WO2014147842A1 - ポリビニルアセタール組成物 - Google Patents
ポリビニルアセタール組成物 Download PDFInfo
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- WO2014147842A1 WO2014147842A1 PCT/JP2013/058440 JP2013058440W WO2014147842A1 WO 2014147842 A1 WO2014147842 A1 WO 2014147842A1 JP 2013058440 W JP2013058440 W JP 2013058440W WO 2014147842 A1 WO2014147842 A1 WO 2014147842A1
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10605—Type of plasticiser
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use 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; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2337/00—Characterised by the use 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 a heterocyclic ring containing oxygen; Derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present invention relates to a polyvinyl acetal composition, a sheet thereof, and an application thereof.
- Polyvinyl acetal typified by polyvinyl butyral is excellent in adhesiveness and compatibility with various organic and inorganic substrates and solubility in organic solvents.
- Various adhesives, binders for ceramics, various inks, paints, etc. It is widely used as an intermediate film for safety glass.
- interlayer films for laminated glass In recent years, various high performance products have been developed for use in interlayer films for laminated glass. For example, for the purpose of imparting high sound insulation performance to an interlayer film for laminated glass, an interlayer film for laminated sound insulation laminated glass in which a plurality of polyvinyl acetal layers having different compositions such as different content ratios of polyvinyl acetal and plasticizer are laminated is disclosed. (For example, see Patent Documents 1 and 2).
- the interlayer film for laminated glass in general, in order to make the amount of plasticizer contained in each layer different, those having different average residual hydroxyl groups are used as the polyvinyl acetal used in each layer.
- the interlayer film for laminated glass is generally manufactured using an extruder from the viewpoint of production cost.
- the interlayer film for laminated sound insulation laminated glass is produced by a co-extrusion method.
- a certain amount of trim, composition and thickness are not uniform. Off-spec products that are difficult to use as products can be obtained.
- Trim and off-spec products for interlayer films for single-layer laminated glass can generally be recycled by putting them into the extruder again, melt-kneading and extrusion molding.
- a polyvinyl acetal composition having a different composition is mixed and used as a trim or off-spec product, the resulting interlayer film for laminated glass may become opaque.
- the interlayer film for laminated sound insulation laminated glass in the polyvinyl acetal composition constituting each layer, since polyvinyl acetals having different average residual hydroxyl groups are used, it is difficult to make these polyvinyl acetals compatible with each other,
- the interlayer film for laminated glass obtained by recycling the trim or off-spec product generated in the process for producing the interlayer film for laminated glass has a problem of poor transparency.
- polyvinyl alcohol which is a raw material for polyvinyl acetal resin
- an aldehyde such as butyraldehyde
- an acid catalyst such as hydrochloric acid and nitric acid
- the degree of acetalization reaches a certain level
- the partially acetalized polyvinyl alcohol that cannot be dissolved in water precipitates to form particles, and then the acetalization reaction proceeds in a heterogeneous system in which the particles are dispersed in water.
- a polyvinyl acetal is obtained through neutralization, washing and drying of the acid catalyst as appropriate.
- the batch type precipitation method is suitable because the resin is obtained in the form of particles, and the obtained resin is excellent in purification by washing with water and handling of the resin after drying.
- the average degree of acetalization of the resulting polyvinyl acetal varies from batch to batch (ie, the average amount of residual hydroxyl groups (mol%) varies from batch to batch) even when the production conditions are uniform because of the batch reaction. There is.
- Plasticizers commonly used for polyvinyl acetals such as triethylene glycol di-2-ethylhexanoate (3GO), which are two or more types of polyvinyl acetals with different average acetalization degrees, which are derived from such batch-to-batch variations When used in a mixture, the transparency of the resulting composition may be reduced.
- 3GO triethylene glycol di-2-ethylhexanoate
- the acetalization reaction after the precipitation of particles proceeds in a heterogeneous system, depending on the reaction formulation, even in the same batch, it has a relatively wide acetalization degree distribution (that is, residual hydroxyl amount (mol% )) (Polyvinyl acetal may be obtained).
- the acetalization reaction is performed under reaction conditions that increase the particle size of the polyvinyl acetal, the aldehyde concentration and acid catalyst concentration are different between the inside and outside of the particles in the reaction, so that even in the same batch, it is relatively wide. Polyvinyl acetal having an acetalization degree distribution tends to be obtained.
- a laminated glass having an intermediate film made of a sheet composed of a mixture of polyvinyl acetal having a relatively wide acetalization degree distribution in the same batch and a plasticizer generally used for polyvinyl acetal such as 3GO In some cases, it may appear cloudy under light irradiation and is exposed to strong light, for example, a windshield of an automobile (when heading from an oncoming vehicle when driving at night).
- This invention solves the said subject, and it aims at providing the composition which can shape
- the object consists of 0.5 to 100% by mass of a plasticizer having a polar group and 0 to 99.5% by mass of a plasticizer having no polar group, based on 100 parts by mass of polyvinyl acetal.
- a plasticizer having a polar group a plasticizer having no polar group
- the polyvinyl acetal is surfaced with an octadecylsilyl group having an inner diameter of 4 mm and a length of 1 cm.
- the difference in elution time between the first peak and the second peak is preferably 2 to 10 minutes.
- the first peak appears at an elution time of less than 22 minutes and the second peak appears at an elution time of 22 minutes or more.
- the ratio of the square root of the area of the mountain having the first peak to the square root of the area of the mountain having the second peak is preferably 20:80 to 98: 2.
- the peak having the fastest peak elution time is the first peak and the other peak is the peak having the largest area and the second largest area.
- the peak constituting the second peak is the sum of the square root of the area of the mountain having the first peak and the square root of the area of the mountain having the second peak
- each peak derived from polyvinyl acetal It is preferably 50 to 100% with respect to the sum of the square roots of the areas of the peaks.
- the dropwise addition amount of hexane until the solution becomes cloudy is preferably 140 mL or more.
- the amount of deionized water added until the solution becomes cloudy is preferably 10 mL or more.
- the plasticizer having a polar group is preferably a compound having a hydroxyl group.
- the plasticizer having a polar group is preferably a compound having a molecular weight of 200 to 2,000.
- the number average molecular weight based on the hydroxyl value of the compound having a hydroxyl group is preferably 200 to 2,000.
- the compound having a hydroxyl group is an ester compound.
- ester compound is a polyester compound.
- the compound having a hydroxyl group is preferably an ether compound.
- the ether compound is preferably a polyether compound.
- 0.5 to 5% by mass of the plasticizer is a compound having a hydroxyl group, and 70 to 99.5% by mass of the plasticizer is a diester of a monovalent carboxylic acid with a compound selected from triethylene glycol and tetraethylene glycol. It is preferable that the compound has no polar group.
- the polyvinyl acetal is preferably a mixture of polyvinyl acetal (A) and polyvinyl acetal (B) having different average residual hydroxyl groups.
- X 15.0 to 27.0
- Y 33.0 to 50.0
- the polyvinyl acetal preferably satisfies the definition 1 and the definition 2.
- Rule 1 When 1 g of polyvinyl acetal is dissolved in 100 g of methanol, the undissolved content is 2.5 to 90% by mass.
- Rule 2 When 1 g of polyvinyl acetal is dissolved in 100 g of chloroform, the undissolved content is 5 to 70% by mass.
- the mixing ratio of polyvinyl acetal (A) and polyvinyl acetal (B) is preferably 20:80 to 98: 2 in terms of mass ratio.
- the average residual hydroxyl group content of polyvinyl acetal is preferably 20 to 33 mol%.
- the present invention relates to a sheet comprising the composition.
- the present invention relates to a laminated glass including the sheet.
- the present invention relates to a laminated glass having a haze of 0.01 to 2%.
- composition of the present invention is derived from polyvinyl acetal when HPLC analysis is performed using a column (ODS column) in which spherical silica gel surface-modified with octadecylsilyl groups having an inner diameter of 4 mm and a length of 1 cm is packed with a stationary phase (ODS column).
- ODS column spherical silica gel surface-modified with octadecylsilyl groups having an inner diameter of 4 mm and a length of 1 cm is packed with a stationary phase (ODS column).
- Polyvinyl acetal in which at least two peaks appear is included as an essential component.
- the ODS column is a column using porous spherical silica gel whose surface is modified with octadecyl group as a filler.
- the retention time depends on the polarity of the analyte compound ( The compound can be separated by elution time), and the shorter the elution time, the higher the polarity of the analyte compound. That is, when analyzed by HPLC using an ODS column having an inner diameter of 4 mm and a length of 1 cm, the polyvinyl acetal in which the first peak and the second peak appear as peaks derived from polyvinyl acetal corresponds to each peak. This indicates that at least two kinds of polyvinyl acetals having different polarities are contained.
- Polyvinyl acetals having different polarities for example, polyvinyl acetals containing polyvinyl acetal molecules having different amounts of residual hydroxyl groups were mixed with compounds commonly used as plasticizers for polyvinyl acetals such as triethylene glycol di-2-ethylhexanoate. In some cases, a composition having poor transparency may be obtained.
- the composition of the present invention contains a plasticizer containing 0.5 to 100% by mass of a plasticizer having a polar group as an essential component.
- the plasticizer having a polar group can mutually dissolve polyvinyl acetal molecules having different residual hydroxyl amounts, or can be dispersed microscopically to a level that does not affect the transparency, a transparent composition can be obtained as a result. Presumed to be possible. Therefore, the composition of the present invention particularly includes polyvinyl acetals having different polarities such as trim generated when the laminated interlayer film is produced by extrusion molding, or polyvinyl acetals having batch-to-batch variation or batch-to-batch variation. Even when it is used as a raw material, it is a plasticized polyvinyl acetal composition excellent in transparency, and a sheet excellent in transparency can be formed from the composition.
- the polyvinyl acetal used in the present invention will be described.
- the polyvinyl acetal used in the present invention is analyzed by HPLC using an ODS column having an inner diameter of 4 mm and a length of 1 cm
- the polyvinyl acetal is prepared based on the detection amount obtained by the detector. If the 1st peak and 2nd peak originating in appear, it will not specifically limit.
- An example of an HPLC analysis chart is shown in FIG.
- the first peak and the second peak are peaks having the largest area and the second largest area among peaks having peaks derived from polyvinyl acetal, which are detected in the HPLC analysis chart in the present invention.
- the peak constituting the peak of the peak peak elution time is the first peak, and the peak constituting the other peak is the second peak.
- the detector for example, an evaporative light scattering detector “ELSD-LTII” manufactured by Shimadzu Corporation or an apparatus equivalent thereto can be used.
- an HPLC analysis chart (chromatogram) of the polyvinyl acetal used in the present invention will be described with reference to FIG.
- the detection amount is plotted on the vertical axis and the elution time is plotted on the horizontal axis, and the first peak 12 and the second peak 22 derived from polyvinyl acetal appear.
- the difference in elution time between the peak 12 and the peak 22 is preferably 2 to 10 minutes, more preferably 2 to 8 minutes, and further preferably 2 to 6 minutes. When the difference in elution time is greater than 10 minutes, the transparency of the resulting composition may be lowered.
- the peak in this specification means the maximum point of the detection amount in each mountain.
- the polyvinyl acetal used in the present invention has an elution time of less than 22 minutes, preferably less than 21.8 minutes, more preferably less than 21.6 minutes, and the first peak 12 appears, and the elution time is 22 minutes or more.
- the second peak 22 appears at 22.2 minutes or more, more preferably at 22.4 minutes or more.
- An elution time t less than 12 22 minutes of the first peak 12, and the elution time t 22 of the second peak 22 is at 22 minutes or more, excellent sheet adhesion to mechanical strength and glass obtained Tend to be.
- a peak having a peak with an elution time of less than 22 minutes usually indicates a polyvinyl acetal having a residual hydroxyl group amount of approximately 30 mol% or more, and a peak having a peak with an elution time of 22 minutes or more usually has a residual hydroxyl group content of approximately 20 mol. % Of polyvinyl acetal is shown.
- the ratio of the square root of the mountain area having the first peak 12 to the square root of the mountain area having the second peak 22 is preferably 20:80 to 98: 2. : 70 to 97: 3 is more preferable, 50:50 to 95: 5 is more preferable, and 50:50 to 90:10 is particularly preferable. It is preferable from the viewpoint of obtaining a composition having excellent transparency that the ratio of the square root of the area of the peaks having the first peak 12 and the second peak 22 satisfies this range.
- the area of the peak having a peak is the peak immediately after the elution time corresponding to the peak from the elution time at the intersection of the peak and the baseline immediately before the elution time corresponding to each peak in the HPLC analysis chart.
- the area of the peak having the first peak 12 is the peak 12 immediately after the first peak 12 from the elution time t 11 at the intersection 11 of the peak having the peak immediately before the first peak 12 and the baseline.
- a detectable amount of up to elution time t 13 at the intersection 13 between the peaks and the baseline with means integrated value. That is, it means the area of the shaded portion in FIG.
- the area of the peak having the second peak 22 is determined from the elution time t 21 at the intersection 21 of the peak having the peak 22 immediately before the second peak 22 and the baseline, to the second peak 22. It refers to integrated value of the detected amount of up to elution time t 23 at the intersection 23 between the peaks and the baseline with a peak just after.
- the actual ratio of each polyvinyl acetal content is roughly the same as the ratio of the square root (peak area square root) of the area of each peak, rather than the ratio of the area of the peak having each peak.
- the mountains having peaks and peak 22 with peak 12 overlap as shown in FIG. 2, to calculate the area of the same mountain elution time at the intersection of the mountain as a t 13 and t 21, respectively.
- the sum of the square root of the peak area having the first peak 12 and the square root of the peak area having the second peak 22 is the sum of all the peaks having peaks derived from the polyvinyl acetal. It is preferably 50 to 100% with respect to the sum of the square roots of the areas.
- the resulting composition is such that the sum of the square roots of the areas of the peaks having the first peak 12 and the second peak 22 satisfies this range for the sum of the square roots of all areas of the peaks having each peak. From the viewpoint of transparency and mechanical strength.
- the polyvinyl acetal of the present invention is a solution in which 1 g of the polyvinyl acetal is dissolved in 100 g of ethanol, and titrated with hexane at 23 ° C.
- the dropwise addition amount of hexane in which the solution becomes cloudy is preferably 140 mL or more, more preferably 150 mL or more, It is more preferable to use polyvinyl acetal that is particularly preferably 160 mL or more.
- Polyvinyl acetal having a hexane dropping amount of less than 140 mL contains a polyvinyl acetal molecule having a low residual hydroxyl amount and a low affinity with hexane (low polarity solvent). Since such a polyvinyl acetal molecule has low compatibility with the plasticizer used in the present invention, the transparency of a sheet formed from the resulting composition may be inferior.
- the polyvinyl acetal of this invention titrates the solution which melt
- the dripping amount that a solution becomes cloudy is 10 mL or more, More preferably, 20 mL or more More preferably, it is more preferable to use polyvinyl acetal that is 23 mL or more, particularly preferably 25 mL or more.
- Polyvinyl acetal with a drop amount of deionized water of less than 10 mL includes a polyvinyl acetal molecule having a low affinity for water (high polarity solvent) and a small amount of residual hydroxyl group. Since such a polyvinyl acetal molecule has low compatibility with the plasticizer used in the present invention, the transparency of a sheet formed from the resulting composition may be inferior.
- the polyvinyl acetal used in the present invention preferably satisfies the following definition 1 and / or definition 2.
- Rule 1 When 1 g of polyvinyl acetal is dissolved in 100 g of methanol, the undissolved content is 2.5 to 90% by mass.
- Rule 2 When 1 g of polyvinyl acetal is dissolved in 100 g of chloroform, the undissolved content is 5 to 70% by mass.
- the undissolved content is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, and still more preferably 70 to 90% by mass.
- the polyvinyl acetal having an undissolved content of less than 2.5% by mass or a polyvinyl acetal of greater than 90% by mass is one of the objects of the present invention.
- the problem to be solved by the present invention that the sheet is inferior in transparency and looks cloudy when used in laminated glass is hardly generated in the first place.
- usable polyvinyl acetals are limited, and the recycling efficiency may be lowered.
- each particle or lump of polyvinyl acetal used in the present invention is larger than 3 mm
- the particle or lump is treated with a method that does not change its composition, such as cutting the particles or lump with scissors, and the major axis is 3 mm. The following may be used.
- the filtration of the solution (including the undissolved portion) obtained when 1 g of polyvinyl acetal is dissolved in 100 g of methanol at 25 ° C. is performed by the following method. Attach a Buchner funnel to an appropriately sized suction bottle, set the filter paper, and wet the filter paper with methanol in advance. The solution (including the undissolved content) is poured onto a filter paper, and suction filtered using aspirator or the like under reduced pressure (differential pressure 0.010 ⁇ 0.002 MPa). When 95% or more of the poured solution is filtered, 100 mL of methanol is further poured onto the filter paper, and the undissolved portion remaining on the filter paper is washed.
- the polyvinyl acetal satisfying the stipulation 1 includes specific amounts of polyvinyl acetal molecules that are difficult to dissolve in methanol due to a small amount of residual hydroxyl groups and polyvinyl acetal molecules that dissolve in methanol.
- the undissolved content is 5 to 70%.
- the undissolved content of Regulation 2 is preferably 7 to 70% by mass, more preferably 10 to 70% by mass, and still more preferably 20 to 70% by mass.
- the polyvinyl acetal having an undissolved content of less than 5% by mass and the polyvinyl acetal of greater than 70% by mass are transparent for the trim and off-spec products of multilayer interlayer films having different residual hydroxyl content, which is one of the objects of the present invention.
- the problem solved by the present invention that the sheet is inferior in transparency and looks cloudy when used for laminated glass is hardly generated in the first place.
- usable polyvinyl acetals are limited, and the recycling efficiency may be lowered.
- the polyvinyl acetal satisfying the stipulation 2 includes specific amounts of polyvinyl acetal molecules that are difficult to dissolve in chloroform due to a large amount of residual hydroxyl groups and polyvinyl acetal molecules that dissolve in chloroform.
- the polyvinyl acetal used in the present invention is one in which the first peak and the second peak derived from the polyvinyl acetal appear in the HPLC analysis, and can be prepared by various methods. For example, a mixture of polyvinyl acetal (A) and polyvinyl acetal (B) each having a different average residual hydroxyl group content, and a solution obtained by dissolving 1 g of polyvinyl acetal in 100 g of ethanol was titrated with hexane and deionized water.
- the solution becomes cloudy with a predetermined drop amount or more, or further satisfies the above-mentioned regulations 1 and / or 2, or is a polyvinyl acetal having a large batch-to-batch variation, and 1 g of polyvinyl acetal is dissolved in 100 g of ethanol.
- a solution in which the solution becomes cloudy with a predetermined amount or more, or a solution satisfying the above definition 1 and / or 2 can be used.
- the polyvinyl acetal of the present invention when using a mixture of polyvinyl acetal (A) and polyvinyl acetal (B), each having a different average residual hydroxyl group amount, the polyvinyl acetal to be used is not particularly different from the gist of the present invention. It is not limited.
- the polyvinyl acetal obtained by mixing the polyvinyl acetal (A) and the polyvinyl acetal (B) with an ODS column having an inner diameter of 4 mm and a length of 1 cm was analyzed by HPLC using the ODS column having the inner diameter of 4 mm, the first derived from the polyvinyl acetal. It is preferable that the peak and the second peak appear.
- the first peak and the second peak derived from polyvinyl acetal appear.
- X 15.0 to 27.0, preferably 16.0 to 27.0, more preferably 17.0 to 27.0
- Y 33.0 to 50.0, preferably Is 33.0 to 45.0, more preferably 33.0 to 41.0, and an ODS in which polyvinyl acetal obtained by mixing the polyvinyl acetal (A) and the polyvinyl acetal (B) has an inner diameter of 4 mm and a length of 1 cm.
- the polyvinyl acetal used in the present invention preferably has an average residual hydroxyl group content of 20 to 33 mol%, more preferably 23 to 32.5 mol%, still more preferably 27 to 32.0 mol%. is there.
- the average residual hydroxyl group amount of the polyvinyl acetal after mixing is the said range.
- the polyvinyl acetal, polyvinyl acetal (A), and polyvinyl acetal (B) used in the present invention are usually produced using polyvinyl alcohol as a raw material.
- the polyvinyl alcohol can be obtained by a conventionally known method, that is, by polymerizing a vinyl ester compound and saponifying the obtained polymer.
- a method for polymerizing the vinyl ester compound conventionally known methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method can be applied.
- As the polymerization initiator an azo initiator, a peroxide initiator, a redox initiator, or the like can be appropriately selected depending on the polymerization method.
- a conventionally known alcoholysis or hydrolysis using an alkali catalyst or an acid catalyst can be applied.
- a saponification reaction using methanol as a solvent and a caustic soda (NaOH) catalyst is simple and most preferable.
- vinyl ester compound examples include conventionally known carboxylic acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, and vinyl benzoate, with vinyl acetate being particularly preferred.
- modified polyvinyl alcohol obtained by copolymerizing the vinyl ester compound and other conventionally known monomers can be used as long as it does not contradict the gist of the present invention.
- This conventionally known monomer is usually used in a proportion of less than 10 mol% with respect to the vinyl ester monomer.
- the viscosity average polymerization degree of polyvinyl alcohol used as a raw material for the polyvinyl acetal used in the present invention is not particularly limited and is appropriately selected according to the use, but is preferably 150 to 3,000, preferably 200 to 2,500. More preferred are those of 1,000 to 2,000.
- the viscosity average polymerization degree of polyvinyl alcohol is less than 150, the strength tends to be insufficient when the resulting composition is molded, and when it is greater than 3,000, the handleability of the resulting composition tends to be poor. It is in.
- the polyvinyl acetal used in the present invention can be synthesized, for example, under the following reaction conditions, but is not limited thereto.
- an aqueous polyvinyl alcohol solution having a concentration of 3 to 40% by mass is maintained in a temperature range of 80 to 100 ° C., and then the temperature is gradually cooled over 10 to 60 minutes.
- an aldehyde and an acid catalyst are added, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant (this temperature is defined as a reaction temperature during precipitation).
- this temperature is defined as a reaction temperature during precipitation.
- polyvinyl acetal having a certain degree of acetalization is deposited.
- the temperature of the reaction solution is raised to a temperature of 30 to 80 ° C. over 30 to 300 minutes, and the temperature is maintained for 10 to 500 minutes (this temperature is set as a reaction temperature for driving in).
- a neutralizing agent such as alkali is added to the reaction solution as necessary to neutralize the acid catalyst, and the resin is washed with water and dried to obtain the polyvinyl acetal used in the present invention.
- the acid catalyst used in the acetalization reaction is not particularly limited, and any of organic acids and inorganic acids can be used. Examples thereof include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, and hydrochloric acid. Of these, hydrochloric acid, sulfuric acid, and nitric acid are preferably used.
- the aldehyde used in the acetalization reaction of the present invention is not particularly limited. From the viewpoint of easy acetalization and easy removal of aldehyde remaining after the reaction, acetalization with a conventionally known aldehyde having 1 to 8 carbon atoms is possible. Among them, aldehydes having 4 to 6 carbon atoms are preferable, and n-butyraldehyde is particularly preferable. In the present invention, polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.
- the average degree of acetalization of the polyvinyl acetal used in the present invention is not particularly limited, but is preferably 66 to 78 mol%, more preferably 66.5 to 75 mol%, and more preferably 67 to 72 from the viewpoint of excellent transparency and mechanical strength. More preferred is mol%.
- the average residual amount of vinyl carboxylate group is 0.1 to 20 mol% from the viewpoint of excellent balance between transparency and mechanical strength and excellent durability when the composition of the present invention is used for a long period of time. Is preferably 0.3 to 13 mol%, more preferably 0.5 to 10 mol%.
- the plasticizer used in the present invention is mixed by mixing 30 to 70 parts by weight, preferably 33 to 68 parts by weight, more preferably 50 to 66 parts by weight with respect to 100 parts by weight of the polyvinyl acetal used in the present invention. And a plasticized composition is obtained.
- the plasticizer having a polar group is 0.5 to 100% by mass, preferably 2 to 100% by mass, more preferably 5 to 100% by mass.
- plasticizers having a polar group in the plasticizer are less than 0.5% by mass, the transparency of the sheet obtained from the composition tends to be insufficient.
- the plasticizer used in the present invention contains 100% by mass of a plasticizer having a polar group and 0% by mass of a plasticizer not having a polar group, the plasticizer used in the present invention has a polar group. It means that it contains only plasticizer.
- the plasticizer having a polar group is obtained when the composition of the present invention is treated at high humidity, for example, at 23 ° C. and 90% RH, Alternatively, there is an effect of preventing bleeding of a plasticizer not containing a polar group.
- the compound used as a plasticizer having a polar group is not particularly limited, has compatibility with the polyvinyl acetal used in the present invention, and has a plasticizing effect on the polyvinyl acetal, and is further defined by the analytical value of the HPLC. It will not specifically limit if polyvinyl acetal is mutually compatible, You may use individually and may use 2 or more types together.
- the polar group include a hydroxyl group, a polyethylene oxide group having a polymerization degree of 10 or more, a polypropylene oxide group having a polymerization degree of 10 or more, a carboxyl group, and an amino group.
- the plasticizer having a polar group is particularly preferably a compound having a hydroxyl group.
- the molecular weight is not particularly limited, but a compound having a molecular weight of 200 to 2000, preferably a molecular weight of 220 to 1000, more preferably a molecular weight of 250 to 700 is transparent in the present invention. From the viewpoint of obtaining a sheet having excellent properties.
- the number average molecular weight based on the hydroxyl value of the compound having a hydroxyl group is not particularly limited, but is preferably 200 to 2000, more preferably 220 to 1700, and further preferably 240 to 1500.
- the number average molecular weight based on the hydroxyl value is smaller than 200, the boiling point of the compound may not be sufficiently high, and high volatility may be a problem.
- the number average molecular weight based on the hydroxyl value is larger than 2000, the compatibility between the compound and polyvinyl acetal may be insufficient.
- This is a value obtained by (number of hydroxyl groups per molecule) / ((hydroxyl value of a compound having a hydroxyl group) / 56).
- the number of hydroxyl groups per molecule having a hydroxyl group in the case of using a mixture of two or more compounds having a hydroxyl group refers to the average value per molecule of the compound having a hydroxyl group contained in the mixture.
- the compound having a hydroxyl group is not particularly limited as long as it has 1 or more, preferably 1 to 4, more preferably 1 to 3 hydroxyl groups, and may be used alone or in combination of two or more. May be.
- it is an ether compound which has.
- the ester compound having a hydroxyl group is a compound having at least one ester bond and having a hydroxyl group
- the ether compound having a hydroxyl group is a compound having at least one ether bond and having a hydroxyl group.
- ester compounds having a hydroxyl group include methyl ricinoleate, butyl ricinoleate, 2-ethylhexyl ricinoleate, ricinoleic acid (2-hydroxyethyl), glycerin monoricinoleate, glycerin diricinoleate, glycerin triricinol.
- Acid ester glycerin diricinoleate monooleate, oleic acid (2-hydroxyethyl), 2-ethylhexanoic acid (2-hydroxyethyl), ricinoleic acid ⁇ 2- [2- (2-hydroxyethoxy) ethoxy] Ethyl ⁇ 2-ethylhexanoic acid ⁇ 2- [2- (2-hydroxyethoxy) ethoxy] ethyl ⁇ , methyl ricinoleate, ethyl ricinoleate, butyl ricinoleate, octyl ricinoleate, octyl 6-hydroxyhexanoate 12-hydroxystearic acid methyl other such castor, and polyester compounds having a hydroxyl group.
- a polyester compound having a hydroxyl group is used because it is compatible with the polyvinyl acetal used in the present invention, has excellent plasticizing effect on the polyvinyl acetal, and can obtain a transparent sheet by compatibilizing the polyvinyl acetal. It is preferable.
- Castor oil is a glycerin tricarboxylic acid ester obtained from castor seeds, and most of the carboxylic acid ester portion, usually 80 to 95% by mass, is ricinoleic acid ester, and the remainder is palmitic acid ester, stearic acid ester, It is a compound composed of oleic acid ester, linoleic acid ester, linolenic acid ester and the like.
- polyester (C) The polyester compound having a hydroxyl group
- polyester (C) is not particularly limited.
- a polyester (C-1) (condensation copolymer of a polyhydric alcohol and a polycarboxylic acid having a hydroxyl group) ( Hereinafter, simply referred to as polyester (C-1)), a polymer of hydroxycarboxylic acid and having a hydroxyl group (C-2) (hereinafter simply referred to as polyester (C-2)), a hydroxyl group-containing polycarbonate polyol (C-3) (hereinafter simply referred to as polyester (C-3)).
- Polyester (C-1) can be obtained by condensation polymerization of polyhydric alcohol and polyhydric carboxylic acid in an excess of polyhydric alcohol.
- the polyhydric alcohol include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, -Hexanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, 1,2-nonanediol, 1,8-nonanediol, 1,9-nonanediol, 1,2-cyclohexanediol, Aliphatic dihydric alcohols such as 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, diethylene glycol and triethylene glycol; aliphatic trihydric alcohols such as glycerin;
- aliphatic dihydric alcohols are preferable because they are excellent in weather resistance of polyester (C-1), compatibility with polyvinyl acetal, and plasticizing effect on polyvinyl acetal.
- polyvalent carboxylic acids include succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, dodecanedioic acid, 1,2-cyclohexanedicarboxylic acid and other aliphatic divalent carboxylic acids, 1,2,3-propane
- aliphatic trivalent carboxylic acids such as tricarboxylic acid and 1,3,5-pentatricarboxylic acid, aromatic divalent carboxylic acids such as phthalic acid and terephthalic acid, and aromatic trivalent carboxylic acids such as trimellitic acid.
- aliphatic dicarboxylic acids particularly aliphatic dicarboxylic acids having 6 to 10 carbon atoms are also excellent in the plasticizing effect of the obtained polyester on polyvinyl acetal, and the transparent sheet is obtained by compatibilizing polyvinyl acetal. This is preferable in that it can be performed.
- a copolymer of polyhydric carboxylic acid and polyhydric alcohol obtained by using monohydric alcohol or monohydric carboxylic acid as a raw material in addition to the polyhydric alcohol or polyhydric carboxylic acid unless it is contrary to the spirit of the invention A compound which is a polymer and has a hydroxyl group can also be used.
- Polyester (C-2) can be obtained by condensation polymerization of hydroxycarboxylic acid.
- the hydroxycarboxylic acid include glycolic acid, lactic acid, 2-hydroxybutanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 6-hydroxyhexanoic acid, ricinoleic acid and the like.
- a lactone compound obtained by intramolecular condensation of these hydroxycarboxylic acids can also be used as a raw material.
- the lactone compound include, but are not limited to, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, 4-methyl- ⁇ -valerolactone, and the like.
- polyester (C-2) can be obtained by ring-opening polymerization.
- 6-hydroxycarboxylic acid or ⁇ -caprolactone is preferred from the viewpoints of heat resistance of the polyester (C-2), compatibility with polyvinyl acetal and plasticizing effect.
- the ether compound having a hydroxyl group examples include ethylene glycol monooctyl ether and a polyether compound having a hydroxyl group.
- a polyether compound having a hydroxyl group from the viewpoint of compatibility with the polyvinyl acetal used in the present invention, excellent plasticizing effect on the polyvinyl acetal, and a viewpoint of compatibilizing the polyvinyl acetal, it is preferable to use a polyether compound having a hydroxyl group.
- the ether compound is a polymer of a polyhydric alcohol such as ethylene glycol and 1,2-propylene glycol, and has a hydroxyl group.
- polyethylene glycol and polypropylene glycol are preferable.
- water-insoluble means that the amount dissolved in 100 g of water at 20 ° C. is 100 g or less, preferably 50 g or less, more preferably 10 g or less, and even more preferably 2 g or less.
- the hydroxyl value of the compound having a hydroxyl group used in the present invention is not particularly limited, but is preferably 50 to 600 mgKOH / g, more preferably 70 to 500 mgKOH / g, and 100 to 400 mgKOH / g. Is more preferable.
- the hydroxyl value is less than 50 mgKOH / g, the transparency of the sheet obtained from the polyvinyl acetal composition of the present invention may be lowered.
- the hydroxyl value exceeds 600 mgKOH / g, the compound having a hydroxyl group and polyvinyl acetal In some cases, the compatibility of the resin may be reduced, transparency may be lowered, and bleeding may occur from the molded product.
- the hydroxyl value in the present invention is a value obtained by measurement by the method described in JIS K1557-1 (2007).
- the hydroxyl value in the case of using a mixture of two or more compounds having a hydroxyl group refers to the hydroxyl value of the mixture (a mixture of compounds having a hydroxyl group having the same mixing ratio as in the polyvinyl acetal composition of the present invention).
- the plasticizer having no polar group contained in the plasticizer of the present invention has a polar group such as a hydroxyl group, a polyethylene oxide group having a polymerization degree of 10 or more, a polypropylene oxide group having a polymerization degree of 10 or more, a carboxyl group, or an amino group. More specifically, it is an ester compound of a polyhydric alcohol and a monovalent carboxylic acid and has no polar group, and is an ester compound of a polyhydric carboxylic acid and a monohydric alcohol that is polar. Examples thereof include compounds having no group.
- Examples of the compound having a polyhydric alcohol and a monovalent carboxylic acid and having no polar group include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate and the like. .
- ester compounds of polyvalent carboxylic acid and monohydric alcohol having no polar group include dihexyl adipate, dioctyl adipate, di (butoxyethyl) adipate, di (butoxyethoxyethyl) adipate, Examples include dibutyl sebacate, dioctyl sebacate, dioctyl phthalate, di (2-ethylhexyl) phthalate, di (octyl) cyclohexanedicarboxylate, and di (isononyl) cyclohexanedicarboxylate.
- a compound which does not have is preferable from the viewpoints of plasticizing effect on polyvinyl acetal, low volatility and the like.
- the plasticizer used in the present invention contains 0.5 to 100% by mass of the plasticizer having a polar group and 0 to 99.5% by mass of a plasticizer having no polar group, and has a polar group.
- the total content of the plasticizer having no polar group is 100% by mass, there is no particular limitation.
- the obtained composition is a compound having a hydroxyl group as a plasticizer having a polar group, 0.5 to 5.0% by mass of the whole plasticizer, More preferably 0.5 to 4.0% by mass, still more preferably 0.5 to 2.0% by mass, and particularly preferably 1.0 to 2.0% by mass.
- a plasticizer not having a polar group a compound which is a diester of at least one compound selected from triethylene glycol and tetraethylene glycol and a monovalent carboxylic acid and does not have a polar group is used for the entire plasticizer. 70 to 99.5% by mass, preferably 90 to 99.5% by mass, more preferably 95 to 99.5% by mass, and the total of the plasticizer having a polar group and the plasticizer having no polar group is 100 What is mass% is good.
- 70 to 99.5% by mass of the total plasticizer is a diester of triethylene glycol or tetraethylene glycol and a monovalent carboxylic acid and having no polar group.
- the plasticizer having the polar group is a compound having a hydroxyl group, and two ester bonds contained in the diester compound. It is preferable that it is a compound which has a structure obtained by hydrolyzing any one of these, and each has one hydroxyl group and one ester bond.
- composition of the present invention may further contain an antioxidant, an ultraviolet absorber, a plasticizer, an adhesion improver, and other additives as long as it is not contrary to the gist of the present invention.
- the kind thereof is not particularly limited, and examples thereof include conventionally known phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like. Of these, phenolic antioxidants are preferred, and alkyl-substituted phenolic antioxidants are particularly preferred. These antioxidants can be used alone or in combination of two or more.
- the addition amount of the antioxidant is not particularly limited, but is in the range of 0.0001 to 5% by mass, preferably 0.001 to 1% by mass with respect to the mass of the composition. If the addition amount of the antioxidant is less than 0.0001% by mass, a sufficient effect may not be obtained, and if it is more than 5% by mass, no remarkable effect can be expected.
- the kind thereof is not particularly limited.
- a conventionally known benzotriazole ultraviolet absorber, oxalic anilide ultraviolet absorber, benzoate ultraviolet absorber and the like can be used. .
- These ultraviolet absorbers can be used alone or in combination of two or more.
- the addition amount of the ultraviolet absorber is not particularly limited, but is in the range of 0.0001 to 5% by mass, preferably 0.001 to 1% by mass with respect to the mass of the composition. If the addition amount of the ultraviolet absorber is less than 0.0001% by mass, a sufficient effect may not be obtained, and if it is more than 5% by mass, no remarkable effect can be expected.
- the adhesiveness adjustment agent is contained in the composition of this invention. It may be added.
- the adhesion adjusting agent conventionally known ones can be used. For example, sodium salts and potassium salts of organic acids such as acetic acid, propionic acid, butanoic acid, hexanoic acid, 2-ethylbutanoic acid and 2-ethylhexanoic acid. Magnesium salts and the like are used, and these may be used alone or in combination of two or more.
- the addition amount is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 0.1% by mass, and still more preferably 0.001 to 0.03% by mass with respect to the mass of the composition. .
- the composition of the present invention can be obtained by mixing the specific polyvinyl acetal defined in the present invention, the specific plasticizer, and other components by a conventionally known method.
- examples thereof include a method in which components constituting the composition of the present invention are dissolved in an organic solvent in which they can be dissolved, and then the organic solvent is distilled off; a method in which the components are melt-kneaded using an extruder or the like.
- the glass transition temperature of the composition of the present invention is not particularly limited and can be appropriately selected depending on the purpose, but is preferably in the range of 0 to 50 ° C., more preferably 0 to 45 ° C., and 0 More preferably, it is ⁇ 40 ° C.
- the glass transition temperature of the composition of the present invention satisfies the above range, it is particularly suitable when the composition of the present invention is formed into a sheet and used as an interlayer film for laminated glass.
- the composition of the present invention is excellent in transparency and flexibility, it is particularly suitable as an interlayer film for laminated glass when formed into a sheet.
- the thickness of the sheet is not particularly limited, but from the viewpoint of use as an interlayer film for laminated glass, it is preferably 0.05 to 5.0 mm, and more preferably 0.1 to 2.0 mm. More preferably, the thickness is 0.1 to 1.2 mm.
- the glass used in that case is not particularly limited.
- organic glasses such as polymethyl methacrylate and polycarbonate can be used, and these may be colorless or colored, or transparent or non-transparent. These may be used alone or in combination of two or more.
- the thickness of glass is not specifically limited, Usually, it is preferable that it is 100 mm or less.
- the shape of the outermost surface of the sheet is not particularly limited, but from the viewpoint of handleability (bubble removal property) when laminating with glass, the outermost surface of the laminate. It is preferable to form a concavo-convex structure by a conventionally known method such as melt fracture or embossing.
- the laminated glass of the present invention can be produced by a conventionally known method.
- apparatus methods such as a vacuum laminator apparatus, a vacuum bag, a vacuum ring, a nip roll, etc. are mentioned.
- the method of carrying out the temporary crimping by the said method and throwing the obtained temporary crimping body into an autoclave can also be performed additionally.
- laminated glass can be produced at a temperature of 100 to 200 ° C., particularly 130 to 160 ° C. under a reduced pressure of 1 ⁇ 10 ⁇ 6 to 3 ⁇ 10 ⁇ 2 MPa.
- a method using a vacuum bag or a vacuum ring is described in, for example, European Patent No. 1235683, and laminated glass can be produced at 130 to 145 ° C. under a pressure of about 2 ⁇ 10 ⁇ 2 MPa, for example.
- a method in which the first temporary pressure bonding is performed at a temperature equal to or lower than the flow start temperature of the composition of the present invention, and then pressure bonding is performed under conditions close to the flow start temperature Specifically, for example, a sheet comprising the composition of the present invention is heated to 30 to 70 ° C. with an infrared heater or the like and then deaerated with a roll, and then heated to 50 to 120 ° C. and then pressure-bonded with the roll to adhere or temporarily The method of making it adhere
- the autoclave process which may be additionally performed after the temporary pressing, varies depending on the thickness and configuration of the laminated glass, but for example, at a pressure of 1.0 to 1.5 MPa and a temperature of 130 to 145 ° C. for 0.5 to 3 hours. Do.
- PVB-1 polyvinyl butyral
- PVB-2 polyvinyl butyral
- PVB-3 polyvinyl butyral
- PVB-4 polyvinyl butyral
- PVB-5 was obtained in the same manner except that the amount of butyraldehyde used was changed to 395 g in the preparation of PVB-1.
- the properties of the obtained PVB-5 were measured according to JIS K6728.
- the average degree of butyralization (average degree of acetalization) was 71 mol%, the content of residual vinyl acetate groups was 1 mol%, and the content of vinyl alcohol groups was 28 mol% (see Table 1).
- PVB-6 was obtained in the same manner except that the amount of butyraldehyde used was changed to 440 g in the preparation of PVB-4.
- the properties of the obtained PVB-6 were measured according to JIS K6728.
- the average degree of butyralization (average degree of acetalization) was 70 mol%, the content of residual vinyl acetate groups was 12 mol%, and the content of vinyl alcohol groups was 18 mol% (see Table 1).
- PVB-7 was obtained in the same manner except that the amount of butyraldehyde used was changed to 350 g in the preparation of PVB-1.
- the properties of PVB-7 were measured according to JIS K6728.
- the average degree of butyralization (average degree of acetalization) was 63 mol%, the content of residual vinyl acetate groups was 1 mol%, and the content of vinyl alcohol groups was 36 mol%. (See Table 1).
- PVB-8 was obtained in the same manner except that the amount of butyraldehyde used was changed to 467 g in the preparation of PVB-2.
- the properties of PVB-8 were measured according to JIS K6728.
- the average degree of butyralization (average degree of acetalization) was 74 mol%, the content of residual vinyl acetate groups was 9 mol%, and the content of vinyl alcohol groups was 17 mol%. (See Table 1).
- PVB-9 was obtained in the same manner as in the preparation of PVB-1, except that the amount of butyraldehyde used was changed to 524 g. PVB-9 was measured according to JIS K6728. The average degree of butyralization (average degree of acetalization) was 82 mol%, the content of residual vinyl acetate groups was 1 mol%, and the content of vinyl alcohol groups was 17 mol%. (See Table 1).
- castor oil glycerin tricarboxylic acid ester, and the mass% of the
- composition-1 The composition is shown in Table 4.
- Composition-1 was hot pressed (150 ° C., 30 minutes) to obtain a sheet-1 of 10 cm ⁇ 10 cm ⁇ 0.8 mm.
- Sheet-1 adjusted to a moisture content of 0.5% (held for 24 hours in an environment of 20 ° C. and 30% RH) is sandwiched between two pieces of 10 cm ⁇ 10 cm ⁇ 3.2 mm glass and temporarily pressed in a vacuum bag. Thereafter, it was treated in an autoclave at 140 ° C. and 1.2 MPa for 40 minutes to obtain a laminated glass-1.
- HPLC measurement “Prominence” manufactured by Shimadzu Corporation as an HPLC system and “Shim-pack G-ODS (4)” manufactured by Shimadzu Corporation as an HPLC column (ODS column having an inner diameter of 4 mm and a length of 1 cm).
- ELSD-LT II manufactured by Shimadzu Corporation was used as a detector.
- the ethanol ratio in the mobile phase was increased at a constant rate (5 vol% / min) over 20 minutes immediately after sample injection, and after 20 minutes ( At this point, from the mobile phase (A) is completely replaced with ethanol), ethanol alone was used as the mobile phase.
- Width 30 seconds immediately after sample injection, 200 seconds from 5 minutes to the end Slope: 50 ⁇ m
- Drift 0 ⁇ V / min
- DBL 0 minutes
- Minimum area 10,000 counts
- the baseline was determined by analyzing a blank test solution prepared in the same manner as in the preparation of the analysis sample except that polyvinyl acetal was dissolved. The results are shown in Table 2. In this analysis, peaks other than the first peak and the second peak derived from polyvinyl acetal were not detected.
- Example 2 Polyvinyl acetal having the composition shown in Table 4 was mixed in the same manner as in Example 1 to obtain polyvinyl acetal-2 to 20 and comparative polyvinyl acetal-1 to 4, and HPLC measurement was performed. The results are shown in Table 2. Similarly, titration with hexane and deionized water after dissolution in ethanol, and measurement of undissolved content when dissolved in methanol and chloroform were performed. The results are shown in Table 3.
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Abstract
Description
規定1:ポリビニルアセタール1gをメタノール100gに溶解させた場合の未溶解分が2.5~90質量%である。
規定2:ポリビニルアセタール1gをクロロホルム100gに溶解させた場合の未溶解分が5~70質量%である。
規定1:ポリビニルアセタール1gをメタノール100gに溶解させた場合の未溶解分が2.5~90質量%である。
規定2:ポリビニルアセタール1gをクロロホルム100gに溶解させた場合の未溶解分が5~70質量%である。
本発明において、HPLC分析は、以下の方法で行う。HPLCシステム内部をエタノール/水=4/1(v/v)混合溶剤(以下、移動相(A)と称する)で満たした状態で、サンプルには、ポリビニルアセタール0.5質量%エタノール溶液30μLを注入する。カラム温度45℃、流速0.4mL/min、の条件下において、サンプル注入直後から20分かけて、移動相中のエタノールの割合を一定速度(5vol%/分)で増加させ、20分後(この時点で移動相(A)は完全にエタノールに置換される)からは、エタノール単独を移動相とする。
規定1:ポリビニルアセタール1gをメタノール100gに溶解させた場合の未溶解分が2.5~90質量%である。
規定2:ポリビニルアセタール1gをクロロホルム100gに溶解させた場合の未溶解分が5~70質量%である。
また、多価カルボン酸としてはコハク酸、グルタル酸、アジピン酸、スベリン酸、セバシン酸、ドデカン二酸、1,2-シクロヘキサンジカルボン酸などの脂肪族2価カルボン酸、1,2,3-プロパントリカルボン酸、1,3,5-ペンタトリカルボン酸などの脂肪族3価カルボン酸、フタル酸、テレフタル酸などの芳香族2価カルボン酸、トリメリット酸などの芳香族3価カルボン酸などが挙げられるが、これらに限定されない。中でも脂肪族2価カルボン酸、特に炭素数6~10の脂肪族2価カルボン酸が、また、得られるポリエステルのポリビニルアセタールに対する可塑化効果に優れ、ポリビニルアセタールを相溶化して透明なシートを得ることができる点で、好適である。また本発明の趣旨に反しない限り、多価アルコール、多価カルボン酸に追加して、1価アルコールや1価カルボン酸を原料として使用して得られる、多価カルボン酸と多価アルコールの共重合体であって水酸基を有する化合物も使用することができる。
還流冷却器、温度計、イカリ型攪拌翼を備えた10L(リットル)のガラス製容器に、イオン交換水8100g、ポリビニルアルコール(PVA-1:粘度平均重合度1700、けん化度99モル%)660gを仕込み(PVA濃度7.5%)、内容物を95℃に昇温して完全に溶解させた。次に、120rpmで攪拌下、5℃まで約30分かけて徐々に冷却後、ブチルアルデヒド384gと20%の塩酸540mLを添加し、ブチラール化反応を150分間行った。その後、60分かけて50℃まで昇温し、50℃にて120分間保持した後、室温まで冷却した。析出した樹脂をイオン交換水で洗浄後、過剰量の水酸化ナトリウム水溶液を添加して残存する酸を中和し、さらに過剰の水で再洗浄、乾燥してポリビニルブチラール(PVB-1)を得た。得られたPVB-1の特性をJIS K6728に従って測定したところ、平均ブチラール化度(平均アセタール化度)は69モル%、残存酢酸ビニル基の含有量は1モル%、平均残存水酸基量は30モル%であった(表1参照)。
還流冷却器、温度計、イカリ型攪拌翼を備えた10Lのガラス製容器に、イオン交換水8100g、ポリビニルアルコール(PVA-2:粘度平均重合度1700、けん化度92モル%)723gを仕込み(PVA濃度8.2%)、内容物を95℃に昇温して完全に溶解させた。次に、120rpmで攪拌下、5℃まで約30分かけて徐々に冷却後、ブチルアルデヒド453gと20%の塩酸540mLを添加し、ブチラール化反応を150分間行った。その後、60分かけて65℃まで昇温し、65℃にて120分間保持した後、室温まで冷却した。析出した樹脂をイオン交換水で洗浄後、過剰量の水酸化ナトリウム水溶液を添加して残存する酸を中和し、さらに過剰の水で洗浄、乾燥してポリビニルブチラール(PVB-2)を得た。得られたPVB-2の特性をJIS K6728に従って測定したところ、平均ブチラール化度(平均アセタール化度)は74モル%、残存酢酸ビニル基の含有量は6モル%、平均残存水酸基量は20モル%であった(表1参照)。
還流冷却器、温度計、イカリ型攪拌翼を備えた10Lのガラス製容器に、イオン交換水8100g、ポリビニルアルコール(PVA-3:粘度平均重合度1700、けん化度89モル%)723gを仕込み(PVA濃度8.2%)、内容物を95℃に昇温して完全に溶解させた。次に、120rpmで攪拌下、5℃まで約30分かけて徐々に冷却後、ブチルアルデヒド430gと20%の塩酸540mLを添加し、ブチラール化反応を150分間行った。その後、60分かけて58℃まで昇温し、58℃にて120分間保持した後、室温まで冷却した。析出した樹脂をイオン交換水で洗浄後、過剰量の水酸化ナトリウム水溶液を添加して残存する酸を中和し、さらに過剰の水で洗浄し、乾燥してポリビニルブチラール(PVB-3)を得た。得られたPVB-3の特性をJIS K6728に従って測定したところ、平均ブチラール化度(平均アセタール化度)は69モル%、残存酢酸ビニル基の含有量は9モル%、ビニルアルコール基の含有量(平均残存水酸基量)は22モル%であった(表1参照)。
還流冷却器、温度計、イカリ型攪拌翼を備えた10Lのガラス製容器に、イオン交換水8100g、ポリビニルアルコール(PVA-4:粘度平均重合度1700、けん化度86モル%)723gを仕込み(PVA濃度8.2%)、内容物を95℃に昇温して完全に溶解させた。次に、120rpmで攪拌下、5℃まで約30分かけて徐々に冷却後、ブチルアルデヒド427gと20%の塩酸540mLを添加し、ブチラール化反応を150分間行った。その後、60分かけて66℃まで昇温し、66℃にて110分間保持した後、室温まで冷却した。析出した樹脂をイオン交換水で洗浄後、過剰量の水酸化ナトリウム水溶液を添加して残存する酸を中和し、さらに過剰の水で洗浄し、乾燥してポリビニルブチラール(PVB-4)を得た。得られたPVB-4の特性をJIS K6728に従って測定したところ、平均ブチラール化度(平均アセタール化度)は68モル%、残存酢酸ビニル基の含有量は12モル%、ビニルアルコール基の含有量は20モル%であった(表1参照)。
PVB-1の調製において、ブチルアルデヒドの使用量を395gに変更した以外は同様にしてPVB-5を得た。得られたPVB-5の特性をJIS K6728に従って測定したところ、平均ブチラール化度(平均アセタール化度)は71モル%、残存酢酸ビニル基の含有量は1モル%、ビニルアルコール基の含有量は28モル%であった(表1参照)。
PVB-4の調製において、ブチルアルデヒドの使用量を440gに変更した以外は同様にしてPVB-6を得た。得られたPVB-6の特性をJIS K6728に従って測定したところ、平均ブチラール化度(平均アセタール化度)は70モル%、残存酢酸ビニル基の含有量は12モル%、ビニルアルコール基の含有量は18モル%であった(表1参照)。
PVB-1の調製において、ブチルアルデヒドの使用量を350gに変更した以外は同様にして、PVB-7を得た。PVB-7の特性をJIS K6728に従って測定したところ、平均ブチラール化度(平均アセタール化度)は63モル%、残存酢酸ビニル基の含有量は1モル%、ビニルアルコール基の含有量は36モル%であった(表1参照)。
PVB-2の調製において、ブチルアルデヒドの使用量を467gに変更した以外は同様にして、PVB-8を得た。PVB-8の特性をJIS K6728に従って測定したところ、平均ブチラール化度(平均アセタール化度)は74モル%、残存酢酸ビニル基の含有量は9モル%、ビニルアルコール基の含有量は17モル%であった(表1参照)。
PVB-1の調製において、ブチルアルデヒドの使用量を524gに変更した以外は同様にして、PVB-9を得た。PVB-9をJIS K6728に従って測定したところ、平均ブチラール化度(平均アセタール化度)は82モル%、残存酢酸ビニル基の含有量は1モル%、ビニルアルコール基の含有量は17モル%であった(表1参照)。
ポリビニルアセタール-1(PVB-1:PVB-2=80:20の質量比で混合したもの)100質量部、ひまし油(グリセリントリカルボン酸エステルであって、カルボン酸エステル部分の質量%がリシノール酸エステルであり、13質量%がパルミチン酸エステル、ステアリン酸エステル、オレイン酸エステル、リノール酸エステル、リノレン酸エステルのいずれかであり、1質量%がその他のカルボン酸エステルで構成;1分子あたりの水酸基の数2.6個、水酸基価160mgKOH/g、水酸基価に基づく平均分子量910)50質量部をラボプラストミルで溶融混練(150℃、5分)して組成物-1を得た。組成を表4に示す。組成物-1を熱プレス(150℃、30分)して、10cm×10cm×0.8mmのシート-1を得た。含水量を0.5%に調整(20℃、30%RHの環境下で24時間保持)したシート-1を、10cm×10cm×3.2mmのガラス2枚に挟んでバキュームバック内で仮圧着後、オートクレーブで140℃、1.2MPa、40分間処理して合わせガラス-1を得た。
(1)分析サンプルの調整
耐圧試験管にポリビニルアセタール100mg、エタノール(99.5%)20mLを量りとり、完全に密閉した後、振とう式恒温水槽に浸漬して、振とうしながら70℃、4時間処理して溶解させた(3.5時間の時点で、完全に溶解していた)。室温で放冷後、孔径0.45μm、直径13mmの親水化PTFEメンブレンフィルターでろ過して、HPLC検液を得た。
HPLCシステムとして(株)島津製作所製「Prominence」、HPLCカラムとして(株)島津製作所製「Shim-pack G-ODS(4)」(内径4mm、長さ1cmのODSカラム)を使用し、また検出器として(株)島津製作所製「ELSD-LT II」を使用した。HPLC分析は、以下の方法で行った。HPLCシステム内部をエタノール/水=4/1(v/v)混合溶剤(以下、移動相(A)と称する)で満たした状態で、サンプルには、ポリビニルアセタール0.5質量%エタノール溶液30μLを注入した。カラム温度45℃、流速0.4mL/min、の条件下において、サンプル注入直後から20分かけて、移動相中のエタノールの割合を一定速度(5vol%/分)で増加させ、20分後(この時点で、移動相(A)は完全にエタノールに置換される)からは、エタノール単独を移動相とした。検出器のネブライザーガスとして窒素ガスを使用した(ガス供給圧力=350kPa、噴霧温度35℃)。得られたデータの解析を、(株)島津製作所製「LabSolutions LC(ver. 5.42 SP3)」を使用し、下記条件で解析した。
Width:試料注入直後からは30秒、5分後から終了までは200秒
Slope:50μm
Drift:0μV/分
T.DBL:0分
最小面積:10,000カウント
なおベースラインの決定は、ポリビニルアセタールを溶解すること以外は前記分析サンプルの調整と同様の方法で準備した空試験液を分析して行った。結果を表2に示す。なお、本分析ではポリビニルアセタールに由来する第一のピーク、第二のピーク以外のピークは検出されなかった。
1gのポリビニルアセタール-1をエタノール100gに溶解して透明な溶液を得て、23℃で該溶液を撹拌下でヘキサンにより滴定したところ、滴下量が181mLになった時点で溶液が白濁した。一方、1gのポリビニルアセタール-1をエタノール100gに溶解して透明な溶液を得て、23℃で該溶液を撹拌下で脱イオン水により滴定したところ、滴下量が28mLになった時点で溶液が白濁した。結果を表3に示す。
また、1gのポリビニルアセタール-1をメタノール100gに溶解させた場合の未溶解分は、19%であった。未溶解分は、メタノール100gを撹拌下、各粒子または各塊の長径が3mm以下である1gのポリビニルアセタール-1を塊状にならないように添加し、25℃で72時間処理した後、得られた溶液(未溶解分を含む)をJIS P3801の規定における5種Aのろ紙を使用して差圧0.010±0.002MPaで減圧ろ過し、ろ紙上に残存する成分の乾燥質量を測定することで求めた。結果を表3に示す。
一方、1gのポリビニルアセタール-1をクロロホルム100gに溶解させた場合の未溶解分は0%であった。未溶解分は、クロロホルム100gを撹拌下、各粒子または各塊の長径が3mm以下である1gのポリビニルアセタール-1を塊状にならないように添加し、25℃で72時間処理した後、得られた溶液(未溶解分を含む)をJIS P3801の規定における5種Aのろ紙を使用して差圧0.010±0.002MPaで減圧ろ過した場合における、ろ紙上に残存する成分の乾燥質量を測定することで求めた。結果を表3に示す。
シート-1を3mm幅で切断し、ティーエイインスツルメント社製、RSA-G2を使用して動的粘弾性測定を行った(引っ張りモード、周波数0.3Hz、-20℃から測定を開始し、3℃/分で昇温した。100℃まで昇温したところで測定を終了した)。測定範囲内でtanδが最大になる温度(tanδのピーク温度、すなわち本発明におけるガラス転移温度)26℃であった。結果を表5に示す。
シート-1を、23℃、90%RHで2週間静置した後の白濁の有無およびブリードの有無を確認したところ、いずれも見られなかった。結果を表5に示す。
スガ試験機社製、ヘーズメーター(HZ-1)を使用し、合わせガラス-1のヘイズを測定したところ0.6%であった。結果を表5に示す。
合わせガラス-1の面に対して垂直な方向、20cmの距離から2700ルーメンのライトを照射し、光が照射されている部分の曇り発生有無を合わせガラス斜め上方から目視で確認したところ、曇りは発生していなかった。結果を表5に示す。
実施例1と同様の方法で、表4に示す組成でポリビニルアセタールを混合して、ポリビニルアセタール-2~20、比較ポリビニルアセタール-1~4を得、HPLC測定を行った。結果を表2に示す。同様に、エタノールに溶解させた後のヘキサン、脱イオン水による滴定、メタノール、クロロホルムに溶解させた場合の未溶解分の測定を実施した。結果を表3に示す。さらに、実施例1と同様の方法で、表4に示す組成でポリビニルアセタール、水酸基を有する化合物、水酸基を有さない化合物を混合して、組成物-2~20、比較組成物-1~4を得た。さらに、これらの組成物から、実施例1と同様にしてシート-2~20及び比較シート-1~4、並びに、合わせガラス-2~20及び比較合わせガラス-1~4を得た。得られたシート、合わせガラスを実施例1と同様の方法で評価した。結果を表5に示す。なお、これら実施例、比較例で使用するポリビニルアセタールの分析では、ポリビニルアセタールに由来する第一のピーク、第二のピーク以外のピークは検出されなかった。
Claims (25)
- ポリビニルアセタール100質量部に対して、極性基を有する可塑剤0.5~100質量%及び極性基を有さない可塑剤0~99.5質量%からなり、極性基を有する可塑剤と極性基を有さない可塑剤の合計が100質量%である可塑剤30~70質量部を含み、
該ポリビニルアセタールを内径4mm、長さ1cmのオクタデシルシリル基で表面修飾された球状シリカゲルを固定相として充填したカラム(ODSカラム)を用いて高速液体クロマトグラフィー(HPLC)で分析した際に、ポリビニルアセタールに由来する第一のピーク及び第二のピークが現れる組成物。 - 第一のピークと第二のピークの溶出時間の差が2~10分である、請求項1に記載の組成物。
- 溶出時間22分未満に第一のピークが現れ、かつ溶出時間22分以上に第二のピークが現れる請求項1又は2に記載の組成物。
- 第一のピークを有する山の面積の平方根と、第二のピークを有する山の面積の平方根の比が20:80~98:2である、請求項1~3のいずれかに記載の組成物。
- ポリビニルアセタールに由来するピークを有する山のうち、面積が最も広い山及び面積が二番目に広い山について、山のピークの溶出時間が早い山を構成するピークを第一のピークとし、他方の山を構成するピークを第二のピークとした際に、第一のピークを有する山の面積の平方根と、第二のピークを有する山の面積の平方根の和が、ポリビニルアセタールに由来する各ピークを有する山の面積の平方根の和に対して50~100%である、請求項1~4のいずれかに記載の組成物。
- ポリビニルアセタールが、該ポリビニルアセタール1gをエタノール100gに溶解させた溶液をヘキサンで滴定した場合に、溶液が白濁するまでのヘキサンの滴下量が140mL以上である、請求項1~5のいずれかに記載の組成物。
- ポリビニルアセタールが、該ポリビニルアセタール1gをエタノール100gに溶解させた溶液を脱イオン水で滴定した場合に、溶液が白濁するまでの脱イオン水の滴下量が10mL以上である、請求項1~6のいずれかに記載の組成物。
- 極性基を有する可塑剤が水酸基を有する化合物である、請求項1~7のいずれかに記載の組成物。
- 極性基を有する可塑剤が分子量200~2000の化合物である、請求項1~7のいずれかに記載の組成物。
- 水酸基を有する化合物の水酸基価に基づく数平均分子量が200~2000である、請求項8記載の組成物。
- 水酸基を有する化合物がエステル化合物である、請求項10に記載の組成物。
- エステル化合物がポリエステル化合物である、請求項11に記載の組成物。
- 水酸基を有する化合物がエーテル化合物である、請求項10に記載の組成物。
- エーテル化合物がポリエーテル化合物である、請求項13に記載の組成物。
- 可塑剤の0.5~5質量%が水酸基を有する化合物であり、可塑剤の70~99.5質量%がトリエチレングリコール及びテトラエチレングリコールから選ばれる化合物と1価カルボン酸とのジエステルであって極性基を有さない化合物である、請求項1~7のいずれかに記載の組成物。
- ポリビニルアセタールが、平均残存水酸基量の異なるポリビニルアセタール(A)とポリビニルアセタール(B)を混合したものである、請求項1~15のいずれかに記載の組成物。
- ポリビニルアセタール(A)の平均残存水酸基量をXモル%、ポリビニルアセタール(B)の平均残存水酸基量をYモル%としたときに、|X-Y|≧1モル%である、請求項16に記載の組成物。
- X=27.0~33.0、Y=15.0~27.0であり、ポリビニルアセタールが規定1を満たしている、請求項17に記載の組成物。
規定1:ポリビニルアセタール1gをメタノール100gに溶解させた場合の未溶解分が2.5~90質量%である。 - X=27.0~33.0、Y=33.0~50.0であり、ポリビニルアセタールが規定2を満たしている、請求項17に記載の組成物。
規定2:ポリビニルアセタール1gをクロロホルム100gに溶解させた場合の未溶解分が5~70質量%である。 - X=15.0~27.0、Y=33.0~50.0であり、ポリビニルアセタールが規定1及び規定2を満たしている、請求項17に記載の組成物。
規定1:ポリビニルアセタール1gをメタノール100gに溶解させた場合の未溶解分が2.5~90質量%である。
規定2:ポリビニルアセタール1gをクロロホルム100gに溶解させた場合の未溶解分が5~70質量%である。 - ポリビニルアセタール(A)とポリビニルアセタール(B)との混合比率が、質量比で20:80~98:2である、請求項16~20のいずれかに記載の組成物。
- ポリビニルアセタールの平均残存水酸基量が20~33モル%である請求項1~21のいずれかに記載の組成物。
- 請求項1~22のいずれかに記載の組成物からなるシート。
- 請求項23に記載のシートを含む合わせガラス。
- ヘイズが0.01~2%である、請求項24に記載の合わせガラス。
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US14/779,179 US10392495B2 (en) | 2013-03-22 | 2013-03-22 | Polyvinyl acetal composition |
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EP2977403A1 (en) | 2016-01-27 |
JPWO2014147842A1 (ja) | 2017-02-16 |
US10392495B2 (en) | 2019-08-27 |
KR20150133817A (ko) | 2015-11-30 |
JP5529345B1 (ja) | 2014-06-25 |
EP2977403B1 (en) | 2021-01-27 |
KR101992595B1 (ko) | 2019-06-25 |
US20160046784A1 (en) | 2016-02-18 |
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