CN105814123B - Film - Google Patents
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- CN105814123B CN105814123B CN201480069458.0A CN201480069458A CN105814123B CN 105814123 B CN105814123 B CN 105814123B CN 201480069458 A CN201480069458 A CN 201480069458A CN 105814123 B CN105814123 B CN 105814123B
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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
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
[project] provide include polyvinyl alcohol film, the film by heat caused by coloring less, even if comprising surfactant when its dispersity it is excellent.[solution] film, it is 50 ~ 99.99 moles of % it includes saponification degree, viscometric degree of polymerization is 200 ~ 5, 000 polyvinyl alcohol, the content of the alkali metal salt of carboxylic acid in the film is calculated as 0.5 mass % or less with the mass conversion of alkali metal, when carrying out gel permeation chromatography measurement to the aforementioned polyvinyl alcohol that heated 3 hours at 120 DEG C, meet following formula (1) (A-B)/A < 0.75 (1) using the peak molecular weight (A) of differential refraction rate detector measurement and using the peak molecular weight (B) of absorption photometric detector (measurement wavelength 280nm) measurement, and the absorbance of peak molecular weight (B) reaches 0.25 × 10‑3~3.00×10‑3。
Description
Technical field
The present invention relates to films and its manufacturing method comprising specific polyvinyl alcohol.
Background technique
Polyvinyl alcohol (being abbreviated as " PVA " sometimes below) is known as water-soluble synthesis macromolecule.With other conjunctions
It is compared at macromolecule, the strength characteristics of PVA and to make film property especially excellent is reused in the various uses such as film.On the other hand,
PVA is easy to colour because of heating.
Patent document 1 proposes the manufacturing method of PVA a kind of, wherein initiator used in the polymerization as vinyl acetate,
Use the peroxyester based compound with regulation structure.Manufactured PVA is described in patent document 1 to be not easy due to heating
Color.
In addition, patent document 2 describes the manufacturing method of PVA a kind of, wherein the content by inhibitor (polymerization inhibitor) is
10ppm vinyl acetate monomer below is polymerize obtain polyvinyl acetate after, to the polyvinyl acetate carry out water
Solution.The coloring that patent document 2 describes manufactured PVA is few.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 5-320219 bulletin
Patent document 2: Japanese Unexamined Patent Application Publication 2011-508802 bulletin.
Summary of the invention
Subject to be solved by the invention
Reduction coloring however, even if the method recorded using patent document 1 and 2, when heating PVA, film comprising the PVA
Effect it is still insufficient, in addition, manufacture include surfactant film when, there is a problem of its bad dispersibility, surface characteristic difference.
The present invention be carry out in order to solve the above problems, it is intended that provide include PVA film, the film by
Heating caused by coloring less, even if comprising surfactant when its dispersity it is excellent.
The means used to solve the problem
The inventors of the present invention have made intensive studies in order to solve the above problems, as a result, it has been found that: it has used and has met specific item
The coloring caused by heating of the certain films of the PVA of part is few, moreover, excellent its dispersity when even if comprising surfactant
It is different, it further repeats to study based on the opinion, so as to complete the present invention.
That is, the above subject is solved by providing such as lower film, the film includes that saponification degree is 50 ~ 99.99 moles of %, glues
The content of the PVA that the degree of polymerization is 200 ~ 5,000, the alkali metal salt of the carboxylic acid in the film are calculated as 0.5 with the mass conversion of alkali metal
Quality % is hereinafter, carry out gel permeation chromatography (being abbreviated as GPC sometimes below) to the aforementioned PVA that heated 3 hours at 120 DEG C
When measurement, (wavelength is measured using the peak molecular weight (A) of differential refraction rate detector measurement and using absorption photometric detector
280nm) peak molecular weight (B) measured meets following formula (1), and the absorbance of peak molecular weight (B) reaches 0.25 × 10-3~
3.00×10-3,
(A-B)/A < 0.75 (1).
Wherein, in aforementioned GPC measurement,
Mobile phase: the hexafluoroisopropanol of the sodium trifluoroacetate containing 20mmol/L is (hereinafter, sometimes write a Chinese character in simplified form hexafluoroisopropanol
For HFIP.)
Sample solution concentration: 1.00mg/mL
Sample injection rate: 100 μ L
Column: " the GPC HFIP-806M " of Showa Denko K. K's manufacture
Column temperature: 40 DEG C
Flow velocity: 1mL/ minutes
The cell length of absorption photometric detector: 10mm.
The effect of invention
In accordance with the invention it is possible to the film comprising PVA be obtained, even if colouring less caused by heating, including table in the film
Its dispersity is also excellent when the activating agent of face.
Detailed description of the invention
Fig. 1 is the pass of molecular weight and the value using differential refraction rate detector (RI) measurement for the PVA of embodiment 1
The signal of system and molecular weight and the relationship using absorption photometric detector (UV) (measurement wavelength 280nm) absorbance measured
Figure.
Specific embodiment
PVA of the invention is the PVA that saponification degree is 50 ~ 99.99 moles of %, viscometric degree of polymerization is 200 ~ 5,000, to 120
When heated aforementioned PVA progress GPC measurement in 3 hours at DEG C, the peak molecular weight (A) of differential refraction rate detector measurement is utilized
Meet following formula (1) with the peak molecular weight (B) using absorption photometric detector (measurement wavelength 280nm) measurement, and peak position point
The absorbance of son amount (B) reaches 0.25 × 10-3~3.00×10-3。
(A-B)/A < 0.75 (1)
Wherein, in aforementioned GPC measurement,
Mobile phase: the HFIP of the sodium trifluoroacetate containing 20mmol/L
Sample solution concentration: 1.00mg/mL
Sample injection rate: 100 μ L
Column: " the GPC HFIP-806M " of Showa Denko K. K's manufacture
Column temperature: 40 DEG C
Flow velocity: 1mL/ minutes
The cell length of absorption photometric detector: 10mm.
In GPC measurement of the invention, using with differential refraction rate detector and absorption photometric detector and can be simultaneously
The GPC device being measured using these detectors.Absorption photometric detector is needed using the suction that can be measured under wavelength 280nm
The detector of luminosity is, it is preferable to use the inspection of the absorbance under wavelength 280nm and the absorbance under wavelength 320nm can be measured simultaneously
Survey device.The cuvette that the cuvette of the test section of absorption photometric detector is 10mm using cell length (optical path length).It inhales
Light photometric detector can measure the UV Absorption of specific wavelength, can also UV Absorption to the wavelength of particular range into
Row spectroscopic assay.PVA for measurement is separated into each molecular weight constituent by GPC column.It is obtained by differential refraction rate detector
The signal strength arrived is substantially proportional to the concentration of PVA (mg/mL).On the other hand, the PVA detected using absorption photometric detector
Only there is in provision wavelengths the PVA absorbed.It is measured by aforementioned GPC, each molecular weight constituent that can measure PVA is respective dense
Absorbance under degree and provision wavelengths.
It, for dissolving the solvent and mobile phase of the PVA to be measured, uses as in aforementioned GPC measurement with 20mmol/L's
Concentration contains the HFIP of sodium trifluoroacetate.HFIP being capable of dissolving PVA and polymethyl methacrylate (hereinafter abbreviated as PMMA).Separately
Outside, by adding sodium trifluoroacetate, PVA can be prevented to be adsorbed in column packing.Flow velocity in aforementioned GPC measurement is set as 1mL/ points
Clock, column temperature are set as 40 DEG C.
In aforementioned GPC measurement, monodispersed PMMA(hereinafter referred to as standard PMMA is used as standard items).Measure molecule
Different multiple standards PMMA is measured, standard curve is made by the molecular weight that GPC dissolves out capacity and standard PMMA.In the present invention,
In the measurement carried out using differential refraction rate detector, using the detector and made standard curve is used, is utilizing suction
In the measurement that light photometric detector carries out, using the detector and made standard curve is used.Use these standard curves
By GPC dissolution capacity conversion at molecular weight, peak molecular weight (A) and peak molecular weight (B) are found out.
Before aforementioned GPC measurement, PVA is heated 3 hours at 120 DEG C.In the present invention, benefit heats with the following method
PVA.That is, being cast first to the aqueous solution dissolved with PVA powder, then it is dried and obtains at 23 DEG C, 50%RH
Film.The film with a thickness of 30 ~ 75 μm, preferably 40 ~ 60 μm.Then, using air drier, the film is small with 120 DEG C of heating 3
When.From the viewpoint of inhibiting the heat treatment error between sample, as air drier, preferably gear baking oven.
The PVA(film that will have been heated) it is dissolved in aforementioned solvents and obtains measurement sample.The PVA concentration for measuring sample is set as
1.00mg/mL, injection rate are set as 100 μ L.Wherein, when the viscometric degree of polymerization of PVA is more than 2400, excluded volume increases, therefore,
When the concentration of PVA is 1.00mg/mL, it can not be measured sometimes with good reproducibility.At this point, using appropriate diluted sample
(100 μ L of injection rate).Absorbance is proportional to the concentration of PVA.Therefore, using the extinction of sample solution concentration and actual measurement after dilution
Degree finds out absorbance when PVA concentration is 1.00mg/mL.
Fig. 1 is poor to molecular weight obtained from PVA progress GPC measurement and utilization for aftermentioned the embodiment of the present invention
The relationship and molecular weight for showing the value of refractive index detector measurement are surveyed with using absorption photometric detector (measurement wavelength 280nm)
The schematic diagram of the relationship of fixed absorbance.Using Fig. 1, it is further described for the GPC measurement in the present invention.In Fig. 1,
Chromatogram shown in " RI " is to examine relative to the PVA molecular weight (horizontal axis) gone out by dissolution capacity conversion to using differential refraction rate
Obtained from the value of survey device measurement is marked and drawed.In the present invention, the molecular weight at the peak position in the chromatogram is denoted as peak position
Molecular weight (A).It should be noted that the molecular weight at the highest peak position of peak heights is remembered there are when multiple peaks in chromatogram
Make peak molecular weight (A).
In Fig. 1, chromatogram shown in " UV " is relative to the PVA molecular weight (horizontal axis) gone out by dissolution capacity conversion, to benefit
Obtained from being marked and drawed with the absorbance of absorption photometric detector (measurement wavelength 280nm) measurement.In the present invention, by the chromatography
The molecular weight at peak position in figure is denoted as peak molecular weight (B).It should be noted that being incited somebody to action in chromatogram there are when multiple peaks
Molecular weight at the highest peak position of peak heights is denoted as peak molecular weight (B).
When carrying out GPC measurement using the above method to aforementioned PVA, the peak position molecule of differential refraction rate detector measurement is utilized
Amount (A) and the peak molecular weight (B) for utilizing absorption photometric detector (measurement wavelength 280nm) to measure meet following formula (1).
(A-B)/A < 0.75 (1)
Peak molecular weight (A) is the value of the molecule figureofmerit as PVA.On the other hand, peak molecular weight (B) is originated from PVA
Present at 280nm have absorb ingredient.In general, peak molecular weight (A) is greatly than peak molecular weight (B), and therefore, (A-
B)/A becomes positive value.If peak molecular weight (B) becomes larger, (A-B)/A becomes smaller, if peak molecular weight (B) becomes smaller, (A-B)/A
Become larger.That is, referring to that the ingredient of the ultraviolet light of absorbing wavelength 280nm in the low molecular weight compositions in PVA is more when (A-B)/A is big.
(A-B) when/A is 0.75 or more, as it appears from the above, the ultraviolet light of the absorbing wavelength 280nm in low molecular weight compositions
Ingredient becomes more.At this time, it is difficult to obtain excellent its dispersity when coloring is less and even if comprising surfactant caused by heating
Different film.From this point of view, preferably less than 0.70, more preferably less than 0.65 (A-B)/A.
When aforementioned PVA carries out GPC measurement using the above method, the absorbance (measurement wavelength 280nm) of peak molecular weight (B)
It needs to reach 0.25 × 10-3~3.00×10-3.Aforementioned absorbance is less than 0.25 × 10-3When, it is difficult to obtain point of surfactant
The excellent film of bulk state.On the other hand, aforementioned absorbance is more than 3.00 × 10-3When, it is difficult to it is few to obtain the coloring caused by heating
Film.Aforementioned absorbance is preferably 0.50 × 10-3~2.80×10-3, more preferably 0.75 × 10-3~2.50×10-3。
Between the effect for reducing the coloring caused by heating and the effect for the dispersity for improving surfactant
From the perspective of balance, being inhaled using the peak molecular weight (A) and utilization of differential refraction rate detector measurement in aforementioned GPC measurement
The peak molecular weight (C) of light photometric detector (measurement wavelength 320nm) measurement preferably satisfies following formula (2).
(A-C)/A < 0.75 (2)
Other than the measurement wavelength of absorption photometric detector is 320nm, measured with peak molecular weight (B) equally operation
Peak molecular weight (C).Peak molecular weight (C) is originated from has the ingredient absorbed at 320nm present in PVA.In general, peak position point
Greatly than peak molecular weight (C), therefore, (A-C)/A becomes positive value to son amount (A).If peak molecular weight (C) becomes larger, (A-C)/A becomes
Small, if peak molecular weight (C) becomes smaller, (A-C)/A becomes larger.That is, referring in the low molecular weight compositions in PVA when (A-C)/A is big
Absorbing wavelength 320nm ultraviolet light ingredient it is more.
(A-C) when/A is 0.75 or more, as it appears from the above, the ultraviolet light of the absorbing wavelength 320nm in low molecular weight compositions
Ingredient becomes more.Between the effect for reducing the coloring caused by heating and the effect for the dispersity for improving surfactant
From the perspective of balance, (A-C)/A more preferably less than 0.70, more preferably less than 0.65.
Between the effect for reducing the coloring caused by heating and the effect for the dispersity for improving surfactant
From the perspective of balance, when aforementioned PVA carries out GPC measurement using the above method, absorbance (the measurement wave of peak molecular weight (C)
Long 320nm) it is preferably 0.20 × 10-3~2.90×10-3.From viewpoint as described above, aforementioned absorbance is more preferably
0.40×10-3~2.70×10-3, further preferably 0.60 × 10-3~2.40×10-3。
In addition, from reduce by heat caused by coloring effect and improve surfactant dispersity effect it
Between balance from the perspective of, the aforementioned PVA found out using differential refraction rate detector in the aforementioned GPC of aforementioned PVA measurement
Weight average molecular weight Mw relative to the ratio Mw/Mn of number-average molecular weight Mn be preferably 2.2 ~ 6.0.Mw and Mn are by relative to aforementioned
Chromatogram obtained from the molecular weight of PVA marks and draws the value measured using differential refraction rate detector is found out.The present invention
In Mw and Mn be PMMA conversion value.
In general, Mn is that obviously the average molecular weight by the influence of low molecular weight compositions, Mw are obviously by high score
The average molecular weight of the influence of son amount ingredient.Mw/Mn is often used as the index of high molecular molecular weight distribution.If Mw/Mn is small,
Indicate that it is the small macromolecule of the ratio of low molecular weight compositions, if Mw/Mn is big, then it represents that it is big for the ratio of low molecular weight compositions
Macromolecule.
Therefore, in the present invention, when Mw/Mn is less than 2.2, indicate that the ratio of the low molecular weight compositions in PVA is small.From obtaining table
From the perspective of the superior film of the dispersity of face activating agent, Mw/Mn is more preferably 2.3 or more.On the other hand, Mw/Mn is super
When 6.0, indicate that the ratio of the low molecular weight compositions in PVA is big.From the viewpoint for obtaining colouring less film caused by heating
It sets out, Mw/Mn is more preferably 3.5 or less, further preferably 3.0 or less.It is considered that the low molecular weight compositions in PVA can shadow
Ring the coloring, the dispersity of surfactant caused by heating of film.
The viscometric degree of polymerization of aforementioned PVA is measured according to JIS-K6726.I.e., it is possible to by PVA resaponifying to saponification degree 99.5
Mole % or more, and refined, then found out according to the inherent viscosity [η] measured in 30 DEG C of water by following formula.
P=([η] × 10,000/8.29)(1/0.62)
The viscometric degree of polymerization of aforementioned PVA is 200 ~ 5,000.When viscometric degree of polymerization is less than 200, it is formed by film-strength not
Foot.On the other hand, when viscometric degree of polymerization is more than 5,000, the viscosity of the aqueous solution comprising the PVA gets higher and is difficult to be film-made.It is viscous equal
The degree of polymerization is preferably 250 ~ 4,500, more preferably 300 ~ 4,000, further preferably 400 ~ 3,500.
The saponification degree of aforementioned PVA is measured according to JIS-K6726.The saponification degree of aforementioned PVA is 50 ~ 99.99 moles of %.
When saponification degree is less than 50 moles of %, the water-soluble of PVA is significantly reduced.It on the other hand, can not when saponification degree is more than 99.99 moles of %
Steadily manufacture PVA.Saponification degree is preferably 60 ~ 99.8 moles of %, more preferably 70 ~ 99.7 moles of %, further preferably 80 ~
99.6 mole %.
As the vinyl acetate for manufacturing aforementioned PVA, such as vinyl formate, vinyl acetate, propionic acid second can be enumerated
Enester, vinyl valerate, caprate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, pivalic acid ethylene
Ester and tertiary ethylene carbonate etc., particularly preferably vinyl acetate.
In addition, aforementioned PVA can also be by 2 mercapto ethanol, n-dodecyl mercaptan, thioacetic acid, 3- mercaptopropionic acid
Vinyl acetate is polymerize in the presence of equal mercaptan compounds, and gained polyvinyl ester is saponified to manufacture.Pass through the party
Method can obtain the PVA that end is imported with the functional group from mercaptan compound.
As the method being polymerize to vinyl acetate, can enumerate mass polymerization, solution polymerization process, suspension polymerization,
Method well known to emulsion polymerization etc..In these methods, it is typically employed in the mass polymerization or use of solvent-free lower progress
The solution polymerization process that alcohol equal solvent carries out.From the viewpoint of improving effect of the present invention, preferably it polymerize together with lower alcohol
Solution polymerization process.As lower alcohol, be not particularly limited, preferably the carbon atom numbers such as methanol, ethyl alcohol, propyl alcohol, isopropanol be 3 with
Under alcohol, methanol usually can be used.When carrying out polymerization reaction using mass polymerization, solution polymerization process, reactive mode can also
Using any way in intermittent and continous way.As initiator used in polymerization reaction, 2,2 '-azos can be enumerated
Double isobutyronitriles, 2,2 '-azos bis- (2,4- methyl pentane nitriles), 2,2 '-azos bis- (4- methoxyl group -2,4- methyl pentane nitriles) etc. are even
Nitrogen series initiators；Organic peroxides series initiators such as benzoyl peroxide, n-propyl peroxycarbonates etc. do not damage this hair
Known initiator in the range of obvious results fruit.Wherein, the organic peroxy that the half-life period at preferably 60 DEG C is 10 ~ 110 minutes
Object series initiators particularly preferably use peroxy dicarbonate.It is not limited especially for polymerization temperature when carrying out polymerization reaction
It is fixed, it is suitably for 5 DEG C ~ 200 DEG C of range.
When polymerizeing vinyl acetate by the methods of free radical polymerization, if within the scope of the effect of the invention,
Then can according to need is copolymerized copolymerizable monomer.As this monomer, ethylene, propylene, 1- butylene, different can be enumerated
The alpha-olefins such as butylene, 1- hexene；Carboxylic acids such as fumaric acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride or derivatives thereof；Third
The acrylate such as olefin(e) acid or its salt, methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate；Metering system
The first such as acid or its salt, methyl methacrylate, ethyl methacrylate, n propyl methacrylate, isopropyl methacrylate
Base acrylate；Acrylamide；The acrylamide derivatives such as N methacrylamide, N- ethyl acrylamide；Methacryl
Amine；The methacrylamide derivatives such as N- methyl methacrylamide, N- ethyl methacrylamide；Methyl vinyl ether, second
The vinyl ethers such as base vinyl ethers, n-propyl vinyl ether, isopropyl-ethylene base ether, n-butyl vinyl ether；Ethylene glycol ethylene
The vinyl ethers of the hydroxyls such as base ether, 1,3- propylene glycol vinyl ethers, 1,4- butanediol vinyl ethers；Allyl acetate, propyl
The allyl ethers such as allyl ether, butyl allyl ether, hexyl allyl ether；Monomer with oxyalkylene；Methylvinyl acetate；
3- butene-1-ol, 4- amylene-1-ol, 5- hexen-1-ol, 7- octen-1-ol, 9- decene-1-alcohol, 3- methyl-3- butene-1-
The alpha-olefin of the hydroxyls such as alcohol；Vinyl sulfonic acid, allyl sulphonic acid, methallylsulfonic acid, 2- acrylamide-2-methyl propane sulfonic
Deng with sulfonic monomer；Ethyleneoxy ethyl-trimethyl salmiac, ethyleneoxy butyl trimethyl ammonium chloride, ethyleneoxy
Dimethylamine, ethyleneoxy methyl-diethyl-amine, N acrylamide methyl trimethoxy ammonium chloride, N acrylamide ethyl-trimethyl
Ammonium chloride, N acrylamide dimethylamine, allyl trimethyl ammonium chloride, methacrylic trimethyl ammonium chloride, dimethallyl
Amine, allyl ethamine etc. have the monomer of cationic base；Vinyltrimethoxysilane, vinyl methyl dimethoxysilane,
Vinyl-dimethyl methoxylsilane, vinyltriethoxysilane, vinyl methyl diethoxy silane, vinyl-dimethyl base
Ethoxysilane, 3-(methyl) acrylamide propyl trimethoxy silane, 3-(methyl) acrylamide propyl triethoxysilane
Deng the monomer etc. with silicyl.The dosage of these monomers that can be copolymerized with vinyl acetate is also because it uses purpose and purposes etc.
And it is different, in general, being 20 moles of % or less, preferably 10 moles of % in terms of using all monomers used in copolymerization as the ratio of benchmark
Below.
By that will be saponified in alcoholic solvent using polyvinyl ester obtained by the above method, PVA can be obtained.
The catalyst of saponification as polyvinyl ester can enumerate hydrogen as its example usually using alkaline matter
The alkali metal alcoholates such as the alkali metal hydroxides such as potassium oxide, sodium hydroxide and sodium methoxide.With the vinyl acetate monomer of polyvinyl ester
Molar ratio computing of the unit as benchmark, the dosage of alkaline matter preferably in the range of 0.002 ~ 0.2, particularly preferably 0.004 ~
In the range of 0.1.The catalyst of saponification can add together at the initial stage of saponification, alternatively, can also be anti-in saponification
The initial stage addition a part answered, and additional remainder during saponification.
As the solvent that can be used in saponification, it is sub- that methanol, methyl acetate, dimethyl sulfoxide, diethyl can be enumerated
Sulfone, dimethylformamide etc.., it is preferable to use methanol among these solvents.At this point, it is preferred that by the moisture content of methanol adjust to
0.001 ~ 1 mass %, it more preferably adjusts to 0.003 ~ 0.9 mass %, particularly preferably adjust to 0.005 ~ 0.8 mass %.
Saponification preferably carries out at 5 ~ 80 DEG C, more preferably 20 ~ 70 DEG C at a temperature of carry out.Saponification preferably into
It row 5 minutes ~ 10 hours, more preferably carries out 10 minutes ~ 5 hours.Saponification can also be used any in batch process and continuity method
Mode carries out.After saponification, remaining catalyst can be neutralized as needed.As workable neutralization
Agent can enumerate esters such as the organic acids such as acetic acid, lactic acid and methyl acetate etc..
The alkaline matter containing alkali metal added when saponification is typically by the propulsion of saponification and generates
The esters such as methyl acetate neutralize, or the carboxylic acids such as acetic acid added after being reacted neutralize.At this point, generating the alkali gold of the carboxylic acids such as sodium acetate
Belong to salt.As described later, in film of the invention, the content of the alkali metal salt of carboxylic acid is needed with the mass conversion of alkali metal for 0.5
Quality % or less.In order to obtain this film, PVA can be cleaned after saponification.
As the cleaning solution used at this time, the lower alcohols such as methanol can be enumerated, comprising the 100 mass parts lower alcohol and 20 matter
Measure the solution of part water below, comprising solution of esters such as the methyl acetate that generates in the lower alcohol and saponifying process etc..Comprising low
Ester content in the solution of the pure and mild ester of grade is not particularly limited, relative to 100 mass parts of lower alcohol, preferably 1, and 000 mass parts
Below.As the additive amount of cleaning solution, relative to by obtained from saponification, PVA because alcohol is swollen gel 100 obtained from
Mass parts, preferably 100 ~ 10,000 mass parts, more preferably 150 ~ 5,000 mass parts, further preferably 200 ~ 1,000 matter
Measure part.When the additive amount of cleaning solution is less than 100 mass parts, the content of the alkali metal salt of the carboxylic acid in gained film is possible to be more than upper
State range.On the other hand, the additive amount of cleaning solution is more than 10, when 000 mass parts, is not easy to observe that increasing additive amount imitates cleaning
The improvement of fruit.The method of cleaning is not particularly limited, and can enumerate: addition gel (PVA) and cleaning solution for example into slot, and
It is stirred at 5 ~ 100 DEG C or stands 5 ~ 180 minutes or so, then carry out de- liquid, repeat above-mentioned operation until the alkali of carboxylic acid is golden
Belong to salt content reach expected range until intermittent mode.In addition, can enumerate: in temperature substantially identical with intermittent mode
Under degree, identical time, PVA is continuously added from tower top, and continuously add lower alcohol from tower bottom, makes the two contact ac
Continuation mode etc..
As when preparing aforementioned PVA with the extinction of peak molecular weight (A), peak molecular weight (B), peak molecular weight (B)
The absorbance of degree, peak molecular weight (C) and peak molecular weight (C) meets the method that the mode of above-mentioned condition is adjusted, such as
The following method can be enumerated.
A) by eliminate in advance include in feed ethylene ester radical polymerization inhibitor obtained from vinyl acetate be used to polymerize.
B it is preferably) 1 ~ 1,200ppm in feed ethylene ester by the total content for the impurity for including, is more preferably 3 ~ 1,
It 100ppm, is more preferably the vinyl acetate of 5 ~ 1,000ppm for free radical polymerization.As impurity, can enumerate acetaldehyde, bar
The aldehyde such as beans aldehyde, methacrylaldehyde；Acetaldehyde dimethyl acetal obtained from acetalation is carried out to the aldehyde with solvent alcohol, crotonaldehyde dimethyl contracts
The acetals such as aldehyde, acrolein dimethyl acetal；The ketone such as acetone；Esters such as methyl acetate, ethyl acetate etc..
C one that radical polymerization merges the unreacted vinyl acetate of recycling and reusing) is carried out to feed ethylene ester in alcoholic solvent
In serial process, in order to which inhibit the vinyl acetate as caused by alcohol, micro-moisture plus alcohol decomposes, hydrolysis, addition organic acid, it is specific and
The hydroxycarboxylic acids such as speech addition glycolic, glyceric acid, malic acid, citric acid, lactic acid, tartaric acid, salicylic acid；Malonic acid, succinic acid,
Polybasic carboxylic acids such as maleic acid, fumaric acid, oxalic acid, glutaric acid etc. inhibit the generation of the aldehyde such as the acetaldehyde generated by decomposition as far as possible.Make
It preferably 1 ~ 500ppm, is more preferably 3 ~ 300ppm relative to feed ethylene ester for the additive amount of organic acid, is further preferred
For 5 ~ 100ppm.
D) as solvent used in polymerization, the total content using impurity is preferably 1 ~ 1,200ppm, is more preferably 3 ~ 1,
The solvent of 100ppm, further preferably 5 ~ 1,000ppm.As the impurity for including in solvent, can enumerate as feed ethylene
The impurity that includes in ester and impurity as described above.
When E) carrying out free radical polymerization to vinyl acetate, ratio of the solvent relative to vinyl acetate is improved.
F) as the radical polymerization initiator for use when free radical polymerization to vinyl acetate, organic peroxy is used
Object.As organic peroxide, acetyl peroxide, peroxidating isobutyl group, diisopropyl peroxycarbonates, diene can be enumerated
Peroxydicarbonate, diη-propyl peroxy dicarbonate, myristyl peroxy dicarbonate, two (2- ethoxies
Base ethyl) peroxy dicarbonate, two (2- ethylhexyl) peroxy dicarbonates, two (methoxyisopfopyl) peroxidating, two carbon
Acid esters, two (4- tert-butylcyclohexyl) peroxy dicarbonates etc. are particularly preferably 10 ~ 110 points using the half-life period at 60 DEG C
The peroxy dicarbonate of clock.
G when) addition is for inhibiting the polymerization inhibitor of polymerization after the free radical polymerization of vinyl acetate, relative to remaining undecomposed
Radical polymerization initiator, add 5 molar equivalents polymerization inhibitor below.As the type of polymerization inhibitor, molecular weight can be enumerated
It is 1,000 compound below with conjugated double bond, and the compound keeps free radical stable and inhibits polymerization reaction.It is specific and
Speech, can enumerate such as isoprene, 2,3- dimethyl -1,3-butadiene, 2,3- diethyl -1,3-butadiene, 2- tert-butyl -
1,3- butadiene, 1,3- pentadiene, 2,3- dimethyl -1,3- pentadiene, 2,4- dimethyl -1,3- pentadiene, 3,4- dimethyl -
1,3- pentadiene, 3- ethyl -1,3- pentadiene, 2- methyl-1,3-pentylene, 3- methyl-1,3-pentylene, 4- methyl-1,3-
Pentadiene, 1,3- hexadiene, 2,4- hexadiene, 2,5- dimethyl -2,4- hexadiene, 1,3- octadiene, 1,3- cyclopentadiene, 1,
3- cyclohexadiene, 1- methoxyl group -1,3- butadiene, 2- methoxyl group -1,3- butadiene, 1- ethyoxyl -1,3- butadiene, 2- ethoxy
Base -1,3- butadiene, 2- nitro -1,3- butadiene, chlorobutadiene, the chloro- 1,3- butadiene of 1-, the bromo- 1,3- butadiene of 1-, 2-
Bromo- 1,3- butadiene, fulvene, tropone, ocimenum, phellandrene, myrcene, farnesene, cembrene, sorbic acid, sorb
Acid esters, sorbate, rosin acid etc. include the conjugated diene of the conjugated structure of 2 carbon-to-carbon double bonds；1,3,5- hexatriene, 2,4,
6- sarohornene -1- carboxylic acid, eleostearic acid, tung oil, Vitamin D3 etc. include the conjugated triene of the conjugated structure of 3 carbon-to-carbon double bonds；Ring is pungent
Tetraene, 2,4,6,8- decatetraene -1- carboxylic acid, retinol, retinoic acid etc. include being total to for the conjugated structure of 4 or more carbon-to-carbon double bonds
The polyenoid such as nonconjugated polyene.It should be noted that there are multiple alloisomerisms like that for 1,3-pentadiene, myrcene, farnesene
Any kind therein can be used in the substance of body.In turn, 1,4-benzoquinone, quinhydrones, hydroquinone monomethyl ether, 2- phenyl -1- can be enumerated
Propylene, 2- phenyl -1- butylene, 2,4- diphenyl -4-methyl-1-pentene, 3,5- diphenyl -5- methyl -2- heptene, 2,4,6- tri-
Phenyl -4,6- dimethyl -1- heptene, 3,5,7- triphenyl -5- ethyl -7- methyl -2- nonene, 1,3- diphenyl -1- butylene, 2,
4- diphenyl -4- methyl -2- amylene, 3,5- diphenyl -5- methyl -3- heptene, 1,3,5- triphenyl -1- hexene, 2,4,6- tri-
Phenyl -4,6- dimethyl -2- heptene, 3,5,7- triphenyl -5- ethyl -7- methyl -3- nonene, 1- phenyl -1,3- butadiene, 1,
The aromatic systems compounds such as 4- diphenyl -1,3- butadiene.
H) by removal as far as possible the alcoholic solution of polyvinyl ester obtained from remaining vinyl acetate be used for saponification.Using residual
The removal rate for staying monomer is preferably 99% or more, more preferably 99.5% or more, further preferably 99.8% or more solution.
Pass through appropriately combined A) ~ H) obtain desired PVA.Carboxylic is manufactured by using PVA obtained from such operation
The content of the alkali metal salt of acid is in the film of particular range, colours less caused by heating, even if can be readily available comprising table
Its dispersity also excellent film when the activating agent of face.
Film of the invention contains the alkali metal salt of carboxylic acid, content with the mass conversion of alkali metal be 0.5 mass % or less,
Preferably 0.37 mass % or less, more preferably 0.28 mass % or less, further preferably 0.23 mass % or less.The content is super
When crossing 0.5 mass %, it is difficult to obtain the film that coloring is few caused by heating.Film with this content can be by adjusting manufacture institute
The content of the alkali metal salt for the carboxylic acid for including in the raw material of the PVA used etc. obtains.
In the present invention, the content (the mass conversion value of alkali metal) of the alkali metal salt about carboxylic acid can be by by PVA or film
After being ashed with platinum crucible, gained ash content is measured using ICP luminesceence analysis, and according to thus obtained alkali metal
Ionic weight is found out.
As the alkali metal salt of carboxylic acid, including following substance: by base catalyst used in above-mentioned saponifying process, such as hydrogen
Substance obtained from sodium oxide molybdena, potassium hydroxide, sodium formate etc. are neutralized with carboxylic acid；In addition, in order to inhibit to make in above-mentioned polymerization process
Substance obtained from the carboxylic acid for adding alcohol to decompose and adding of the vinyl acetates such as vinyl acetate is neutralized in saponifying process；Make
When using the carboxylic acid with conjugated double bond for the polymerization inhibitor added for terminating free radical polymerization, the carboxylic acid is in saponifying process
In be neutralized obtained from substance；Or the substance etc. actively added.As concrete example, sodium acetate, potassium acetate, third can be enumerated
Sour sodium, potassium propionate, sodium glycerinate, glyceric acid potassium, natrium malicum, potassium malate, sodium citrate, potassium citrate, sodium lactate, lactic acid
Potassium, sodium tartrate, potassium tartrate, sodium salicylate, potassium salicylate, sodium malonate, malonic acid potassium, sodium succinate, Potassium Suceinate, horse
Come sour sodium, maleic acid potassium, sodium phthalate, phthalic acid potassium, sodium oxalate, potassium oxalate, Sodium glutarate, glutaric acid potassium, pine
Fragrant acid sodium, potassium rosinate, sodium sorbate, potassium sorbate, 2,4,6- sarohornene -1- carboxylic acid sodium, 2,4,6- sarohornene -1- carboxylic acid
Potassium, eleostearic acid sodium, eleostearic acid potassium, 2,4,6,8- decatetraene -1- carboxylic acid sodium, 2,4,6,8- decatetraene -1- carboxylic acid potassium, retinoic acid sodium, view
Potassium xanthate etc., but it is not limited to them.
Film of the invention may include plasticizer.The type of plasticizer is not particularly limited, preferably glycerol, trimethylene
The polyalcohols such as glycol, propylene glycol, diethylene glycol system plasticizer, particularly preferably glycerol.Relative to 100 mass parts PVA, plasticizer
Content be preferably that 30 below the mass, more preferably 25 below the mass.When the content of plasticizer is more than 30 mass parts, plasticising
Agent oozes out into the surface of film sometimes.
Film of the invention may include surfactant.As surfactant, Anionic surfactants can be enumerated
1 kind among these can be used in agent, nonionic surfactant, cationic surfactant, amphoteric surfactant
Or two or more.
As anionic surfactant, the carboxylic acid type such as potassium laurate can be enumerated；The sulfuric acid such as octyl salicylate
Ester type；The sulfonic acid types such as dodecylbenzenesulfonate, sodium alkyl benzene sulfonate；Polyoxyethylene lauryl ether phosphate monoethanolamine salt,
Octyl phosphate sylvite, Tryfac 5573 sylvite, stearyl phosphate kalium salt, octyl ether phosphate kalium salt, dodecylphosphoric acid
Ester sodium salt, myristyl phosphoric acid ester sodium, dioctyl phosphoric acid ester sodium, trioctyl phosphate sodium salt, polyoxyethylene aryl phenyl
Ether phosphate sylvite, polyoxyethylene aryl phenyl ether phosphate amine salt etc..
As nonionic surfactant, can enumerate such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether
Alkyl ether type；The alkyl phenyls ether type such as NONIN HS 240；The alkyl esters such as polyoxyethylene laurate；Polyoxyethylene
The alkyl amine type such as lauryl amino ether；The alkylamides type such as polyoxyethylene laural amide；Polyoxyethylene poly-oxygen propylene aether etc. poly- third
Glycol ether type；The alkylol amide types such as lauric acid diethyl amide, oleic acid diethyl amide；Polyoxyalkylene allyl phenyl ether etc.
Allyl phenyl ether type etc..
As cationic surfactant, the amine such as lauryl amine hydrochloride can be enumerated；Lauryl trimethyl
The quaternary ammonium salts such as ammonium chloride；Lauryl chloride pyridine drone equal pyridiniums salt etc..
As amphoteric surfactant, such as N- alkyl-N, TMSDMA N dimethylamine glycine betaine etc. can be enumerated.
Relative to 100 mass parts PVA, the content of surfactant is preferably in the range of 0.01 ~ 5 mass parts, more preferably
In the range of 0.02 ~ 3 mass parts.
Film of the invention may include inorganic filler.As inorganic filler, such as silica can be enumerated, can be carried out
The heavy or the calcium carbonate of lightweight, aluminium hydroxide, aluminium oxide, titanium oxide, diatomite, mica, magnesium carbonate, kaolinite of surface treatment
The clays such as soil, galapectite, pyrophyllite, sericite, talcum etc. can be used one kind or two or more among these.Among these,
Dispersibility from the viewpoint of in PVA, preferably silica, talcum.The content of inorganic filler is relative to 100 mass parts
PVA is preferably 10 below the mass.
In film of the invention, in addition to the foregoing, can also further include as needed crosslinking agent, colorant,
Resin (such as the water solubility other than PVA other than fragrance, incremental agent, defoaming agent, remover, ultraviolet absorbing agent, starch, PVA
Macromolecule etc.) etc. other ingredients.PVA, plasticizer, surfactant in the present invention and the gross mass of inorganic filler are in the total matter of film
In amount shared ratio preferably in the range of 50 ~ 100 mass %, more preferably in the range of 80 ~ 100 mass %, it is further excellent
It is selected in the range of 90 ~ 100 mass %.
The thickness of film of the invention is not particularly limited, can film according to the present invention purposes, usage mode etc. come it is appropriate
Setting, preferably in the range of 1 ~ 100 μm, more preferably in the range of 3 ~ 50 μm.It should be noted that the thickness of film can pass through
It measures the thickness at any 5 and finds out as their average value.
The manufacturing method that the content of the alkali metal salt of carboxylic acid is in the film of the invention of above range is not particularly limited, root
According to the manufacturing method of the present invention for having the process that the film stoste comprising aforementioned PVA is dried, can effectively manufacture
Film of the invention, so it is preferred that.
As the liquid medium for being used to prepare film stoste, such as water, dimethyl sulfoxide, dimethyl formyl can be enumerated
Amine, dimethyl acetamide, N-Methyl pyrrolidone, ethylene glycol, glycerol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol,
Trimethylolpropane, ethylenediamine, diethylenetriamine etc. can be used one kind or two or more among these.Wherein, to environment
Caused by from the perspective of the small, recyclability of burden, preferably water.PVA concentration in film stoste is not particularly limited, such as can
To be set as 0.1 ~ 50 mass %.
When preparation film stoste, the additives such as PVA and aforementioned plasticizer, surfactant, inorganic filler, other ingredients
Mixed method is not particularly limited, and can enumerate for example following method: the pellet of PVA is made and is mixed with additives mixed
Object, the method that it is further mixed with liquid medium；The side that the PVA for being dissolved in liquid medium is mixed with additive
Method；After so that additive is scattered in surfactant, then the method mixed with PVA；After so that additive is scattered in plasticizer, then with
The method etc. of PVA mixing.Among these, the film of additive is more evenly dispersed with due to that can be readily derived, it is therefore preferable that using
The method mixed again with PVA after making additive be scattered in surfactant, more preferably using makes additive be scattered in surface-active
The method mixed again with PVA and liquid medium after agent.
Cooperate 1 among the additives such as plasticizer as described above, surfactant, inorganic filler, other ingredients in film
Kind or two or more when, contain these ingredients in above-mentioned film stoste.When the cooperation of these ingredients
Machine is not particularly limited, and the following methods can be enumerated: operation as above, and further cooperation mixes PVA and surfactant
Obtained from substance method, alternatively, mixing PVA and surfactant before cooperate in PVA and surfactant in advance
The method of one or both.
In it will be film-made the dry process of stoste, specific drying means is not particularly limited, can be using manufacture pressure
The drying means generallyd use when prolonging film.Heat treatment can be implemented in manufactured film as needed.The temperature of the heat treatment is preferred
In the range of 70 ~ 145 DEG C, more preferably in the range of 100 ~ 135 DEG C.As the time of heat treatment, can enumerate such as 1 second
In the range of ~ 1 hour.It should be noted that being exposed to excessively high temperature in by the manufacturing process of the film the heat treatment
When, the water-swellable of gained film reduces sometimes, it is therefore preferable that the film during using until film stoste manufacture film is former
The temperature of liquid and film is kept to 180 DEG C hereinafter, preferably remaining to 150 DEG C hereinafter, further preferably keeping to 145 DEG C hereinafter, special
It does not preferably remain to 135 DEG C or less.
In addition, as needed, can also before it is dried, it is dry in or it is dry after among either one or two of more than rank
The stretching of Duan Jinhang uniaxially or biaxially.As temperature when stretching, preferably in the range of 20 ~ 120 DEG C.In addition, stretching ratio
Based on the length before stretching preferably in the range of 1.05 ~ 5 times, more preferably in the range of 1.1 ~ 3 times.And then as needed,
Heat fixation can also be carried out to film after the stretch and reduce residual stress.
The coloring caused by heating of film of the invention is few.YI value when being heated 3 hours at 120 DEG C of film of the invention
Preferably 7 or less, be more preferably 5 or less, further preferably 4 or less, particularly preferably 2 hereinafter, additionally, it is preferred that for 0.3 with
On.YI value can be found out according to JIS K 7105, specifically, can be found out by method aftermentioned in embodiment.
The purposes of film of the invention is not particularly limited, and the coloring caused by heating of film of the invention is few, even if comprising
Its dispersity is also excellent when surfactant, thus, it may be preferable to which ground is used for, with fibre packing materials, film for agricultural use, (vegetables are protected
The film of warm purposes, vegetable growth purposes etc.), gas-barrier material, filter, the hydraulic pressure headed by the purposes such as optical films such as polarization film turns
Print purposes, packaging applicationss, agricultural use, building purposes, medical application, industrial use, household items purposes, toy purposes etc.
The purposes of water-solubility membrane, biological degradability film.
Embodiment
Hereinafter, the present invention is described in more detail by embodiment and comparative example.It should be noted that embodiment below
In comparative example, " part " and " % " is quality criteria in the absence of special restrictions." degree of polymerization " refers to " viscous homopolymerization
Degree ".
[degree of polymerization and saponification degree of PVA]
The degree of polymerization and saponification degree of PVA is found out by method described in JIS-K6726.
[content of the sodium acetate in PVA and film]
The content (the mass conversion value of sodium) of sodium acetate in PVA and film is by using ジ ャ ー for after PVA or film ashing
The ICP apparatus for analyzing luminosity " IRIS AP " of レ Le ア ッ シ ュ company manufacture measures the sodium amount in gained ash content to find out.
[GPC of PVA is measured]
(heating of PVA)
By in the powder of PVA investment water, with 95 DEG C are heated 1 hour and after making it dissolve, be cooled to room temperature, to obtain
2% aqueous solution of PVA.Then, by obtained aqueous solution curtain coating in polyethylene terephthalate film (20cm × 20cm),
23 DEG C, make it dry two weeks under conditions of 50%RH, obtain the film with a thickness of 50 μm.Gained film is fixed on stainless steel with fixture
The metal die frame (metal frame of 20cm × 20cm and width 1cm) of system is heated 3 hours with gear baking oven with 120 DEG C.
(measurement device)
GPC measurement is carried out using " GPCmax " that VISCOTECH company manufactures.As differential refraction rate detector, use
" TDA305 " of VISCOTECH company manufacture.As UV, visible light absorption photometric detector, VISCOTECH company has been used
" the UV Detector2600 " of manufacture.The optical path length of the detection of absorption photometric detector cuvette is 10mm.GPC column
" the GPC HFIP-806M " for having used Showa Denko K. K to manufacture.In addition, analysis software has used device subsidiary
OmniSEC(4.7.0.406 version).
(determination condition)
Sample is nearby taken from using the center of the film after heating obtained by the above method.By the sample be dissolved in containing
In the HFIP of the sodium trifluoroacetate of 20mmol/L, the 1.00mg/mL solution of PVA is prepared.By 0.45 μm of polytetrafluoro of the solution
After the filter filtering of ethylene, for measuring.
Mobile phase has used the HFIP of the sodium trifluoroacetate containing 20mmol/L.The flow velocity of mobile phase is set as 1.0mL/ minutes.
Sample injection rate is set as 100 μ L, is measured at being 40 DEG C in GPC column temperature.
It should be noted that the viscometric degree of polymerization of PVA be more than 2400 sample in the case where, using molten after appropriate dilution
Liquid (100 μ L) carries out GPC measurement.By following formula by measured value calculate sample solution concentration be 1.00mg/mL when absorbance.α
(mg/mL) be diluted sample concentration.
Absorbance=(1.00/ α) × absorbance measured value when sample solution concentration is 1.00mg/mL
(production of standard curve)
As standard items, the PMMA(peak molecular weight of Agilent Technologies manufacture is measured: 1,944,000,
790,000,467,400,271,400,144,000,79,250,35,300,13,300,7,100,1,960,1,020,690),
It is directed to differential refraction rate detector and absorption photometric detector respectively, production will be for that will dissolve out capacity conversion into PMMA molecular weight
Standard curve.Such analysis software has been used when making each standard curve.
It should be noted that in the measurement, the measurement of PMMA used can to 1,944,000 and 271,400 both
The column that the mutual peak of the standard sample of molecular weight is separated.In addition, in the device, the peak that is obtained by differential refraction rate detector
Intensity is with mV(millivolts) it indicates, the peak intensity obtained by UV, visible light absorption photometric detector (abs unit: is inhaled with absorbance
Photometric units) it indicates.
[coloring of film]
In the project of " GPC of PVA is measured "-" heating of PVA ", by film of the above method production comprising PVA and add
Heat.Also, for the film after heating, the SM color computer manufactured using Suga Test Instruments Co., Ltd.
" SM-T-H " finds out yellow chromaticity (YI value) according to JIS K 7105, the index as the film coloring caused by heating.
[dispersity of the surfactant in film]
100 parts of PVA and 0.1 part of lauric acid diethyl amide are heated 1 hour at 95 DEG C and make it dissolve Yu Shuihou, it is cold
But to room temperature, to obtain 4% aqueous solution of PVA.By obtained aqueous solution curtain coating in polyethylene terephthalate film
(20cm × 20cm) makes it dry 1 week under conditions of 23 DEG C, 50%RH, to obtain 50 μm of thickness of film.With 200 times of light
It learns microscope to observe gained film, to evaluate the dispersity of surfactant (whether there is or not aggregations).
[synthesis of polyvinyl acetate]
(PVAc-1)
It puts into the separable flask of 6L for having blender, thermometer, nitrogen ingress pipe, return pipe and is taken off in advance
Oxygen and vinyl acetate (VAM) 2,555g for containing acetaldehyde (AA) 500ppm, acetaldehyde dimethyl acetal (DMA) 50ppm；Contain second
Methanol (MeOH) 945g of aldehyde dimethylacetal 50ppm and acetaldehyde less than 1ppm；Tartaric acid content in vinyl acetate
Reach 1% methanol solution of tartaric acid of the amount of 20ppm.Be blown into nitrogen into aforementioned flask, and by the temperature in flask keep to
60℃.It should be noted that recycling -10 DEG C of glycol/water solution in return pipe.Prepare two carbon of diη-propyl peroxidating
0.55 mass % methanol solution of acid esters, Xiang Qianshu flask is interior to be added 18.6mL and causes polymerization.Diη-propyl peroxidating at this time
The additive amount of two carbonic esters is 0.081g.Diη-propyl peroxy dicarbonate is gradually added with 20.9mL/ hours speed
Methanol solution is until polymerization terminates.In polymerization process, the temperature in flask is kept to 60 DEG C.After auto polymerization has started 4 hours,
At the time of the solid component concentration of polymer fluid reaches 25.1%, addition is equivalent in polymer fluid not containing sorbic acid 0.0141g(
Decompose and 3 molar equivalents of remaining diη-propyl peroxy dicarbonate) methanol 1200g after, cooling polymer fluid and make to gather
It closes and terminates.The aggregate rate of vinyl acetate when polymerization is 35.0%.After polymer fluid is cooled to room temperature, taken out using water flow
Haustorium, to distill removal vinyl acetate and methanol, is precipitated polyvinyl acetate to depressurizing in flask.To precipitation
Methanol 3,000g is added in polyvinyl acetate, after heat preservation dissolves polyvinyl acetate to 30 DEG C, reuses water flow pumping
Haustorium, to distill removal vinyl acetate and methanol, is precipitated polyvinyl acetate to depressurizing in flask.It will make poly- second
Vinyl acetate is dissolved in the operation being precipitated again after methanol and is further repeated 2 times.First is added into the polyvinyl acetate of precipitation
Alcohol, the methanol solution of 40 mass % of the polyvinyl acetate (PVAc-1) that the removal rate for obtaining vinyl acetate is 99.8%.
A part of the methanol solution of PVAc-1 obtained by use measures viscometric degree of polymerization.With sodium hydroxide relative to poly- second
The molar ratio of vinyl acetate monomer units in vinyl acetate reaches 0.1 mode, adds into the methanol solution of PVAc-1
10% methanol solution of sodium hydroxide.Gel is crushed at the time of generating gel compound, carries out three days Soxhlet extractions with methanol.It will
Gained PVA drying and the measurement for viscometric degree of polymerization.Viscometric degree of polymerization is 1700.
(PVAc-2 ~ PVAc-20)
Other than being altered to condition described in table 1, using method identical with PVAc-1, polyvinyl acetate is obtained
(PVAc-2 ~ PVAc-20).It should be noted that " ND " in table 1 refers to less than 1ppm.It is found out with same operate of PVAc-1
The viscometric degree of polymerization of each polyvinyl acetate of gained.It the results are shown in table 1.
[table 1]
。
[embodiment 1]
With total solid content concentration (saponification concentration) relative to the 40 mass % methanol solutions of PVAc-1 reach 30 mass % and
Sodium hydroxide reaches 0.02 mode relative to the molar ratio of the vinyl acetate monomer units in PVAc-1, adds under stiring
8% methanol solution of methanol and sodium hydroxide, starts saponification at 40 DEG C.With the propulsion of saponification, gel is being generated
Gel is crushed at the time of compound, smashed gel is transferred to 40 DEG C of container, by 60 minutes since saponification
At the time of, it is impregnated in the solution of methanol/methyl acetate/water (25/70/5 mass ratio), is neutralized.It is solidifying to gained swelling
Glue is centrifuged, and is impregnated in the methanol relative to swell gel quality for 2 times of quality, after placing 30 minutes, is centrifuged
Separation, which is repeated 4 times, 2 hours dry with 100 DEG C after being dried 1 hour with 60 DEG C, to obtain PVA.
The viscometric degree of polymerization of gained PVA is 1,700, saponification degree is 99.1 moles of %, the content of sodium acetate is 0.7%(with sodium
(Na) mass conversion is 0.20%).These data are also depicted in table 2.
PVA obtained by use carries out GPC measurement using the above method.Fig. 1 is molecular weight and utilization differential refraction rate detector
Relationship and molecular weight between the value of measurement and the absorbance using absorption photometric detector (measurement wavelength 280nm) measurement
Between relationship schematic diagram.Molecular weight at this time is (the PMMA conversion to be converted according to dissolution capacity using standard curve
Molecular weight).It is 100,000 by the peak molecular weight (A) using the measurement of differential refraction rate detector that Fig. 1 is found out, utilizes extinction
The peak molecular weight (B) of photometric detector (280nm) measurement is 53,000.Resulting value is substituted into following formula (A-B)/A and is obtained
Value be 0.47.The absorbance of peak molecular weight (B) is 1.30 × 10-3.These results are also depicted in table 2.
With same operate of method for finding out peak molecular weight (B) and find out using absorption photometric detector (320nm) survey
Fixed peak molecular weight (C) is 50,000.Peak molecular weight (A) and peak molecular weight (C) are imported into following formula (A-C)/A and obtained
The value arrived is 0.50.The absorbance of peak molecular weight (C) is 1.05 × 10-3.These results are also depicted in table 2.
PVA obtained by use, using the above method, carry out the content (the mass conversion value of sodium (Na)) of sodium acetate, film
Each measurement or evaluation of the dispersity of surfactant in color and film.It the results are shown in table 2.
[embodiment 2 ~ 20,22 ~ 24, comparative example 1 ~ 21 and 23 ~ 28]
Other than being altered to condition shown in table 2 and 3, operated similarly to Example 1 to synthesize each PVA, use gained
PVA, operation is similarly to Example 1 to carry out each measurement or evaluation.It the results are shown in table 2 and 3.
[embodiment 21]
With total solid content concentration (saponification concentration) relative to the 55 mass % methanol solutions of PVAc-3 reach 40 mass % and
Sodium hydroxide reaches 0.005 mode relative to the molar ratio of the vinyl acetate monomer units in PVAc-3, adds under stiring
8% methanol solution for adding methanol and sodium hydroxide, starts saponification at 40 DEG C.It should be noted that in system at this time
Moisture rate reach 1.2% mode and add distilled water to carry out saponification.After the methanol solution for adding sodium hydroxide, by 1
After hour, the 1% acetic acid water and a large amount of distilled water of 0.8 molar equivalent of sodium hydroxide are added, terminates saponification.By gained
Solution is transferred to drying machine, 2 hours dry with 100 DEG C after being dried 12 hours with 65 DEG C, to obtain PVA.
PVA obtained by use, operates similarly to Example 1, carries out each measurement or evaluation.It the results are shown in table 3.
[comparative example 22]
With total solid content concentration (saponification concentration) relative to the 55 mass % methanol solutions of PVAc-3 reach 40 mass % and
Sodium hydroxide reaches 0.005 mode relative to the molar ratio of the vinyl acetate monomer units in PVAc-3, adds under stiring
8% methanol solution for adding methanol and sodium hydroxide, starts saponification at 40 DEG C.It should be noted that in system at this time
Moisture rate reach 3.0% mode, add distilled water and carry out saponification.After the methanol solution for adding sodium hydroxide, pass through
After 1 hour, the 1% acetic acid water and a large amount of distilled water of 0.8 molar equivalent of sodium hydroxide are added, terminates saponification.By gained
Solution is transferred to drying machine, 2 hours dry with 100 DEG C after being dried 12 hours with 65 DEG C, to obtain PVA.
PVA obtained by use, operates similarly to Example 1, it is intended to each measurement or evaluation are carried out, but gained PVA is not soluble in water,
Therefore it can not prepare the film measured for GPC, thus only will be partially evaluation result is shown in table 2.
[table 2]
。
[table 3]
。
Can also be defined by result above: the coloring caused by heating of film of the invention is few, even if including surface-active
Its dispersity is also excellent when agent.
Claims (9)
1. film, it includes the polyvinyl alcohol that saponification degree is 50 ~ 99.99 moles of %, viscometric degree of polymerization is 200 ~ 5,000, in the film
The content of the alkali metal salt of carboxylic acid 0.5 mass % is calculated as with the mass conversion of alkali metal hereinafter,
When carrying out gel permeation chromatography measurement to the polyvinyl alcohol that heated 3 hours at 120 DEG C, differential refraction rate is utilized
The peak molecular weight (A) of detector measurement and the peak position molecule measured using absorption photometric detector with the measurement wavelength of 280nm
Amount (B) meets following formula (1), and the absorbance of peak molecular weight (B) reaches 0.25 × 10-3~3.00×10-3,
(A-B)/A < 0.75 (1),
The Weight-average molecular of the polyvinyl alcohol found out using differential refraction rate detector in the gel permeation chromatography measurement
It measures Mw and reaches 2.2 ~ 6.0 relative to the ratio Mw/Mn of number-average molecular weight Mn.
2. film according to claim 1, wherein the utilization differential refraction rate detector in the gel permeation chromatography measurement
The peak molecular weight (A) of measurement and the peak molecular weight (C) for utilizing absorption photometric detector to measure with the measurement wavelength of 320nm are full
Sufficient following formula (2),
(A-C)/A < 0.75 (2).
3. film according to claim 1 or 2, wherein being detected using absorption photometric in the gel permeation chromatography measurement
The absorbance for the peak molecular weight (C) that device is measured with the measurement wavelength of 320nm reaches 0.20 × 10-3~2.90×10-3。
4. film according to claim 1 or 2 also includes surfactant.
5. film according to claim 1 or 2, YI value when heating 3 hours at 120 DEG C is 7 or less.
6. the manufacturing method of film, the content of the alkali metal salt of the carboxylic acid in the film is calculated as 0.5 mass % with the mass conversion of alkali metal
Hereinafter, have will be comprising saponification degree is 50 ~ 99.99 moles of %, viscometric degree of polymerization is 200 ~ 5,000 polyethylene for the manufacturing method
The process that the film stoste of alcohol is dried,
When carrying out gel permeation chromatography measurement to the polyvinyl alcohol that heated 3 hours at 120 DEG C, differential refraction rate is utilized
The peak molecular weight (A) of detector measurement and the peak position molecule measured using absorption photometric detector with the measurement wavelength of 280nm
Amount (B) meets following formula (1), and the absorbance of peak molecular weight (B) reaches 0.25 × 10-3~3.00×10-3,
(A-B)/A < 0.75 (1),
The Weight-average molecular of the polyvinyl alcohol found out using differential refraction rate detector in the gel permeation chromatography measurement
It measures Mw and reaches 2.2 ~ 6.0 relative to the ratio Mw/Mn of number-average molecular weight Mn.
7. manufacturing method according to claim 6, wherein the utilization differential refraction rate in the gel permeation chromatography measurement
The peak molecular weight (A) of detector measurement and the peak position molecule measured using absorption photometric detector with the measurement wavelength of 320nm
Amount (C) meets following formula (2),
(A-C)/A < 0.75 (2).
8. manufacturing method according to claim 6 or 7, wherein utilize extinction light in the gel permeation chromatography measurement
The absorbance for the peak molecular weight (C) that degree detector is measured with the measurement wavelength of 320nm reaches 0.20 × 10-3~2.90×10-3。
9. manufacturing method according to claim 6 or 7, wherein the film stoste also includes surfactant.
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| KR20210108957A (en) * | 2018-12-28 | 2021-09-03 | 주식회사 쿠라레 | Polyvinyl alcohol film and manufacturing method of polarizing film using same |
| WO2022145488A1 (en) * | 2020-12-28 | 2022-07-07 | 株式会社クラレ | Polyvinyl alcohol film and polarizing film obtained therefrom |
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| CN102245700A (en) * | 2008-10-08 | 2011-11-16 | 可乐丽股份有限公司 | Polyvinyl chloride resin compositions and manufacturing method therefor |
| WO2013146458A1 (en) * | 2012-03-30 | 2013-10-03 | 株式会社クラレ | Polyvinyl alcohol-type polymer film and polarizing film |
| WO2014192773A1 (en) * | 2013-05-31 | 2014-12-04 | 株式会社クラレ | Polyvinyl alcohol and paper coating agent containing same |
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| CN101528817B (en) * | 2006-07-27 | 2012-11-28 | 日本合成化学工业株式会社 | Polyvinyl alcohol-based film for optical uses and polarizing membrane and polarizing plate |
| JP5638533B2 (en) * | 2010-04-20 | 2014-12-10 | 株式会社クラレ | Polyvinyl alcohol polymer film |
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| WO2013146458A1 (en) * | 2012-03-30 | 2013-10-03 | 株式会社クラレ | Polyvinyl alcohol-type polymer film and polarizing film |
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