having 3 or less carbon atoms is 90/10. It is preferably ⁇ 0 / 100.
- polyvinyl acetal resin of this invention it is preferable that it is polyvinyl butyral.
- the total of vinyl alcohol units acetalized with aldehyde is preferably 70 to 88 mol% with respect to all repeating units.
- the content of the plasticizer is preferably 20 parts by mass or less with respect to 100 parts by mass of the polyvinyl acetal resin.
- the polyvinyl acetal resin for thermoforming of the present invention it is preferable that the polyvinyl acetal resin does not contain a plasticizer.
- the polyvinyl acetal resin for thermoforming according to the present invention is preferably obtained by subjecting the slurry obtained by acetalizing the polyvinyl alcohol resin to a pH of 6 to 8 and then performing a drying treatment.
- the moisture content of the polyvinyl acetal resin is preferably adjusted to 0.005 to 2%.
- the present invention includes a molded body and a film made of the polyvinyl acetal resin for thermoforming.
- the present invention is obtained by acetalizing a polyvinyl alcohol resin having a viscosity average polymerization degree of 500 to 2000 and a saponification degree of 99.5 mol% or more with an aldehyde, and the total of vinyl alcohol units acetalized with the aldehyde is A method for producing a molded body in which thermoforming is performed using a polyvinyl acetal resin for thermoforming, which is 65 to 88 mol% with respect to all repeating units and the content of alkali metal or alkaline earth metal is 0.1 to 50 ppm. .
- thermoforming by adjusting the content of the plasticizer to 20 parts by mass or less with respect to 100 parts by mass of the polyvinyl acetal resin.
- the present invention is obtained by acetalizing a polyvinyl alcohol resin having a viscosity average polymerization degree of 500 to 2000 and a saponification degree of 99.5 mol% or more with an aldehyde, and the total of vinyl alcohol units acetalized with the aldehyde is
- This is a method for producing a film in which thermoforming is performed using a polyvinyl acetal resin for thermoforming which is 65 to 88 mol% with respect to all repeating units and the content of alkali metal or alkaline earth metal is 0.1 to 50 ppm.
- thermoforming by adjusting the content of the plasticizer to 10 parts by mass or less with respect to 100 parts by mass of the polyvinyl acetal resin.
- heat stability and heat resistance are excellent without impairing the physical properties of the strength, elastic modulus, surface hardness, surface smoothness, transparency, etc. of the molded product of the conventional polyvinyl acetal resin.
- a polyvinyl acetal resin for thermoforming that can provide a molded product can be provided.
- the polyvinyl acetal resin of this invention is resin which has a repeating unit represented by Chemical formula (1), for example.
- n is the number of aldehyde types (natural number) used for acetalization
- R 1 , R 2 ,..., R n are alkyl residues of the aldehyde used for the acetalization reaction or It is a hydrogen atom
- k (1) , k (2) ,..., k (n) are ratios (mol ratio) of acetal units containing R 1 , R 2 ,..., R n , respectively
- l is a ratio of vinyl alcohol units.
- Mol ratio m is the ratio (mol ratio) of vinyl acetate units.
- the repeating units are not limited to the arrangement order shown in the chemical formula (1), and may be arranged randomly, arranged in blocks, or arranged in a tapered shape. Good.
- the polyvinyl acetal resin of the present invention can be obtained by reacting a polyvinyl alcohol resin (hereinafter sometimes abbreviated as PVA) and an aldehyde.
- PVA polyvinyl alcohol resin
- the PVA used in the production of the polyvinyl acetal resin of the present invention is not only a PVA homopolymer, but also a modified PVA copolymerized with other monomers, or a functional group introduced by terminal modification and post-modification. Modified PVA is also included.
- the viscosity average degree of polymerization of PVA (hereinafter simply referred to as the degree of polymerization) is 500 to 2000, preferably 800 to 1700, and more preferably 1000 to 1500.
- the polymerization degree of PVA is less than 500, the mechanical properties of the obtained polyvinyl acetal resin are insufficient, and the toughness may be particularly insufficient.
- the polymerization degree of PVA exceeds 2000, the melt viscosity at the time of thermoforming as a polyvinyl acetal resin becomes high, and it becomes difficult to produce a molded product.
- the degree of polymerization (P) of PVA is measured according to JIS-K6726. That is, it is obtained by the general formula (i) from the intrinsic viscosity [ ⁇ ] (dl / g) measured in water at 30 ° C. after completely re-saponifying and purifying PVA.
- the degree of saponification of PVA is 99.5 mol% or more, preferably 99.7 mol% or more, particularly preferably 99.9 mol% or more.
- the degree of saponification is less than 99.5 mol%, the resulting polyvinyl acetal resin is not sufficiently heat stable, and it may be difficult to perform stable melt molding by thermal decomposition or cross-linking gelation.
- PVA is not particularly limited by its production method, and can be obtained by saponifying vinyl ester units of a vinyl ester polymer.
- Vinyl compound monomers for forming vinyl ester units include vinyl formate, vinyl acetate, vinyl propionate, vinyl valenate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate and Examples include vinyl versatate, and among these, vinyl acetate is preferable in that PVA can be obtained with high productivity.
- the PVA used for the production of the polyvinyl acetal resin of the present invention may be a homopolymer or a modified PVA introduced with copolymerized units.
- the comonomer include ⁇ -olefins such as ethylene, propylene, 1-butene, isobutene and 1-hexene, acrylic acid and salts thereof, methyl acrylate, ethyl acrylate, and acrylic acid n- Acrylic esters such as propyl and i-propyl acrylate, methacrylic acid and salts thereof, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, and i-propyl methacrylate, acrylamide, N- Acrylamide derivatives such as methyl acrylamide and N-ethyl acrylamide, methacrylamide derivatives such as methacrylamide, N-methyl methacrylamide and N-ethyl methacrylamide, methyl vinyl ether, eth
- N-vinylamides such as N-vinylformamide, N-vinylacetamide, N-vinylpyrrolidone, fumaric acid, maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, anhydrous Monomers having a carboxyl group derived from trimellitic acid or itaconic anhydride; sulfonic acid groups derived from ethylenesulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc.
- Monomer having: vinyloxyethyltrimethylammonium chloride, vinyloxybutyltrimethylammonium chloride, vinyloxyethyldimethylamine, vinyloxymethyldiethylamine, N-acrylamidomethyltrimethylammonium chloride, N-acrylic Bromide trimethylammonium chloride, N- acrylamide dimethylamine, allyl trimethyl ammonium chloride, methallyl trimethylammonium chloride, dimethyl allyl amine include monomers having a cationic group derived from the allyl ethyl amine.
- the content of these monomers is usually 20 mol% or less when the mol number of all units constituting the modified PVA is 100%. Moreover, in order to exhibit the merit of being copolymerized, it is preferable that 0.01 mol% or more is the said copolymerization unit.
- Examples of methods for producing PVA used in the present invention include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among them, a bulk polymerization method or a solution polymerization method in which polymerization is performed without solvent or in a solvent such as alcohol is usually employed. Examples of alcohol used as a solvent during solution polymerization include lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol.
- Initiators used for copolymerization include ⁇ , ⁇ ′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl-valeronitrile), benzoyl peroxide, n-propyl peroxycarbonate And known initiators such as azo initiators or peroxide initiators.
- the polymerization temperature is not particularly limited, but a range of 0 ° C. to 200 ° C. is appropriate.
- examples of the alkaline substance used as a catalyst when saponifying PVA include potassium hydroxide and sodium hydroxide.
- the molar ratio of the alkaline substance used for the saponification catalyst is preferably from 0.004 to 0.5, particularly preferably from 0.005 to 0.05, based on the vinyl acetate unit.
- the saponification catalyst may be added all at the beginning of the saponification reaction, or may be added additionally during the saponification reaction.
- Examples of the saponification solvent include methanol, methyl acetate, dimethyl sulfoxide, dimethylformamide and the like.
- methanol is preferable, methanol whose water content is controlled to 0.001 to 1% by mass is more preferable, methanol whose water content is controlled to 0.003 to 0.9% by mass is more preferable, and water content is Methanol controlled to 0.005 to 0.8% by mass is particularly preferable.
- the cleaning liquid include methanol, acetone, methyl acetate, ethyl acetate, hexane, water, and the like. Among these, methanol, methyl acetate, water alone or a mixed liquid is more preferable.
- the amount of the cleaning liquid is set so as to satisfy the alkali metal content, but is usually preferably 300 to 10,000 parts by mass, more preferably 500 to 5000 parts by mass with respect to 100 parts by mass of PVA.
- the washing temperature is preferably 5 to 80 ° C, more preferably 20 to 70 ° C.
- the washing time is preferably 20 minutes to 100 hours, more preferably 1 hour to 50 hours.
- the content of the alkali metal in the PVA used in the present invention is preferably 0.00001 to 1 part by mass, more preferably 0.0001 to 0.1 part by mass with respect to 100 parts by mass of PVA. Those having an alkali metal content of less than 0.00001 parts by mass are difficult to produce industrially. Moreover, when there is more content of an alkali metal than 1 mass part, content of the alkali metal which remains in the obtained polyvinyl acetal resin increases, and it may be unable to be stably melt-molded by decomposition and gelation. is there. Examples of the alkali metal include sodium and potassium. The alkali metal content can be determined by atomic absorption method.
- the aldehyde used for the production of the polyvinyl acetal resin is not particularly limited.
- formaldehyde including paraformaldehyde
- acetaldehyde including paraacetaldehyde
- propionaldehyde butyraldehyde
- n-octylaldehyde amylaldehyde, hexylaldehyde, heptylaldehyde, 2-ethylhexylaldehyde, cyclohexylaldehyde, furfural, glyoxal
- Examples include glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, ⁇ -phenylpropionaldehyde and the like.
- a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin with an aldehyde mainly composed of butyraldehyde is particularly referred to as polyvinyl butyral.
- the reaction (acetalization reaction) between the polyvinyl alcohol resin and the aldehyde can be performed by a known method.
- aqueous solution method in which an aqueous solution of a polyvinyl alcohol resin and an aldehyde are acetalized in the presence of an acid catalyst to precipitate resin particles, the polyvinyl alcohol resin is dispersed in an organic solvent, and the aldehyde and the aldehyde are present in the presence of an acid catalyst.
- Examples thereof include a solvent method in which an acetalization reaction is performed and the reaction solution is precipitated with water or the like which is a poor solvent for the polyvinyl acetal resin.
- the acid catalyst is not particularly limited, and examples thereof include organic acids such as acetic acid and p-toluenesulfonic acid; inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid; gases that show acidity when made into an aqueous solution such as carbon dioxide, cation exchange And solid acid catalysts such as metal oxides and metal oxides.
- organic acids such as acetic acid and p-toluenesulfonic acid
- inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid
- gases that show acidity when made into an aqueous solution such as carbon dioxide, cation exchange
- solid acid catalysts such as metal oxides and metal oxides.
- the degree of acetalization of the polyvinyl acetal resin used in the present invention is 65 to 88 mol%, and 70 to 86 mol%. Preferably, it is 72 to 86 mol%, more preferably 75 to 84 mol%.
- Polyvinyl acetal resins having an acetalization degree of less than 65 mol% are not sufficiently heat stable and have poor melt processability.
- Polyvinyl acetal resins having a degree of acetalization exceeding 88 mol% are very difficult to produce, and a long time is required for the acetalization reaction, resulting in an increased production cost.
- the acetalization degree (mol%) of polyvinyl acetal resin can be defined by the following formula
- the degree of acetalization of the polyvinyl acetal resin is determined by titration of the mass ratio of vinyl alcohol units (l 0 ) and the mass ratio of vinyl acetate units (m 0 ) according to the method described in JIS K6728 (1977).
- the mol ratio of vinyl acetal units (k k (1) + k (2) +...
- the polyvinyl acetal resin dissolved in deuterated dimethyl sulfoxide may be calculated by 1 H-NMR analysis or 13 C-NMR,.
- the ratio of acetalization with butyraldehyde is particularly called the degree of butyralization.
- the degree of butyralization is defined by the general formula (iii).
- the polyvinyl butyral resin used in the present invention preferably has a butyralization degree of 65 to 83 mol%, more preferably 70 to 83 mol%. That is, 0.65 ⁇ k (1) ⁇ 0.83 is preferable, and 0.70 ⁇ k (1) ⁇ 0.83 is more preferable.
- a polyvinyl acetal resin having a butyralization degree in the above range is used, it is excellent in mechanical properties, particularly toughness, and a molded product can be obtained easily and inexpensively.
- polyvinyl acetal resin of the present invention includes a resin having a repeating unit represented by the chemical formula (2).
- R 3 is a hydrocarbon group or hydrogen atom derived from an aldehyde having 3 or less carbon atoms used in the acetalization reaction
- R 4 is a carbonization derived from an aldehyde having 4 or more carbon atoms used in the acetalization reaction.
- the hydrogen group (the carbon number of the hydrocarbon groups R 3 and R 4 is an integer i obtained by subtracting 1 from the carbon number of the aldehyde used in the acetalization reaction.
- i is zero
- R 3 is a hydrogen atom. That is, R 3 is a hydrocarbon group having 2 or less carbon atoms, and R 4 is a hydrocarbon group having 3 or more carbon atoms, where R 3 and R 4 are concepts including all hydrocarbon groups.
- K (3) the molar ratio of vinyl alcohol units acetalized with the number 3 or less aldehyde carbon
- k (4) are vinyl alcohol units acetalized with 4 or more aldehyde carbon
- L is the molar proportion of vinyl alcohol units that are not acetalized
- m is the molar proportion of vinyl acetate units.
- k (4) and m may be zero.
- Each unit is not particularly limited by the arrangement order shown in chemical formula (2), and may be arranged randomly, in a block shape, or in a tapered shape.
- the polyvinyl acetal resin having a repeating unit represented by the chemical formula (2) can be obtained by reacting the above PVA with an aldehyde.
- aldehyde having 3 or less carbon atoms used in the production of the polyvinyl acetal resin having a repeating unit represented by the chemical formula (2) include formaldehyde (including paraformaldehyde), acetaldehyde (including paraacetaldehyde), and propionaldehyde. Can be mentioned. These aldehydes having 3 or less carbon atoms can be used alone or in combination of two or more. Of these aldehydes having 3 or less carbon atoms, those mainly composed of acetaldehyde and formaldehyde (including paraformaldehyde) are preferable, and acetaldehyde is particularly preferable, from the viewpoint of ease of production and heat resistance.
- aldehyde having 4 or more carbon atoms used in the production of the polyvinyl acetal resin having a repeating unit represented by the chemical formula (2) include butyraldehyde, isobutyraldehyde, n-octylaldehyde, amylaldehyde, hexylaldehyde, heptylaldehyde, 2 -Ethylhexyl aldehyde, cyclohexyl aldehyde, furfural, glyoxal, glutaraldehyde, benzaldehyde, 2-methylbenzaldehyde, 3-methylbenzaldehyde, 4-methylbenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde, phenylacetaldehyde, ⁇ -phenylpropionaldehyde, etc.
- aldehydes having 4 or more carbon atoms can be used singly or in combination of two or more.
- those mainly composed of butyraldehyde are preferred from the viewpoint of ease of production.
- butyraldehyde and acetaldehyde are preferable from the viewpoint of ease of production, heat resistance and mechanical properties.
- the total of the acetalized vinyl alcohol units is 65 to 88 mol% and 70 to 86 mol% with respect to all the repeating units. Is more preferably 72 to 86 mol%, and further preferably 75 to 84 mol%.
- a polyvinyl acetalized resin in which the total of acetalized vinyl alcohol units is less than 65 mol% with respect to all repeating units is not sufficiently heat stable and has poor melt processability.
- a polyvinyl acetal resin exceeding 88 mol% is very difficult to produce and requires a long time for the acetalization reaction, resulting in an increased production cost.
- the mol% of the repeating unit refers to a unit consisting of two main chain carbons (for example, a vinyl alcohol unit, a vinyl acetate unit, an ethylene unit, etc.) in the polyvinyl alcohol resin that is a raw material for producing the polyvinyl acetal resin.
- the polyvinyl acetal resin having a repeating unit represented by the chemical formula (2) is acetalized with a vinyl alcohol unit acetalized with an aldehyde having 4 or more carbon atoms / an aldehyde with 3 or less carbon atoms from the viewpoint of mechanical properties and heat resistance.
- the molar ratio of the vinyl alcohol units formed is 90/10 to 0/100, preferably 80/20 to 0/100, more preferably 50/50 to 0/100, and 40/60 to 1/99 is particularly preferable.
- the reaction (acetalization reaction) between the polyvinyl alcohol resin and the aldehyde can be performed by a known method.
- aqueous solution method in which an aqueous solution of a polyvinyl alcohol resin and an aldehyde are acetalized in the presence of an acid catalyst to precipitate resin particles, the polyvinyl alcohol resin is dispersed in an organic solvent, and the aldehyde and the aldehyde are present in the presence of an acid catalyst.
- Examples thereof include a solvent method in which an acetalization reaction is performed and the reaction solution is precipitated with water or the like which is a poor solvent for the polyvinyl acetal resin.
- Aldehydes used for acetalization may be charged all at the same time or may be charged separately one by one.
- the randomness of the vinyl acetal unit in the polyvinyl acetal resin can be changed.
- the acid catalyst is not particularly limited, and examples thereof include organic acids such as acetic acid and p-toluenesulfonic acid; inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid; Examples thereof include solid acid catalysts such as ion exchangers and metal oxides.
- the total degree of acetalization of the polyvinyl acetal resin having a repeating unit represented by the chemical formula (2) is determined according to the method described in JIS K6728 (1977).
- the total degree of acetalization (mol%) k / ⁇ k + 1 + m ⁇ ⁇ 100, or polyvinyl acetate
- the Lumpur resin dissolved in deuterated dimethyl sulfoxide may be calculated by 1 H-NMR analysis or 13 C-NMR,.
- the molar ratio of vinyl alcohol units acetalized with butyraldehyde is particularly called the degree of butyralization.
- the molar ratio of vinyl alcohol units acetalized with acetaldehyde is particularly called the degree of acetoacetalization.
- the molar ratio of vinyl alcohol units acetalized with formaldehyde is called the degree of formalization.
- a polyvinyl acetal resin obtained by acetalizing a polyvinyl alcohol resin with butyraldehyde, acetaldehyde and formaldehyde the molar ratio of vinyl alcohol units acetalized with butyraldehyde is k (BA)
- vinyl acetalized with acetaldehyde The molar proportion of alcohol units is k (AA)
- the molar proportion of vinyl alcohol units acetalized with formaldehyde is k (FA)
- the molar proportion of vinyl alcohol units not acetalized is l
- the molar proportion of vinyl acetate units the molar proportion of vinyl acetate units.
- the degree of butyralization is determined by the formula: k (BA) / ⁇ k (BA) + k (AA) + k (FA) + l + m ⁇ ⁇ 100.
- the degree of acetoacetalization is determined by the formula: k (AA) / ⁇ k (BA) + k (AA) + k (FA) + l + m ⁇ ⁇ 100.
- the degree of formalization is determined by the formula: k (FA) / ⁇ k (BA) + k (AA) + k (FA) + l + m ⁇ ⁇ 100.
- the content of the vinyl ester unit is 0.5 mol% or less.
- the content of vinyl ester units in the polyvinyl acetal resin is 0.5 mol% or less, preferably 0.3 mol% or less, and particularly preferably 0.1 mol% or less.
- the thermal stability of the polyvinyl acetal resin is not sufficient, and it becomes difficult to perform stable melt molding by thermal decomposition or cross-linking gelation.
- the polymerization degree of the polyvinyl alcohol resin and the polyvinyl acetal resin obtained by acetalizing the polyvinyl alcohol resin are the same. Since the polyvinyl acetal resin of the present invention is obtained by acetalizing PVA having a polymerization degree of 500 to 2000, the polymerization degree is also 500 to 2000.
- the degree of polymerization of the polyvinyl acetal resin is preferably 800 to 1700, and more preferably 1000 to 1500. If the degree of polymerization of the polyvinyl acetal resin is less than 500, the mechanical properties of the polyvinyl acetal resin may be insufficient, and particularly the toughness may be insufficient. If the degree of polymerization exceeds 2000, the melt viscosity during thermoforming increases. This makes it difficult to produce a molded product.
- the slurry produced in the water medium method and the solvent method is usually acidic by an acid catalyst.
- the pH of the slurry is preferably adjusted to 6 to 8, and more preferably adjusted to 6.5 to 7.5.
- the pH of the slurry is less than 6, decomposition or crosslinking of the polyvinyl acetal resin may occur due to the acid, and a stable molded product may not be obtained.
- the pH of the slurry exceeds 8, polymer degradation may progress, and the molded product may be colored.
- Examples of the method for adjusting the pH include a method for adjusting the slurry repeatedly by washing with water, a method for adjusting the slurry by adding a neutralizing agent, a method for adding alkylene oxides, and the like.
- Examples of the neutralizing agent include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydrogen carbonate, and potassium carbonate, alkaline earth metal compounds such as calcium hydroxide, and ammonia. And an aqueous ammonia solution.
- alkylene oxides include ethylene oxide, propylene oxide; glycidyl ethers such as ethylene glycol diglycidyl ether.
- the polymer may be deteriorated and stable thermoforming may not be performed.
- the alkali metal or alkaline earth metal contained in the compound used as a neutralizing agent tends to cause thermal decomposition, and if it remains in a large amount, it causes severe polymer decomposition and cross-linking gelation, and stable melt molding cannot be performed.
- the content of alkali metal or alkaline earth metal in the polyvinyl acetal resin is 0.1 to 50 ppm, preferably 0.1 to 10 ppm, and particularly preferably 0.1 to 1 ppm. preferable.
- the content of the alkali metal or alkaline earth metal is less than 0.1 ppm, it is difficult to produce industrially, and it takes a long time for washing, resulting in an increase in production cost.
- the method for removing the residue is not particularly limited, and as the cleaning liquid, water or a mixed liquid obtained by adding an alcohol such as methanol or ethanol to water is used, and a method such as repeated liquid removal and cleaning is usually used. .
- the cleaning liquid water or a mixed liquid obtained by adding an alcohol such as methanol or ethanol to water is used, and a method such as repeated liquid removal and cleaning is usually used.
- the polyvinyl acetal resin After neutralizing the polyvinyl acetal resin, it is removed with a mixed solution of water / alcohol (methanol, ethanol, etc.) until the pH is 6 to 8, preferably 6.5 to 7.5.
- the method of repeating the liquid and washing is preferable in that the alkali metal or alkaline earth metal can be efficiently reduced, and the polyvinyl acetal resin of the present invention can be stably produced.
- the mixing ratio of water / alcohol is preferably 50/50 to 95/5, more preferably 60/40 to 90/10 in terms of mass ratio.
- the ratio of water is less than 50/50, the elution of the polyvinyl acetal resin into the mixed solution may increase, and when the ratio of water is greater than 95/5, the alkali metal or alkaline earth metal is efficiently removed. It becomes impossible to obtain the polyvinyl acetal resin of the present invention, and stable thermoforming tends to be impossible.
- the water-containing polyvinyl acetal resin from which residues and the like have been removed is dried as necessary, processed into powder, granules, or pellets as necessary, and used as a molding material. It is preferable to reduce unreacted aldehyde, moisture, and the like by degassing under reduced pressure when processing into powder, granules, or pellets.
- the moisture content of the polyvinyl acetal resin of the present invention is preferably adjusted to 0.005 to 2%, more preferably 0.01 to 1%. Products with a moisture content of less than 0.005% are difficult to manufacture and have an excessive heat history, which may cause deterioration in quality such as coloring. On the other hand, if the moisture content exceeds 2%, it may be difficult to perform stable thermoforming with a normal forming method. The moisture content can be measured by the Karl Fischer method.
- the polyvinyl acetal resin of the present invention has a sinusoidal vibration of 10 Hz and a heating rate of 3 ° C./min.
- the main dispersion peak temperature T ⁇ measured under the conditions is preferably 85 ° C. to 125 ° C., more preferably 90 ° C. to 120 ° C.
- T ⁇ is less than 85 ° C., it may be difficult to provide a molded article having excellent heat resistance.
- T ⁇ exceeds 125 ° C., the moldability may be lowered, and the use range may be limited.
- the polyvinyl acetal resin for thermoforming of the present invention contains various additives as necessary, for example, antioxidants, stabilizers, lubricants, processing aids, antistatic agents, colorants, impact resistance aids, foaming agents, Fillers, matting agents and the like may be blended.
- a softener and a plasticizer are not included in a large amount from the viewpoint of the mechanical properties and surface hardness of the obtained molded product or film.
- the plasticizer contained in the thermosetting polyvinyl acetal resin of the present invention is 20 parts by mass or less and preferably 10 parts by mass or less with respect to 100 parts by mass of the polyvinyl acetal resin. More preferably, the polyvinyl acetal resin does not contain a plasticizer. When the amount of the plasticizer exceeds 20 parts by mass, the plasticizer bleeds out and tends to adversely affect the molded product or film obtained.
- the plasticizer contained in the polyvinyl acetal resin for thermoforming according to the present invention include carboxylic acid ester plasticizers such as monovalent carboxylic acid esters and polyvalent carboxylic acid esters, phosphoric acid ester plasticizers, and organic phosphorous acid.
- polymer plasticizers such as carboxylic acid polyesters, carbonic acid polyesters, and polyalkylene glycols can also be used. These plasticizers may be used alone or in combination of two or more. Among them, triethylene glycol di-2-ethylhexanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate are excellent in the plasticizing effect. And tetraethylene glycol n-heptanoate are preferred.
- an ultraviolet absorber can be added for the purpose of improving the weather resistance.
- the kind of ultraviolet absorber is not specifically limited, A benzotriazole type, a benzophenone type, or a triazine type is preferable.
- the addition amount of the ultraviolet absorber is usually 0.1 to 10% by mass, preferably 0.1 to 5% by mass, more preferably 0.1 to 2% by mass with respect to the polyvinyl acetal resin for thermoforming. is there.
- the polyvinyl acetal resin for thermoforming of the present invention is used, for example, as a molding material in powder form or pellet form. And, using this molding material, various molded products can be manufactured by performing known molding methods such as extrusion molding, injection molding, vacuum molding, pressure molding, blow molding, transfer molding, rotational molding, powder slush, etc. it can.
- the polyvinyl acetal resin for thermoforming of the present invention is kneaded in a molten state with other resins using a known kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a brabender, an open roll, or a kneader. It can also be used.
- a twin screw extruder is preferable because of excellent productivity and a large shearing force.
- polyvinyl acetal resin for thermoforming of the present invention is used for melt-kneading with other resins
- specific examples of other resins include, for example, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, etc.
- Aromatic polyesters and copolymers thereof aliphatic polyesters such as polylactic acid, polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polyhydroxybutyrate-polyhydroxyvalylate copolymer, polycaprolactone, and copolymers thereof Polymer, Nylon 6, Nylon 66, Nylon 610, Nylon 10, Nylon 12, Nylon 6-12 and other aliphatic polyamides and copolymers thereof, polypropylene, polyethylene, polybutene, polymer Polyolefins such as rupentene and copolymers thereof, polystyrene, polydiene, chlorine, polyolefin, polyester, polyurethane, polyamide, fluorine elastomer, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n- Examples thereof include polyalkyl methacrylates such as butyl methacrylate, sec-butyl meth
- the ratio of the polyvinyl acetal resin to the total of the polyvinyl acetal resin and the other resin when kneaded with another resin is preferably 1% by mass or more, and more preferably 5% by mass or more.
- the ratio of the polyvinyl acetal resin is less than 1% by mass, the physical properties of the polyvinyl acetal resin are difficult to obtain, and the blending effect of the polyvinyl acetal resin tends to decrease.
- the polyvinyl acetal resin for thermoforming of the present invention can obtain a film and a molded article having excellent transparency and mechanical properties by a melt extrusion molding method such as a T-die method, a calender method, an inflation method or an injection molding method. Is possible.
- the T-die method is preferably used from the viewpoint of economy.
- the preferred resin temperature for melt extrusion is 150 to 250 ° C.
- the molded body is preferably cooled rapidly.
- it is preferable that the film-like molded body immediately after being extruded is brought into contact with a cooling roll and rapidly cooled.
- the film obtained from the polyvinyl acetal resin for thermoforming according to the present invention may be a single layer film or a laminate with another resin or substrate.
- the film which consists of the polyvinyl acetal resin for thermoforming of this invention may be used for an inner layer or a part thereof, and may be used for an outermost layer. There is no particular limitation on the number of laminated films.
- the method for producing the laminate is not particularly limited, and examples thereof include a method for directly producing a multilayer film by a co-extrusion method, a method for bonding a film produced by a single layer, and the like.
- thermoformable polyvinyl acetal resin of the present invention can be applied to various molded products.
- Applications include, for example, billboard parts and marking films such as advertising towers, stand signs, sleeve signs, bamboard signs, and rooftop signs; display parts such as showcases, dividers, and store displays; fluorescent lamp covers, mood lighting covers, and lamps.
- Lighting parts such as shades, light ceilings, light walls, and chandeliers; interior parts such as furniture, pendants, mirrors; doors, domes, safety window glass, partitions, staircases, balconies, balconies, and roofs for leisure buildings Parts; Aircraft windshields, pilot visors, motorcycles, motorboat windshields, bus shading plates, automotive side visors, rear visors, head wings, headlight covers, automotive interior parts, automotive exterior parts such as bumpers, etc .; Name plate for audio images, stereo cover, TV protection mask, Electronic equipment parts such as vending machines, mobile phones, personal computers; medical equipment parts such as incubators and X-ray parts; equipment-related parts such as machine covers, instrument covers, experimental devices, rulers, dials, observation windows; LCD protective plates , Light guide plate, light guide film, Fresnel lens, lenticular lens, optical display parts such as front plate and diffuser for various displays; traffic related parts such as road signs, guide plates, curve mirrors, soundproof walls; Water tank, box water tank, bathroom material, clock panel, bathtub
- Mw (acetal) is the molecular weight per acetalization unit.
- the acetic acid produced is titrated with N / 2 sodium hydroxide solution with phenolphthalein as an indicator until it turns pale red, and the titration is defined as a (ml).
- a blank test was performed, and the titration amount of the N / 2 sodium hydroxide solution required for this was defined as b (ml), and obtained by the following general formula (iv).
- s 1 is the mass of the polyvinyl acetal resin
- P 1 is the pure content (%)
- F 1 is the titer of the N / 2 sodium hydroxide solution.
- s m is the mass of the polyvinyl acetal resin
- P m is the pure content (%)
- F m is the titer of the N / 10 sodium hydroxide solution.
- Haze A film having a thickness of 100 ⁇ m was measured according to JIS-K7136.
- Example 1 A polyvinyl alcohol resin (500 g) having a polymerization degree of 1000 and a saponification degree of 99.5 mol% was dissolved by heating in pure water (5250 g), cooled to 12 ° C., and then 60% by mass nitric acid (365 g) and butyraldehyde (269 g) were added. It was added and held for 2 hours to precipitate the reaction product. Thereafter, the reaction system was maintained at 45 ° C.
- Table 1 shows the results of evaluating the YI, visible light transmittance, and haze of the polyvinyl acetal resin film by the methods (4) and (5) described above. Table 1 shows the results obtained by collecting films 1 hour and 6 hours after the start of pellet injection and counting the number of bumps by the method (6) described above. Compared with the film after 1 hour from the start, the film after 6 hours showed an increase in lumps, but the state of the film was good without change.
- Examples 2-4 instead of the polyvinyl alcohol resin used in Example 1, the polyvinyl alcohol resin described in Table 1 was used, and the reaction conditions were adjusted as appropriate to produce the polyvinyl acetal resin shown in Table 1. Then, pellets and films were formed and evaluated. The results are shown in Table 1.
- Examples 5 to 10 Instead of the polyvinyl acetal resin used in Example 1, molding and evaluation of pellets and films were performed in the same manner as in Example 1 except that the reaction conditions were appropriately adjusted to produce the polyvinyl acetal resin shown in Table 1. It was. The results are shown in Table 1.
- the pH of the slurry of the polyvinyl acetal resin was adjusted to 5 by reducing the amounts of the washing water and the aqueous sodium hydroxide solution.
- Example 7 the pH of the slurry of the polyvinyl acetal resin was adjusted to 9 by using an excess amount of an aqueous sodium hydroxide solution.
- Example 11 10 parts by mass of triethylene glycol di-2-ethylhexanoate was added as a plasticizer to 100 parts by mass of the polyvinyl acetal resin obtained in Example 1.
- About polyvinyl acetal resin obtained by adding a plasticizer, cylinder temperature and T die temperature from a T die having a width of 300 mm using a lab plast mill (25 mm ⁇ uniaxial, L / D 28) manufactured by Toyo Seiki Seisakusho Co., Ltd.
- a polyvinyl acetal resin film having a thickness of 100 ⁇ m was produced by extrusion molding at 220 ° C. and a screw rotation speed of 20 rpm. The produced film was evaluated in the same manner as in Example 1. The results are shown in Table 1.
- Comparative Examples 1 to 3 instead of the polyvinyl alcohol resin used in Example 1, the polyvinyl alcohol resin described in Table 1 was used, and the reaction conditions were adjusted as appropriate to produce the polyvinyl acetal resin shown in Table 1. Then, pellets and films were formed and evaluated. The results are shown in Table 1.
- a polyvinyl acetal resin was prepared using a polyvinyl alcohol resin having a polymerization degree of 360. As a result, since the strength of the film was small and fragile, the film could not be continuously taken up, and the film could not be produced continuously. Conversely, for Comparative Example 2, a polyvinyl acetal resin was prepared using a polyvinyl alcohol resin having a polymerization degree of 2400. As a result, the viscosity of the molten resin is large and the resin cannot be stably discharged from the T-die, so that the take-up cannot be continued, the torque gradually increases, and the film can be manufactured continuously. could not.
- the polyvinyl acetal resin was produced using the polyvinyl alcohol resin of saponification degree 98.5 mol%. As a result, compared with the film after 1 hour from the start, the number of bumps increased in the film after 6 hours, and the state of the film deteriorated.
- Comparative Examples 4 and 5 Instead of the polyvinyl acetal resin used in Example 1, molding and evaluation of pellets and films were performed in the same manner as in Example 1 except that the reaction conditions were appropriately adjusted to produce the polyvinyl acetal resin shown in Table 1. It was. The results are shown in Table 1.
- a polyvinyl acetal resin having an acetalization degree of 55 mol% was prepared. As a result, compared with the film 1 hour after the start, the number of bumps increased significantly in the film after 6 hours, and the film state deteriorated.
- a polyvinyl acetal resin having a sodium content of 80 ppm was prepared. As a result, compared with the film 1 hour after the start, the number of bumps increased significantly in the film after 6 hours, and the film state deteriorated.
- composition of the polyvinyl acetal resin is determined by measuring the 13 C-NMR spectrum, so that the mol% (k (BA) ) of vinyl alcohol units acetalized with an aldehyde having 4 or more carbon atoms with respect to all repeating units and Mol% of vinyl alcohol units acetalized with an aldehyde having 3 or less carbon atoms (k (AA) ) based on all repeating units, mol% of vinyl alcohol units not acetalized based on all repeating units (k (VA) ), Then, mol% (k (AV) ) of vinyl acetate units relative to all repeating units was calculated.
- Example 12 Polyvinyl alcohol resin (500 g) having a polymerization degree of 1000 and a saponification degree of 99.5 mol% was dissolved by heating in pure water (5250 g), cooled to 12 ° C., and then 60% by mass nitric acid (365 g) and butyraldehyde (216 g) and Acetaldehyde (27 g) was added and held for 2 hours to precipitate the reaction product. Thereafter, the reaction system was maintained at 45 ° C.
- Table 2 shows the results of evaluating the YI, visible light transmittance, and haze of the polyvinyl acetal resin film in the same manner as in Example 1.
- Table 2 also shows the results obtained by collecting the films 1 hour and 6 hours after the start of pellet injection and counting the number of spots in the same manner as in Example 1. Compared with the film after 1 hour from the start, the film after 6 hours showed an increase in lumps, but the state of the film was good without change.
- Example 13-15 In place of the polyvinyl acetal resin used in Example 12, the reaction conditions were appropriately adjusted to produce the polyvinyl acetal resin shown in Table 2, and the pellets and film were molded and evaluated in the same manner as in Example 12. It was. The results are shown in Table 2.
- Example 16 instead of the polyvinyl alcohol resin used in Example 12, the polyvinyl alcohol resin described in Table 2 was used, and the reaction conditions were adjusted as appropriate to produce the polyvinyl acetal resin shown in Table 2. Then, pellets and films were formed and evaluated. The results are shown in Table 2.
- Example 17 In place of the polyvinyl acetal resin used in Example 12, the reaction conditions were appropriately adjusted to produce the polyvinyl acetal resin shown in Table 2, and the pellets and film were molded and evaluated in the same manner as in Example 12. It was. The results are shown in Table 2.
- Comparative Example 6 instead of the polyvinyl alcohol resin used in Example 12, the polyvinyl alcohol resin described in Table 2 was used, and the reaction conditions were adjusted as appropriate to produce the polyvinyl acetal resin shown in Table 2. Then, pellets and films were formed and evaluated. The results are shown in Table 2.
- a polyvinyl acetal resin was prepared using a polyvinyl alcohol resin having a saponification degree of 98.5 mol%. As a result, compared with the film after 1 hour from the start, the number of bumps increased in the film after 6 hours, and the state of the film deteriorated.
- Comparative Example 7 In place of the polyvinyl acetal resin used in Example 12, the reaction conditions were appropriately adjusted to produce the polyvinyl acetal resin shown in Table 2, and the pellets and film were molded and evaluated in the same manner as in Example 12. It was. The results are shown in Table 2.
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Abstract
Description
(1)アセタール化度
JIS-K6728(1977年)に従って測定した。まず、ビニルアルコールユニットの質量割合(l0)および酢酸ビニルユニットの質量割合(m0)を後述の方法によって求め、さらに、ビニルアセタールユニットの質量割合(k0)をk0=1-l0-m0によって求めた。
ポリビニルアセタール樹脂約0.4gを共せん付き三角フラスコに正確に量りとり、ピリジン/無水酢酸(体積比92/8)の混合液10mlをピペットで加えて溶解し、冷却器をつけて温度50℃の水浴上で120分間加熱した。冷却後ジクロロエタン20mlを加えてよく振り混ぜ、さらに水50mlを加え、栓をして激しく振り混ぜた後、30分間放置した。生成した酢酸をN/2水酸化ナトリウム溶液でフェノールフタレインを指示薬として激しく振り混ぜながら微紅色をするまで滴定し、その滴定量をa(ml)とする。別にブランク試験を行い、これに要したN/2水酸化ナトリウム溶液の滴定量をb(ml)とし、次の一般式(iv)により求めた。
ポリビニルアセタール樹脂を、白金るつぼ及びホットプレートで炭化し、次いで電気炉で灰化し、残渣を酸に溶解して、原子吸光光度計を用いて測定した。
(4)YI、可視光線透過率
株式会社日立ハイテクノロジーズ社製の分光光度計U-4100を用い、厚さ100μmのフィルムについて測定した。可視光線透過率は、波長380~780nmにおける透過率を測定し、JIS-R3106に従って算出した。
厚さ100μmのフィルムについて、JIS-K7136に従って測定した。
偏光顕微鏡および蛍光顕微鏡を用い、厚さ100μm、サイズ10cm×10cmのフィルムについて、ポリビニルアセタール樹脂由来のブツの数をカウントした。
熱成形時の溶融樹脂の粘度、得られるフィルムの強度等の観点から、連続して、安定してフィルムを製造することができるか否かの評価を行なった。
重合度1000、けん化度99.5mol%のポリビニルアルコール樹脂(500g)を純水(5250g)に加熱溶解し、12℃に冷却した後、60質量%の硝酸(365g)とブチルアルデヒド(269g)を添加し、2時間保持して反応生成物を析出させた。その後、反応系を45℃で3時間保持して反応を完了させ、過剰の水でpH=6になるまで洗浄し、水酸化ナトリウム水溶液で中和した後、水/メタノール=80/20(質量比)の混合液でpH=7になるまで繰り返し洗浄し、水分率が1.0%になるまで乾燥することにより、ポリビニルアセタール樹脂を作製した。なお、水分率はカールフィッシャー法により測定した。得られたポリビニルアセタール樹脂のアセタール化度は76mol%、ポリビニルアセタール樹脂中のナトリウム含有量は5ppmであった。なお、アセタール化度は上で述べた(1)の方法で、ナトリウム含有量は上で述べた(3)の方法で求めた。
実施例1で用いたポリビニルアルコール樹脂の代わりに、表1に記載するポリビニルアルコール樹脂を用い、適宜反応条件を調整して表1に示すポリビニルアセタール樹脂を作製する以外は、実施例1と同様にして、ペレットおよびフィルムの成形、評価を行った。結果を表1に示す。
実施例1で用いたポリビニルアセタール樹脂の代わりに、適宜反応条件を調整して表1に示すポリビニルアセタール樹脂を作製する以外は、実施例1と同様にして、ペレットおよびフィルムの成形、評価を行った。結果を表1に示す。なお、実施例5および8~10についてはアセタール化後の反応系を過剰の水でpH=6になるまで洗浄し、次いで水酸化ナトリウム水溶液で中和し、水/メタノール=80/20(質量比)の混合液で所定のpHになるまで洗浄したが、実施例6では、洗浄水および水酸化ナトリウム水溶液の量を減らすことによってポリビニルアセタール樹脂のスラリーのpHを5に調整した。一方、実施例7では、水酸化ナトリウム水溶液を過剰量用いることによりポリビニルアセタール樹脂のスラリーのpHを9に調整した。
実施例1で得られたポリビニルアセタール樹脂100質量部に対して、可塑剤として、トリエチレングリコールジ2-エチルヘキサノエートを10質量部添加した。可塑剤を添加して得られたポリビニルアセタール樹脂について、株式会社東洋精機製作所製ラボプラストミル(25mmφ単軸、L/D=28)を用い、幅300mmのTダイより、シリンダー温度およびTダイ温度220℃、スクリュー回転数20rpmで押出成形することにより、厚さ100μmのポリビニルアセタール樹脂フィルムを作製した。作製したフィルムについて実施例1と同様にして評価を行なった。結果を表1に示す。
実施例1で用いたポリビニルアルコール樹脂の代わりに、表1に記載するポリビニルアルコール樹脂を用い、適宜反応条件を調整して表1に示すポリビニルアセタール樹脂を作製する以外は、実施例1と同様にして、ペレットおよびフィルムの成形、評価を行った。結果を表1に示す。
実施例1で用いたポリビニルアセタール樹脂の代わりに、適宜反応条件を調整して表1に示すポリビニルアセタール樹脂を作製する以外は、実施例1と同様にして、ペレットおよびフィルムの成形、評価を行った。結果を表1に示す。
(8)組成
ポリビニルアセタール樹脂の組成は、13C-NMRスペクトルを測定することで、炭素数4以上のアルデヒドでアセタール化されたビニルアルコール単位の全繰返し単位に対するモル%(k(BA))および炭素数3以下のアルデヒドでアセタール化されたビニルアルコール単位の全繰返し単位に対するモル%(k(AA))、アセタール化されていないビニルアルコール単位の全繰返し単位に対するモル%(k(VA))、そして酢酸ビニル単位の全繰返し単位に対するモル%(k(AV))を算出した。
株式会社レオロジ製、DVE RHEOSPECTOLER DVE-V4を用いて、長さ20mm×幅3mm×厚さ200μmの試験片を、チャック間距離10mm、正弦波振動10Hzおよび昇温速度3℃/min.の条件で測定し、損失正接(tanδ)の主分散ピーク温度(Tα)を求めた。
重合度1000、けん化度99.5mol%のポリビニルアルコール樹脂(500g)を純水(5250g)に加熱溶解し、12℃に冷却した後、60質量%の硝酸(365g)とブチルアルデヒド(216g)およびアセトアルデヒド(27g)を添加し、2時間保持して反応生成物を析出させた。その後、反応系を45℃で3時間保持して反応を完了させ、過剰の水でpH=6になるまで洗浄し、次いで水酸化ナトリウム水溶液で中和した後、水/メタノール=80/20(質量比)の混合液でpH=7になるまで繰り返し洗浄し、水分率が1.0%になるまで乾燥することにより、ポリビニルアセタール樹脂を作製した。なお、水分率はカールフィッシャー法により測定した。得られたポリビニルアセタール樹脂のアセタール化度は78mol%、k(BA)/k(AA)=84/16、ポリビニルアセタール樹脂中のナトリウム含有量は5ppm、主分散ピーク温度Tαは90℃であった。なお、ナトリウム含有量については実施例1と同様の方法で、アセタール化度及び主分散ピーク温度Tαについては、それぞれ上で述べた(8)、(9)の方法で求めた。
実施例12で用いたポリビニルアセタール樹脂の代わりに、適宜反応条件を調整して表2に示すポリビニルアセタール樹脂を作製する以外は、実施例12と同様にして、ペレットおよびフィルムの成形、評価を行った。結果を表2に示す。
実施例12で用いたポリビニルアルコール樹脂の代わりに、表2に記載するポリビニルアルコール樹脂を用い、適宜反応条件を調整して表2に示すポリビニルアセタール樹脂を作製する以外は、実施例12と同様にして、ペレットおよびフィルムの成形、評価を行った。結果を表2に示す。
実施例12で用いたポリビニルアセタール樹脂の代わりに、適宜反応条件を調整して表2に示すポリビニルアセタール樹脂を作製する以外は、実施例12と同様にして、ペレットおよびフィルムの成形、評価を行った。結果を表2に示す。
実施例12で用いたポリビニルアルコール樹脂の代わりに、表2に記載するポリビニルアルコール樹脂を用い、適宜反応条件を調整して表2に示すポリビニルアセタール樹脂を作製する以外は、実施例12と同様にして、ペレットおよびフィルムの成形、評価を行った。結果を表2に示す。
実施例12で用いたポリビニルアセタール樹脂の代わりに、適宜反応条件を調整して表2に示すポリビニルアセタール樹脂を作製する以外は、実施例12と同様にして、ペレットおよびフィルムの成形、評価を行った。結果を表2に示す。
Claims (14)
- 粘度平均重合度が500~2000で、けん化度が99.5mol%以上であるポリビニルアルコール樹脂をアルデヒドでアセタール化して得られ、アルデヒドでアセタール化されたビニルアルコール単位の合計が全繰り返し単位に対して65~88mol%で、アルカリ金属又はアルカリ土類金属の含有量が0.1~50ppmである熱成形用ポリビニルアセタール樹脂。
- 炭素数4以上のアルデヒドでアセタール化されたビニルアルコール単位/炭素数3以下のアルデヒドでアセタール化されたビニルアルコール単位のモル比が90/10~0/100である請求項1に記載の熱成形用ポリビニルアセタール樹脂。
- ポリビニルアセタール樹脂が、ポリビニルブチラールである請求項1に記載の熱成形用ポリビニルアセタール樹脂。
- アルデヒドでアセタール化されたビニルアルコール単位の合計が全繰り返し単位に対して70~88mol%である請求項1~3のいずれかに記載の熱成形用ポリビニルアセタール樹脂。
- 可塑剤の含有量がポリビニルアセタール樹脂100質量部に対して20質量部以下である請求項1~4のいずれかに記載の熱成形用ポリビニルアセタール樹脂。
- ポリビニルアセタール樹脂に可塑剤が含まれないことを特徴とする請求項5に記載の熱成形用ポリビニルアセタール樹脂。
- ポリビニルアセタール樹脂が、ポリビニルアルコール樹脂をアセタール化して得られたスラリーのpHを6~8に調整した後に乾燥処理を施して得られたものである請求項1~6のいずれかに記載の熱成形用ポリビニルアセタール樹脂。
- 水分率が0.005~2%に調整された請求項1~7のいずれかに記載の熱成形用ポリビニルアセタール樹脂。
- 請求項1~8のいずれかに記載の熱成形用ポリビニルアセタール樹脂からなる成形体。
- 請求項1~8のいずれかに記載の熱成形用ポリビニルアセタール樹脂からなるフィルム。
- 粘度平均重合度が500~2000で、けん化度が99.5mol%以上であるポリビニルアルコール樹脂をアルデヒドでアセタール化して得られ、アルデヒドでアセタール化されたビニルアルコール単位の合計が全繰り返し単位に対して65~88mol%で、アルカリ金属又はアルカリ土類金属の含有量が0.1~50ppmである熱成形用ポリビニルアセタール樹脂を用いて熱成形を行なう成形体の製造方法。
- 可塑剤の含有量をポリビニルアセタール樹脂100質量部に対して20質量部以下に調整して熱成形を行なう請求項11に記載の成形体の製造方法。
- 粘度平均重合度が500~2000で、けん化度が99.5mol%以上であるポリビニルアルコール樹脂をアルデヒドでアセタール化して得られ、アルデヒドでアセタール化されたビニルアルコール単位の合計が全繰り返し単位に対して65~88mol%で、アルカリ金属又はアルカリ土類金属の含有量が0.1~50ppmである熱成形用ポリビニルアセタール樹脂を用いて熱成形を行なうフィルムの製造方法。
- 可塑剤の含有量をポリビニルアセタール樹脂100質量部に対して10質量部以下に調整して熱成形を行なう請求項13に記載のフィルムの製造方法。
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JP2011545522A JP5940301B2 (ja) | 2010-09-28 | 2011-09-26 | 熱成形用ポリビニルアセタール樹脂 |
CN201180047055.2A CN103140509B (zh) | 2010-09-28 | 2011-09-26 | 热成形用聚乙烯醇缩醛树脂 |
KR1020137010861A KR101894974B1 (ko) | 2010-09-28 | 2011-09-26 | 열성형용 폴리비닐 아세탈 수지 |
EP11829009.7A EP2623525B1 (en) | 2010-09-28 | 2011-09-26 | Polyvinyl acetal resin for thermoforming |
US13/876,401 US20130267647A1 (en) | 2010-09-28 | 2011-09-26 | Polyvinyl acetal resin for thermoforming |
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EP2623525A1 (en) | 2013-08-07 |
CN103140509A (zh) | 2013-06-05 |
EP2623525B1 (en) | 2016-12-07 |
CN103140509B (zh) | 2015-06-10 |
JPWO2012043455A1 (ja) | 2014-02-06 |
TW201217412A (en) | 2012-05-01 |
TWI519558B (zh) | 2016-02-01 |
EP2623525A4 (en) | 2014-07-23 |
KR20130124319A (ko) | 2013-11-13 |
US20130267647A1 (en) | 2013-10-10 |
JP5940301B2 (ja) | 2016-06-29 |
KR101894974B1 (ko) | 2018-09-04 |
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