JP6300150B2 - Radical polymerizable resin composition - Google Patents

Description

  The present invention relates to a radical polymerizable resin composition containing polyvinyl acetal, a radical polymerizable monomer and a radical polymerization initiator.

  Polyvinyl acetal is obtained by acetalization reaction in water using polyvinyl alcohol (hereinafter sometimes abbreviated as “PVA”) and an aldehyde compound under acidic conditions. A variety of polymers have been proposed for films made of polyvinyl acetal because the film is tough and has a unique structure having both a hydrophilic hydroxy group and a hydrophobic acetal group. Among them, polyvinyl formal produced from PVA and formaldehyde, polyvinyl acetoacetal produced from PVA and acetaldehyde, and polyvinyl butyral produced from PVA and butyraldehyde occupy commercially important positions.

  In particular, polyvinyl butyral is widely used in various fields such as interlayer films for laminated glass of automobiles and buildings, binders for ceramic molding, binders for ink or paint, binders for molding conductive materials such as electronic parts. Occupies a particularly important position commercially.

  Polyvinyl acetal is used as a raw material for ceramic molding binders and conductive paste binders used in the production of multilayer ceramic capacitors and the like. The performance required for the binder includes a small amount of carbon residue in the obtained sintered body.

  Patent Document 1 describes a resin composition obtained by polymerizing a (meth) acrylate monomer mixture in a resin solution containing a polyvinyl acetal resin having a predetermined structure and an organic solvent. This resin composition is said to have a smaller amount of residual carbon after sintering compared to a resin composition obtained by simply mixing separately polymerized polyvinyl acetal resin and acrylic resin.

  However, the resin composition described in Patent Document 1 has insufficient compatibility between the polyvinyl acetal resin and the radical polymerization polymer, and has been demanded for improvement. Moreover, it was calculated | required that the quantity of the carbon residue generated when the said resin composition was baked was smaller.

JP 2010-83909 A

  In the film obtained by drying the resin composition obtained by polymerization, the present invention has excellent compatibility with the polymer component obtained by polymerizing the polyvinyl acetal component and the radical polymerizable monomer, and is fired. An object of the present invention is to provide a radically polymerizable resin composition having a small amount of carbon residue that is sometimes generated.

The above-mentioned problems are that the degree of acetalization is 50 to 85 mol%, the content of vinyl ester monomer units is 0.1 to 20 mol%, and the viscosity average polymerization degree is 200 to 3000, and the following formulas (1) and ( 2) A polyvinyl acetal satisfying 2), a radical polymerizable monomer and a radical polymerization initiator are contained, and the content of the radical polymerizable monomer is 5 to 500 parts by mass with respect to 100 parts by mass of the polyvinyl acetal. It is solved by providing a radically polymerizable resin composition characterized by the following.
(AB) / A <0.60 (1)
0.50 × 10 ⁻³ ≦ b ≦ 1.00 × 10 ⁻² (2)

In the above formulas (1) and (2), A, B and b are as follows.
A: Peak top molecular weight measured by a differential refractive index detector when the polyvinyl acetal heated at 230 ° C. for 3 hours was measured by gel permeation chromatography (hereinafter sometimes abbreviated as GPC) B: 230 Peak top molecular weight (B) measured with an absorptiometric detector (measurement wavelength: 280 nm) when the polyvinyl acetal heated at 3 ° C. for 3 hours is measured by gel permeation chromatography
b: Absorbance at peak top molecular weight (B)

However, in the GPC measurement,
Mobile phase: 20 mmol / l sodium trifluoroacetate-containing hexafluoroisopropanol (hereinafter, hexafluoroisopropanol may be abbreviated as HFIP.)
Sample concentration: 1.00 mg / ml
Sample injection volume: 100 μl
Column: “GPC HFIP-806M” manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 1 ml / min Absorbance detector cell length: 10 mm
It is.

  The radical polymerizable monomer preferably contains (meth) acrylate.

  In the GPC measurement, the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the polyvinyl acetal obtained by a differential refractive index detector is preferably 2.8 to 12.0. The polyvinyl acetal is preferably polyvinyl butyral.

  A preferred embodiment of the present invention is a resin composition obtained by radical polymerization of the above radical polymerizable resin composition. A ceramic molding binder or a conductive paste binder comprising the resin composition is also a preferred embodiment of the present invention.

  According to the present invention, in the film obtained by drying the resin composition obtained by polymerization, the compatibility between the polyvinyl acetal component and the polymer component obtained by polymerizing the radical polymerization monomer is excellent, and baking is also performed. Thus, it is possible to provide a radical polymerizable resin composition with a small amount of carbon residue generated.

In the polyvinyl acetal used in Example 1, the relationship between the molecular weight and the value measured by the differential refractive index detector (RI), and the molecular weight and the absorbance measured by the absorptiometric detector (UV) (measurement wavelength 280 nm). It is the graph which showed the relationship.

The radical polymerizable resin composition of the present invention has an acetalization degree of 50 to 85 mol%, a vinyl ester monomer unit content of 0.1 to 20 mol%, and a viscosity average polymerization degree of 200 to 3000, A radical polymerizable resin composition comprising a radical polymerizable monomer and a radical polymerization initiator.
(AB) / A <0.60 (1)
0.50 × 10 ⁻³ ≦ b ≦ 1.00 × 10 ⁻² (2)

In the above formulas (1) and (2), A, B and b are as follows.
A: Peak top molecular weight measured with a differential refractive index detector when the polyvinyl acetal heated at 230 ° C. for 3 hours was measured by gel permeation chromatography B: The polyvinyl acetal heated at 230 ° C. for 3 hours Peak top molecular weight (B) measured with an absorptiometric detector (measurement wavelength 280 nm) when measured by gel permeation chromatography
b: Absorbance at peak top molecular weight (B)

However, in the GPC measurement,
Mobile phase: HFIP containing 20 mmol / l sodium trifluoroacetate
Sample concentration: 1.00 mg / ml
Sample injection volume: 100 μl
Column: “GPC HFIP-806M” manufactured by Showa Denko KK
Column temperature: 40 ° C
Flow rate: 1 ml / min Absorbance detector cell length: 10 mm
It is.

  In the GPC measurement in the present invention, a GPC apparatus having a differential refractive index detector and an absorptiometric detector and capable of simultaneously performing measurement by these detectors is used. An absorptiometric detector that can measure absorbance at a wavelength of 280 nm is used. A cell having a cell length (optical path length) of 10 mm is used as the cell of the detection unit of the absorptiometer. The absorptiometric detector may measure the absorption of ultraviolet light having a specific wavelength, or may measure the absorption of ultraviolet light having a specific range of wavelengths. The polyvinyl acetal subjected to the measurement is separated into each molecular weight component by a GPC column. The signal intensity by the differential refractive index detector is approximately proportional to the polyvinyl acetal concentration (mg / ml). On the other hand, polyvinyl acetal detected by an absorptiometric detector is only one having absorption at a predetermined wavelength. By the GPC measurement, it is possible to measure the concentration and absorbance at a predetermined wavelength for each molecular weight component of polyvinyl acetal.

  HFIP containing sodium trifluoroacetate at a concentration of 20 mmol / l is used as the solvent and mobile phase used for dissolving the polyvinyl acetal measured in the GPC measurement. HFIP can dissolve polyvinyl acetal and polymethyl methacrylate (hereinafter abbreviated as PMMA). Further, by adding sodium trifluoroacetate, adsorption of polyvinyl acetal to the column filler is prevented. The flow rate in the GPC measurement is 1 ml / min, and the column temperature is 40 ° C.

  In the GPC measurement, monodisperse PMMA (hereinafter referred to as standard PMMA) is used as a standard. Several types of standard PMMA with different molecular weights are measured, and a calibration curve is created from the GPC elution volume and the molecular weight of the standard PMMA. In the present invention, a calibration curve created using the detector is used for measurement by the differential refractive index detector, and a calibration curve created using the detector is used for measurement by the absorptiometric detector. Using these calibration curves, the GPC elution volume is converted into the molecular weight, and the peak top molecular weight (A) and the peak top molecular weight (B) are determined.

  Prior to the GPC measurement, the polyvinyl acetal is heated at 230 ° C. for 3 hours. In the present invention, polyvinyl acetal is heated by the following method. In order to clearly reflect the difference in hue of the sample after the heat treatment in the difference in absorbance, the polyvinyl acetal (film) heated by pressing the polyvinyl acetal powder at 2 MPa and 230 ° C. for 3 hours. Get. The thickness of the film at this time is 600-800 micrometers, and it is preferable that it is generally 760 micrometers.

  The heated polyvinyl acetal is dissolved in the above-mentioned solvent to obtain a measurement sample. The concentration of polyvinyl acetal in the measurement sample is 1.00 mg / ml, and the injection volume is 100 μl. However, when the viscosity average polymerization degree of the polyvinyl acetal exceeds 2400, the excluded volume increases, and therefore the polyvinyl acetal concentration may not be measured with good reproducibility at a concentration of 1.00 mg / ml. In that case, an appropriately diluted sample (injection amount 100 μl) is used. Absorbance is proportional to the concentration of polyvinyl acetal. Therefore, the absorbance when the polyvinyl acetal concentration is 1.00 mg / ml is determined using the concentration of the diluted sample and the actually measured absorbance.

  FIG. 1 shows the relationship between the molecular weight obtained by GPC measurement of polyvinyl acetal and the value measured by the differential refractive index detector, and the molecular weight and the absorptiometric detector (measurement wavelength). It is the graph which showed the relationship with the light absorbency measured by 280 nm. The GPC measurement in the present invention will be further described with reference to FIG. In FIG. 1, the chromatogram represented by “RI” is a plot of values measured by a differential refractive index detector against the molecular weight (horizontal axis) of polyvinyl acetal converted from the elution volume. In the present invention, the molecular weight at the peak position in the chromatogram is defined as peak top molecular weight (A). When there are a plurality of peaks in the chromatogram, the molecular weight at the peak position where the peak height is the highest is the peak top molecular weight (A).

  In FIG. 1, the chromatogram indicated by “UV” is a plot of the absorbance measured with an absorptiometric detector (measurement wavelength 280 nm) against the molecular weight (horizontal axis) of polyvinyl acetal converted from the elution volume. is there. In the present invention, the molecular weight at the peak position in the chromatogram is defined as peak top molecular weight (B). When there are a plurality of peaks in the chromatogram, the molecular weight at the peak position where the peak height is the highest is the peak top molecular weight (B).

The polyvinyl acetal has a peak top molecular weight (A) measured with a differential refractive index detector and a peak top molecular weight measured with an absorptiometric detector (measurement wavelength 280 nm) when GPC measurement is performed by the method described above. B) satisfies the following formula (1).
(AB) / A <0.60 (1)

  The peak top molecular weight (A) is a value serving as an index of the molecular weight of polyvinyl acetal. On the other hand, the peak top molecular weight (B) is derived from a component present in polyvinyl acetal and having absorption at 280 nm. Usually, since the peak top molecular weight (A) is larger than the peak top molecular weight (B), (AB) / A becomes a positive value. If the peak top molecular weight (B) increases, (AB) / A decreases, and if the peak top molecular weight (B) decreases, (AB) / A increases. That is, when (A-B) / A is large, it means that there are many components that absorb ultraviolet rays having a wavelength of 280 nm in the low molecular weight components in the polyvinyl acetal.

  When (A-B) / A is 0.60 or more, as described above, there are many components that absorb ultraviolet light having a wavelength of 280 nm in the low molecular weight component. In this case, the compatibility between the polyvinyl acetal component and the polymer component obtained by polymerizing the radical polymerizable monomer is lowered. (A−B) / A is preferably less than 0.55, more preferably less than 0.50.

The polyvinyl acetal needs to have an absorbance (measurement wavelength of 280 nm) at a peak top molecular weight (B) of 0.50 × 10 ^{−3 to} 1.00 × 10 ⁻² when GPC measurement is performed by the method described above. . When the absorbance is less than 0.50 × 10 ⁻³ , the compatibility between the polyvinyl acetal component and the polymer component obtained by polymerizing the radical polymerizable monomer is lowered. On the other hand, when the absorbance exceeds 1.00 × 10 ⁻² , the amount of carbon residue increases when the resulting resin composition is baked. The absorbance is preferably 1.00 × 10 ^{−3 to} 8.00 × 10 ^{−3, and} more preferably 1.50 × 10 ^{−3 to} 6.50 × 10 ⁻³ .

  In addition, the polyvinyl acetal has a ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the polyvinyl acetal determined by a differential refractive index detector in the GPC measurement is 2.8 to 12.0. Is preferred. Mw and Mn are determined from the chromatogram obtained by plotting the values measured by the differential refractive index detector with respect to the molecular weight of the polyvinyl acetal described above. Mw and Mn in the present invention are values in terms of PMMA.

  In general, Mn is an average molecular weight that is strongly influenced by a low molecular weight component, and Mw is an average molecular weight that is strongly influenced by a high molecular weight component. Mw / Mn is generally used as an index of molecular weight distribution of a polymer. When Mw / Mn is small, it indicates that the polymer has a small proportion of low molecular weight component, and when Mw / Mn is large, it indicates that the polymer has a large proportion of low molecular weight component.

  Therefore, in this invention, when Mw / Mn is less than 2.8, it shows that the ratio of a low molecular weight component is small in polyvinyl acetal. When Mw / Mn is less than 2.8, the compatibility of the resin composition deteriorates. Mw / Mn is more preferably 2.9 or more, and further preferably 3.1 or more. On the other hand, when Mw / Mn exceeds 12.0, it shows that the ratio of a low molecular weight component is large in polyvinyl acetal. Also when Mw / Mn exceeds 12.0, the compatibility deteriorates. Mw / Mn is more preferably 11.0 or less, and even more preferably 8.0 or less.

  The degree of acetalization of the polyvinyl acetal is 50 to 85 mol%, preferably 55 to 82 mol%, more preferably 60 to 78 mol%, still more preferably 65 to 75 mol%. When the degree of acetalization is less than 50 mol%, the compatibility between the polyvinyl acetal component and the polymer component obtained by polymerizing the radical polymerizable monomer is lowered. On the other hand, when the degree of acetalization exceeds 85 mol%, the compatibility between the polyvinyl acetal component and the polymer component obtained by polymerizing the radical polymerizable monomer is reduced, or the resulting resin composition is baked. Sometimes, the amount of carbon residue increases.

  The degree of acetalization represents the ratio of acetalized vinyl alcohol monomer units to all monomer units constituting polyvinyl acetal. Among the vinyl alcohol monomer units in the raw material PVA, those that are not acetalized remain in the resulting polyvinyl acetal as vinyl alcohol monomer units.

The viscosity average polymerization degree of the polyvinyl acetal is represented by the viscosity average polymerization degree of the raw material PVA measured according to JIS-K6726. That is, after re-saponifying and purifying PVA to a saponification degree of 99.5 mol% or more, it can be obtained from the intrinsic viscosity [η] (l / g) measured in water at 30 ° C. by the following equation. The viscosity average polymerization degree of PVA and the viscosity average polymerization degree of polyvinyl acetal obtained by acetalizing it are substantially the same.
P = ([η] × 10000 / 8.29) ^{(1 / 0.62)}

  The polyvinyl acetal has a viscosity average polymerization degree of 200 to 3,000. When the viscosity average polymerization degree is less than 200, it may be difficult to industrially produce polyvinyl alcohol as a raw material for polyvinyl acetal. The viscosity average degree of polymerization is preferably 300 or more, and more preferably 500 or more. On the other hand, when the viscosity average degree of polymerization exceeds 3000, the compatibility between the polyvinyl acetal component and the polymer component obtained by polymerizing the radical polymerizable monomer may decrease. The viscosity average degree of polymerization is preferably 2400 or less, and more preferably 1700 or less.

  The content of the vinyl ester monomer unit of the polyvinyl acetal is 0.1 to 20 mol%, preferably 0.3 to 18 mol%, more preferably 0.5 to 15 mol%, Preferably it is 0.7-13 mol%. When the content of the vinyl ester monomer unit is less than 0.1 mol%, polyvinyl acetal cannot be stably produced. On the other hand, when the content of the vinyl ester monomer unit exceeds 20 mol%, the amount of carbon residue may increase when the resulting resin composition is baked.

  The content of monomer units other than acetalized monomer units, vinyl ester monomer units and vinyl alcohol monomer units in the polyvinyl acetal is preferably 20 mol% or less, more preferably 10%. It is less than mol%.

  The polyvinyl acetal is usually produced by acetalizing PVA.

  The saponification degree of the raw material PVA is preferably 80 to 99.9 mol%, more preferably 82 to 99.7 mol%, still more preferably 85 to 99.5 mol%, and most preferably 87 to 99.3. Mol%. When the degree of saponification is less than 80 mol%, the amount of carbon residue may increase when the resulting resin composition is baked. On the other hand, when the degree of saponification exceeds 99.9 mol%, PVA may not be produced stably. The degree of saponification of PVA is measured according to JIS-K6726.

  Examples of vinyl esters used in the production of raw material PVA include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate and versatic. Examples thereof include vinyl acid, and vinyl acetate is particularly preferable.

  The raw material PVA is also produced by polymerizing a vinyl ester in the presence of a thiol compound such as 2-mercaptoethanol, n-dodecyl mercaptan, mercaptoacetic acid, 3-mercaptopropionic acid, and saponifying the resulting polyvinyl ester. You can also By this method, PVA in which a functional group derived from a thiol compound is introduced at the terminal is obtained.

  Examples of the method for polymerizing vinyl ester include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Among the methods, a bulk polymerization method performed without a solvent or a solution polymerization method performed using a solvent such as alcohol is usually employed. In terms of enhancing the effect of the present invention, a solution polymerization method in which polymerization is performed together with a lower alcohol is preferable. The lower alcohol is not particularly limited, but an alcohol having 3 or less carbon atoms such as methanol, ethanol, propanol and isopropanol is preferable, and methanol is usually used. When performing the polymerization reaction by the bulk polymerization method or the solution polymerization method, the reaction can be carried out by either a batch method or a continuous method. Examples of the initiator used for the polymerization reaction include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethyl-valeronitrile), 2,2′-azobis (4-methoxy). -2,4-dimethylvaleronitrile) and other azo-based initiators; organic peroxide-based initiators such as benzoyl peroxide, n-propyl peroxycarbonate, peroxydicarbonate and the like, as long as the effects of the present invention are not impaired. Known initiators may be mentioned. Particularly preferred are organic oxide-based initiators having a half-life of 10 to 110 minutes at 60 ° C. Among them, it is preferable to use peroxydicarbonate. Although there is no restriction | limiting in particular about the polymerization temperature at the time of performing a polymerization reaction, The range of 5 to 200 degreeC is suitable.

  When the vinyl ester is radically polymerized, a copolymerizable monomer can be copolymerized as necessary as long as the effects of the present invention are not impaired. Examples of such monomers include α-olefins such as ethylene, propylene, 1-butene, isobutene, and 1-hexene; carboxylic acids such as fumaric acid, maleic acid, itaconic acid, maleic anhydride, and itaconic anhydride; Derivatives thereof; acrylic acid or salts thereof; acrylic esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate; methacrylic acid or salts thereof; methyl methacrylate, ethyl methacrylate, n methacrylate Methacrylic acid esters such as propyl and isopropyl methacrylate; Acrylamide derivatives such as acrylamide, N-methylacrylamide and N-ethylacrylamide; Derivatives of methacrylamide such as methacrylamide, N-methylmethacrylamide and N-ethylmethacrylamide Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether and n-butyl vinyl ether; hydroxy group-containing vinyl ethers such as ethylene glycol vinyl ether, 1,3-propanediol vinyl ether and 1,4-butanediol vinyl ether Allyl ethers such as allyl acetate, propyl allyl ether, butyl allyl ether, hexyl allyl ether; monomers having an oxyalkylene group; isopropenyl acetate, 3-buten-1-ol, 4-penten-1-ol, Hydroxy group-containing α-olefins such as 5-hexen-1-ol, 7-octen-1-ol, 9-decen-1-ol, 3-methyl-3-buten-1-ol; Monomers having a sulfonic acid group such as phonic acid, allylsulfonic acid, methallylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid; vinyloxyethyltrimethylammonium chloride, vinyloxybutyltrimethylammonium chloride, vinyloxyethyl Cationic groups such as dimethylamine, vinyloxymethyldiethylamine, N-acrylamidomethyltrimethylammonium chloride, N-acrylamidoethyltrimethylammonium chloride, N-acrylamidodimethylamine, allyltrimethylammonium chloride, methallyltrimethylammonium chloride, dimethylallylamine, allylethylamine Monomers having a vinyl trimethoxysilane, vinylmethyldimethoxysilane, Monomers having a silyl group such as xylsilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane, 3- (meth) acrylamidopropyltrimethoxysilane, 3- (meth) acrylamidopropyltriethoxysilane, etc. Can be mentioned. The amount of the monomer copolymerizable with these vinyl esters varies depending on the purpose and application of use, but is usually 20 mol in a ratio based on all monomers used for copolymerization. % Or less, preferably 10 mol% or less.

  PVA can be obtained by saponifying the polyvinyl ester obtained by the above-mentioned method in an alcohol solvent.

  As the catalyst for the saponification reaction of the polyvinyl ester, an alkaline substance is usually used. Examples thereof include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal alkoxides such as sodium methoxide. The amount of the alkaline substance used is preferably in the range of 0.002 to 0.2 in the molar ratio based on the vinyl ester monomer unit of the polyvinyl ester, and in the range of 0.004 to 0.1. It is particularly preferred that The saponification catalyst may be added all at once in the early stage of the saponification reaction, or a part thereof may be added in the early stage of the saponification reaction, and the rest may be added and added during the saponification reaction.

  Examples of the solvent that can be used for the saponification reaction include methanol, methyl acetate, dimethyl sulfoxide, diethyl sulfoxide, dimethylformamide, and the like. Of these solvents, methanol is preferably used. At this time, the moisture content of methanol is preferably adjusted to 0.001 to 1% by mass, more preferably 0.003 to 0.9% by mass, and particularly preferably 0.005 to 0.8% by mass.

  The saponification reaction is preferably performed at a temperature of 5 to 80 ° C, more preferably 20 to 70 ° C. The saponification reaction is preferably performed for 5 minutes to 10 hours, more preferably for 10 minutes to 5 hours. The saponification reaction can be performed by either a batch method or a continuous method. After completion of the saponification reaction, the remaining catalyst may be neutralized as necessary. Usable neutralizing agents include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate.

  The alkaline substance containing an alkali metal added during the saponification reaction is usually neutralized by an ester such as methyl acetate generated by the progress of the saponification reaction, or neutralized by a carboxylic acid such as acetic acid added after the reaction. At this time, an alkali metal salt of a carboxylic acid such as sodium acetate is formed. As will be described later, in the present invention, the raw material PVA preferably contains an alkali metal salt of carboxylic acid in an amount of 0.5% by mass or less in terms of the mass of the alkali metal. In order to obtain such PVA, the PVA may be washed after saponification.

  In the present invention, examples of a method for adjusting each value obtained by GPC measurement so as to fall within the above-described range include a method using PVA produced by the following method as a raw material for polyvinyl acetal.

  A) A vinyl ester from which a radical polymerization inhibitor contained in the raw vinyl ester has been removed in advance is used for the polymerization.

  B) A vinyl ester having a total content of impurities contained in the raw material vinyl ester of preferably 1 to 1200 ppm, more preferably 3 to 1100 ppm, and still more preferably 5 to 1000 ppm is used for radical polymerization. Impurities include aldehydes such as acetaldehyde, crotonaldehyde, and acrolein; acetaldehyde such as acetaldehyde dimethyl acetal, crotonaldehyde dimethyl acetal, and acrolein dimethyl acetal obtained by acetalizing the aldehyde with a solvent alcohol; ketones such as acetone; methyl acetate and ethyl acetate And esters.

  C) In order to suppress alcoholic decomposition and hydrolysis of vinyl ester due to alcohol and a small amount of water in a series of steps in which raw material vinyl ester is radically polymerized in alcohol solvent and unreacted monomer is recovered and reused, Organic acids, specifically hydroxycarboxylic acids such as glycolic acid, glyceric acid, malic acid, citric acid, lactic acid, tartaric acid, salicylic acid; malonic acid, succinic acid, maleic acid, phthalic acid, oxalic acid, glutaric acid A carboxylic acid or the like is added to suppress the generation of aldehydes such as acetaldehyde generated by decomposition as much as possible. The addition amount of the organic acid is preferably 1 to 500 ppm, more preferably 3 to 300 ppm, and still more preferably 5 to 100 ppm with respect to the raw material vinyl ester.

  D) As a solvent used for polymerization, a solvent having a total content of impurities of preferably 1 to 1200 ppm, more preferably 3 to 1100 ppm, and still more preferably 5 to 1000 ppm. Examples of the impurities contained in the solvent include those described above as the impurities contained in the raw material vinyl ester.

  E) When the vinyl ester is radically polymerized, the ratio of the solvent to the vinyl ester is increased.

  F) An organic peroxide is used as a radical polymerization initiator used for radical polymerization of vinyl ester. Organic peroxides include acetyl peroxide, isobutyl peroxide, diisopropyl peroxycarbonate, diallyl peroxydicarbonate, di-n-propyl peroxydicarbonate, dimyristyl peroxydicarbonate, and di (2-ethoxyethyl) peroxide. Examples include oxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, di (methoxyisopropyl) peroxydicarbonate, and di (4-tert-butylcyclohexyl) peroxydicarbonate. It is preferable to use peroxydicarbonate with a period of 10 to 110 minutes.

  G) When an inhibitor is added after radical polymerization of the vinyl ester in order to suppress polymerization, an inhibitor of 5 molar equivalents or less is added to the remaining undecomposed radical polymerization initiator. Examples of the inhibitor include a compound having a conjugated double bond having a molecular weight of 1000 or less and a compound that stabilizes a radical and inhibits a polymerization reaction. Specifically, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-t-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-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 2,5-dimethyl-2,4-hexadiene, , 3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1-methoxy-1,3-butadiene, 2-methoxy-1,3-butadiene, 1-ethoxy-1,3- Tadiene, 2-ethoxy-1,3-butadiene, 2-nitro-1,3-butadiene, chloroprene, 1-chloro-1,3-butadiene, 1-bromo-1,3-butadiene, 2-bromo-1, Conjugated dienes composed of a conjugated structure of two carbon-carbon double bonds such as 3-butadiene, fulvene, tropone, osymene, ferrandrene, myrcene, farnesene, semblene, sorbic acid, sorbic acid ester, sorbic acid salt, and abietic acid; 1,3,5-hexatriene, 2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil, conjugated triene having a conjugated structure of three carbon-carbon double bonds such as cholecalciferol Carbons such as cyclooctatetraene, 2,4,6,8-decatetraene-1-carboxylic acid, retinol, retinoic acid, etc. Polyenes such as conjugated polyene consisting Motoni double bond of four or more conjugated structure. Any one having a plurality of stereoisomers such as 1,3-pentadiene, myrcene, and farnesene may be used. Furthermore, p-benzoquinone, hydroquinone, hydroquinone monomethyl ether, 2-phenyl-1-propene, 2-phenyl-1-butene, 2,4-diphenyl-4-methyl-1-pentene, 3,5-diphenyl-5 Methyl-2-heptene, 2,4,6-triphenyl-4,6-dimethyl-1-heptene, 3,5,7-triphenyl-5-ethyl-7-methyl-2-nonene, 1,3- Diphenyl-1-butene, 2,4-diphenyl-4-methyl-2-pentene, 3,5-diphenyl-5-methyl-3-heptene, 1,3,5-triphenyl-1-hexene, 2,4 , 6-triphenyl-4,6-dimethyl-2-heptene, 3,5,7-triphenyl-5-ethyl-7-methyl-3-nonene, 1-phenyl-1,3-butadiene, 1,4 - Aromatic compounds such as Eniru 1,3-butadiene.

  H) An alcohol solution of polyvinyl ester from which the remaining vinyl ester is removed as much as possible is used for the saponification reaction. Preferably, the residual monomer removal rate is 99% or more, more preferably 99.5% or more, still more preferably 99.8% or more.

  It is preferable to acetalize PVA produced by appropriately combining A) to H) to obtain the polyvinyl acetal in the present invention.

  The acetalization of PVA can be performed, for example, under the following reaction conditions, but is not limited thereto. After heating to 80-100 degreeC and dissolving PVA in water, the 3-40 mass% aqueous solution of PVA is obtained by cooling slowly over 10-60 minutes. When the temperature falls to −10 to 30 ° C., an aldehyde and an acid catalyst are added to the aqueous solution, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant. At that time, polyvinyl acetal having reached a certain degree of acetalization is precipitated. Thereafter, the temperature of the reaction solution is raised to 25 to 80 ° C. over 30 to 300 minutes, and the temperature is maintained for 10 minutes to 24 hours (this temperature is set as the reaction temperature for driving in). Next, a neutralizing agent such as an alkali is added to the reaction solution as necessary to neutralize the acid catalyst, and the resultant is washed with water and dried to obtain polyvinyl acetal.

  In general, aggregated particles made of polyvinyl acetal are generated in such a reaction or processing step, and coarse particles are easily formed. When such coarse particles are generated, there is a risk of causing variation between batches. On the other hand, when PVA produced using the above-described predetermined method is used as a raw material, the generation of coarse particles is suppressed as compared with the conventional product.

  It does not specifically limit as an acid catalyst used for acetalization reaction, Either an organic acid and an inorganic acid can be used. For example, acetic acid, p-toluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid and the like can be mentioned. Of these, hydrochloric acid, sulfuric acid, and nitric acid are preferably used. In general, when nitric acid is used, the reaction rate of the acetalization reaction is increased, and improvement in productivity can be expected. On the other hand, the obtained polyvinyl acetal particles tend to be coarse and the variation between batches tends to increase. is there. On the other hand, when PVA produced using the above-described predetermined method is used as a raw material, the generation of coarse particles is suppressed.

  In the present invention, the aldehyde used in the acetalization reaction is not particularly limited, but a known aldehyde having 1 to 8 carbon atoms is preferable, an aldehyde having 4 to 6 carbon atoms is more preferable, and n-butyraldehyde is particularly preferably used. In the present invention, polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.

  The polyvinyl acetal satisfying the formula (2) has an appropriate radical reactivity. Therefore, when the radical polymerizable monomer undergoes radical polymerization, it reacts with the polyvinyl acetal, and a resin composition having a high graft rate is obtained. The resin composition is excellent in compatibility with a polymer component obtained by radical polymerization of a polyvinyl acetal component and a radical polymerizable monomer. A coating film made of such a resin composition has high transparency. Further, the amount of carbon residue generated when the resin composition is baked is small. Furthermore, since the resin composition contains a graft polymerization product, a polymer that is graft-polymerized from the resin composition can be fractionated by selecting an appropriate good solvent and poor solvent.

  The radical polymerizable monomer preferably contains (meth) acrylate from the viewpoint of reactivity. As specific examples of the (meth) acrylate, specific examples of the (meth) acrylate monomer used in the resin composition include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n- Propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, n-nonyl (meth) acrylate, isodenyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, cumyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-di Clopentenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, monoglycerol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, biphenoxyethyl ( Monofunctional (meth) acrylates such as (meth) acrylate, biphenoxyethoxyethyl (meth) acrylate, (meth) acryloylmorpholine; polyethylene glycol (Meth) acrylate, monomethoxypolyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, monomethoxypolypropylene glycol mono (meth) acrylate, etc., and these may be used alone or in combination. it can.

  The method for radical polymerization of polyvinyl acetal and a radical polymerizable monomer is not particularly limited. The method includes a method of polymerizing polyvinyl acetal and a radical polymerizable monomer after initial addition of a radical polymerizable monomer into a polyvinyl acetal solution or dispersion, a solution or dispersion of polyvinyl acetal A method of polymerizing while sequentially adding radical polymerizable monomers therein, a certain amount of the above radical polymerizable monomer is initially added, radical polymerization is started, and the remaining radical polymerizable monomers are sequentially added. The method of superposing | polymerizing is mentioned.

  The addition amount of the radical polymerizable monomer when obtaining the radical polymerizable resin composition is 5 to 500 parts by mass with respect to 100 parts by mass of the polyvinyl acetal. When the addition amount of the radical polymerizable monomer is less than 5 parts by mass with respect to 100 parts by mass of the polyvinyl acetal, the amount of carbon residue may increase when the resulting resin composition is baked. On the other hand, when the content of the radical polymerizable monomer exceeds 500 parts by mass with respect to 100 parts by mass of the polyvinyl acetal, the compatibility between the polyvinyl acetal component and the polymer component obtained by polymerizing the radical polymerizable monomer. May decrease.

  Examples of the radical polymerization initiator used when radically polymerizing polyvinyl acetal and a radical polymerizable monomer include 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethyl- Azo initiators such as valeronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); organic peroxide initiators such as benzoyl peroxide and n-propyl peroxycarbonate Although a well-known initiator is mentioned in the range which does not impair the effect of this invention, It is not limited to these. As a method for adding these radical polymerization initiators, an initial batch addition at the start of polymerization, a method of successively adding them sequentially, or a method of adding them divided into several times may be used. About the addition amount of an initiator, although a range changes suitably with the humidity and density | concentration in the case of radical polymerization, it is 0.01-10 mass parts with respect to 100 mass parts of radical polymerizable monomers, and 0.02-5 mass Part is preferred.

  The radical polymerizable resin composition preferably contains an organic solvent. The organic solvent is not particularly limited as long as it can dissolve or disperse polyvinyl acetal. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate, butyl acetate, terpineol acetate, and dihydroterpineol acetate; methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl butyl ketone, and isophorone. Ketones; alcohols such as ethanol, isopropanol, n-propanol, terpineol, dihydroterpineol, benzyl alcohol, cresol; ethers such as ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Diethylene glycol monomethyl ether, diethylene glycol Hydroxy ethers such as butyl monoisobutyl ether, dipropylene glycol monobutyl ether and phenylpropylene glycol; hydroxy such as butyl lactate, trimethylpentanediol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol 1-isobutyrate Esters; ether esters such as ethylene glycol monoethyl ether acetate and dipropylene glycol monobutyl ether acetate; diesters such as dioctyl phthalate and dioctyl adipate, and the like. These may be used alone or in combination. Of these, methyl ethyl ketone, terpineol acetate, dihydroterpineol, dihydroterpineol acetate, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoisobutyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monobutyl ether acetate, and texanol are preferred, terpineol, terpineol acetate Dihydroterpineol, dihydroterpineol acetate, and dipropylene glycol monobutyl ether acetate are more preferable. These can be used alone or in combination. The usage-amount of a solvent is 50-2000 mass parts normally with respect to 100 mass parts of total amounts of a polyvinyl acetal and a radically polymerizable monomer, Preferably it is 75-1300 weight part.

  The radical polymerizable resin composition may contain an ultraviolet absorber, an adhesion improver, a plasticizer, and other conventionally known additives as long as they do not contradict the gist of the present invention.

  Examples of the ultraviolet absorber include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α′dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3 , 5-Di-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 Benzotriazole ultraviolet absorbers such as' -hydroxy-5'-t-octylphenyl) benzotriazole, 2,2,6,6-tetramethyl-4-pi Peridylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate, 4- (3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) -1- (2- ( Hindered amine UV absorbers such as 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -2,2,6,6-tetramethylpiperidine, 2,4-di-t -Benzoate ultraviolet absorbers such as butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, malo Acid [(4-methoxyphenyl) - methylene] - malonic acid ester ultraviolet absorbers such as dimethyl ester, 2-ethyl-2'-ethoxy - such as oxalic acid anilide-based ultraviolet absorbers such oxalanilide like. These ultraviolet absorbers can be used alone or in combination of two or more. Two or more of these ultraviolet absorbers can be used in combination.

  The plasticizer is not particularly limited as long as the effects of the present invention are not impaired and there is no problem in compatibility with polyvinyl acetal. The plasticizer is not particularly limited as long as the effects of the present invention are not impaired and there is no problem in compatibility with polyvinyl acetal. As the plasticizer, a mono- or diester of an oligoalkylene glycol having a hydroxyl group at both ends and a carboxylic acid, a diester of a dicarboxylic acid and an alcohol, or the like can be used. These can be used alone or in combination of two or more. Specifically, triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-n-heptanoate, tetraethylene glycol-di-n-heptanoate Mono- or diesters of oligoalkylene glycols having hydroxyl groups at both ends, such as tri- or tetraethylene glycol, and the like; diesters of dicarboxylic acids and alcohols such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, dibutyl adipate, etc. . These plasticizers can be used alone or in combination of two or more. Two or more of these plasticizers can be used in combination.

  A resin composition obtained by radical polymerization of the radical polymerizable resin composition obtained as described above is a preferred embodiment of the present invention.

  The resin composition is useful as a ceramic molding binder or a conductive paste binder. The resin composition has a high graft ratio and excellent compatibility. When the resin composition is used as a ceramic molding binder or a conductive paste binder, a ceramic slurry or a conductive paste having excellent storage stability can be obtained. Moreover, it is excellent in the printability at the time of printing on the ceramic green sheet surface. Since the resin composition is also excellent in thermal decomposability, the amount of carbon residue in the obtained sintered body is small.

The case where a ceramic powder is molded using the resin composition as a ceramic molding binder will be described. When molding the ceramic powder, it is preferable to use a ceramic slurry containing the resin composition, the organic solvent and the ceramic powder. Examples of the ceramic powder include metal or non-metal oxide or non-oxide powder used in the production of ceramics. Specific examples thereof include Li, K, Mg, B, Al, Si, Cu, Ca, Sr, Ba, Zn, Cd, Ga, In, Y, lanthanoid, actinoid, Ti, Zr, Hf, Bi, V, and Nb. , Ta, W, Mn, Fe, Co, Ni, and other oxides, carbides, nitrides, borides, sulfides, and the like. Furthermore, when classifying specific examples of the oxide powders usually contain more metal elements referred to as double oxides from the crystal _{structure, NaNbO 3, SrZrO 3, PbZrO} 3, SrTiO 3 as taking a perovskite structure, BaZrO ₃ , PbTiO ₃ , BaTiO _{3 and the} like have a spinel structure, and MgAl ₂ O ₄ , ZnAl ₂ O ₄ , CoAl ₂ O ₄ , NiAl ₂ O ₄ , MgFe ₂ O _{4 and the} like have an ilmenite type structure Examples of MgTiO ₃ , MnTiO ₃ , and FeTiO _{3 that} have a garnet structure include GdGa ₅ O ₁₂ and Y ₆ Fe ₅ O ₁₂ . These ceramic powders may be used alone or as a mixture of two or more.

  The organic solvent contained in the ceramic slurry is not particularly limited, but alcohols such as methanol, ethanol, isopropanol, n-propanol and butanol; cellsolves such as methyl cellsolve and butylcellsolve; ketones such as acetone and methylethylketone; toluene; Aromatic hydrocarbons such as xylene; halogen-based hydrocarbons such as dichloromethane and chloroform. These can be used alone or in combination of two or more. The ceramic slurry preferably contains a plasticizer. The plasticizer is not particularly limited as long as the effects of the present invention are not impaired and there is no problem in compatibility with polyvinyl acetal. The plasticizer is not particularly limited as long as the effects of the present invention are not impaired and there is no problem in compatibility with polyvinyl acetal. As the plasticizer, a mono- or diester of an oligoalkylene glycol having a hydroxyl group at both ends and a carboxylic acid, a diester of a dicarboxylic acid and an alcohol, or the like can be used. These can be used alone or in combination of two or more. Specifically, triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-n-heptanoate, tetraethylene glycol-di-n-heptanoate Mono- or diesters of oligoalkylene glycols having hydroxyl groups at both ends, such as tri- or tetraethylene glycol, and the like; diesters of dicarboxylic acids and alcohols such as dioctyl phthalate, dibutyl phthalate, dioctyl adipate, dibutyl adipate, etc. .

  The case where the said resin composition is used as a binder for electrically conductive paste is demonstrated. When using a resin composition as a binder for electrically conductive paste, it is preferable that an electrically conductive paste contains the said resin composition, a metal powder, and an organic solvent. At this time, as the metal powder, for example, a powder of a metal having high conductivity such as nickel, palladium, platinum, gold, silver, copper, or an alloy of these metals is used. These may be used alone or in combination of two or more. The organic solvent is not particularly limited as long as it can dissolve the resin composition, and examples thereof include dihydroterpinyl acetate; α-terpineol; carbitol such as butyl carbitol; cellosolve such as butyl cellosolve and the like. It is done. The organic solvent contained in the conductive paste preferably has a boiling point of 150 ° C. or higher. When the boiling point is less than 150 ° C., for example, when screen printing is performed using a conductive paste, the viscosity of the conductive paste may increase due to evaporation of the organic solvent during printing, and printing may not be possible.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the following examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. “Polymerization degree” means “viscosity average polymerization degree”.

[Synthesis of polyvinyl acetate]
PVAc-1
A 6 L separable flask equipped with a stirrer, thermometer, nitrogen introduction tube, and reflux tube was deoxygenated in advance, and vinyl acetate monomer (VAM) 2555 g containing 500 ppm acetaldehyde (AA) and 50 ppm acetaldehyde dimethyl acetal (DMA). 945 g of methanol (MeOH) containing 50 ppm of acetaldehyde dimethyl acetal and an acetaldehyde content of less than 1 ppm; 1% methanol solution of tartaric acid in an amount of 20 ppm of tartaric acid in the vinyl acetate monomer was charged. While blowing nitrogen into the flask, the temperature inside the flask was adjusted to 60 ° C. In addition, -10 degreeC ethylene glycol / water solution was circulated through the reflux pipe. A 0.55 mass% methanol solution of di-n-propyl peroxydicarbonate was prepared, and 18.6 mL was added into the flask to initiate polymerization. The amount of di-n-propyl peroxydicarbonate added at this time was 0.081 g. A methanol solution of di-n-propyl peroxydicarbonate was sequentially added at a rate of 20.9 mL / hour until the completion of polymerization. During the polymerization, the temperature in the flask was kept at 60 ° C. Four hours after the start of polymerization, when the solid content concentration of the polymerization solution reached 25.1%, 0.0141 g of sorbic acid (3% of di-n-propyl peroxydicarbonate remaining undecomposed in the polymerization solution) was obtained. After adding 1200 g of contained methanol (corresponding to a molar equivalent), the polymerization solution was cooled to stop the polymerization. When the polymerization was stopped, the polymerization rate of the vinyl acetate monomer was 35.0%. After the polymerization solution was cooled to room temperature, the inside of the flask was depressurized using a water aspirator to distill off the vinyl acetate monomer and methanol, thereby precipitating polyvinyl acetate. 3000 g of methanol was added to the precipitated polyvinyl acetate, and the polyvinyl acetate was dissolved while heating at 30 ° C., and then the inside of the flask was decompressed again using a water aspirator to distill off the vinyl acetate monomer and methanol. Thus, polyvinyl acetate was precipitated. The operation of dissolving polyvinyl acetate in methanol and then precipitating it was further repeated twice. Methanol was added to the precipitated polyvinyl acetate to obtain a 40% by mass methanol solution of polyvinyl acetate (PVAc-1) with a vinyl acetate monomer removal rate of 99.8%.

  The polymerization degree was measured using a part of the methanol solution of PVAc-1 obtained. To a methanol solution of PVAc-1, a 10% methanol solution of sodium hydroxide was added so that the molar ratio of sodium hydroxide to vinyl acetate units in polyvinyl acetate was 0.1. When the gelled product was formed, the gel was pulverized and subjected to Soxhlet extraction with methanol for 3 days. The obtained polyvinyl alcohol was dried and subjected to viscosity average polymerization degree measurement. The degree of polymerization was 1700.

PVAc-2-18, PVAc-20
Except having changed into the conditions described in Table 1, polyvinyl acetate (PVAc-2-18, PVAc-20) was obtained by the same method as PVAc-1. In Table 1, “ND” means less than 1 ppm. The polymerization degree of each obtained polyvinyl acetate was calculated | required similarly to PVAc-1. The results are shown in Table 1.

[Synthesis of polyvinyl alcohol]
PVA-1
Water with respect to vinyl acetate monomer units in methanol and polyvinyl acetate so that the total solid concentration (saponification concentration) is 30% by mass with respect to a 40% by mass methanol solution of polyvinyl acetate of PVAc-1. An 8% methanol solution of sodium hydroxide was added with stirring so that the molar ratio of sodium oxide was 0.020, and the saponification reaction was started at 40 ° C. The gel is pulverized when the gelated product is generated as the saponification reaction proceeds, and the crushed gel is transferred to a container at 40 ° C. When 60 minutes have elapsed from the start of the saponification reaction, methanol / methyl acetate / water ( 25/70/5 mass ratio) solution and neutralized. The obtained swollen gel was centrifuged, and methanol twice as much as the swollen gel was added, immersed, left for 30 minutes, and then centrifuged four times, 60 ° C. for 1 hour, 100 It dried at 2 degreeC for 2 hours, and PVA-1 was obtained.

  The polymerization degree and saponification degree of PVA-1 were determined by the method described in JIS-K6726. The degree of polymerization was 1700, and the degree of saponification was 99.1 mol%. These physical property data are also shown in Table 2.

  After ashing PVA-1, the sodium acetate content of PVA-1 was calculated | required by measuring the amount of sodium in the obtained ash using the ICP emission-analysis apparatus "IRISAP" by Jarrel Ash. . The sodium acetate content was 0.7% (0.20% in terms of sodium). These physical property data are also shown in Table 2.

PVA-2-8, comparative PVA-1-5
Each PVA was synthesize | combined like PVA-1 except having changed into the conditions shown in Table 2. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 2.

PVA-9, comparative PVA-6-8
Each PVA was synthesized in the same manner as PVA-1, except that the conditions shown in Table 3 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 3.

PVA-10, comparative PVA-9 and 10
Each PVA was synthesized in the same manner as PVA-1 except that the conditions shown in Table 4 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 4.

PVA-11, comparative PVA-11 and 12
Each PVA was synthesized in the same manner as PVA-1 except that the conditions shown in Table 5 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 5.

Comparative PVA-13-15
Each PVA was synthesized in the same manner as PVA-1 except that the conditions shown in Table 6 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 6.

PVA-13-19, comparative PVA-16-19
Each PVA was synthesized in the same manner as PVA-1, except that the conditions were changed to those shown in Table 7. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 7.

PVA-20, comparative PVA-20 and 21
Each PVA was synthesized in the same manner as PVA-1 except that the conditions shown in Table 8 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 8.

Comparative PVA-22
Water with respect to vinyl acetate monomer units in methanol and polyvinyl acetate so that the total solid concentration (saponification concentration) is 40% by mass with respect to a 55% by mass methanol solution of polyvinyl acetate in PVAc-3. An 8% methanol solution of sodium hydroxide was added with stirring so that the molar ratio of sodium oxide was 0.005, and the saponification reaction was started at 40 ° C. Note that saponification reaction was performed by adding distilled water so that the water content in the system was 3.0%. One hour after adding the methanol solution of sodium hydroxide, 0.8 mol equivalent of 1% aqueous acetic acid and a large amount of distilled water were added to stop the saponification reaction. The obtained solution was transferred to a dryer, dried at 65 ° C. for 12 hours, and then dried at 100 ° C. for 2 hours to obtain Comparative PVA-22.

  The polymerization degree, saponification degree, and sodium acetate content of Comparative PVA-22 were measured in the same manner as PVA-1. The degree of polymerization was 300, the degree of saponification was 45.3 mol%, and the sodium acetate content was 1.2% (0.34% in terms of sodium). The results are shown in Table 8.

Comparative PVA-23
Water with respect to vinyl acetate monomer units in methanol and polyvinyl acetate so that the total solid concentration (saponification concentration) is 40% by mass with respect to a 55% by mass methanol solution of polyvinyl acetate in PVAc-3. An 8% methanol solution of sodium hydroxide was added with stirring so that the molar ratio of sodium oxide was 0.005, and the saponification reaction was started at 40 ° C. Note that saponification reaction was performed by adding distilled water so that the water content in the system was 1.2%. One hour after adding the methanol solution of sodium hydroxide, 0.8 mol equivalent of 1% aqueous acetic acid and a large amount of distilled water were added to stop the saponification reaction. The resulting solution was transferred to a dryer, dried at 65 ° C. for 12 hours, and then dried at 100 ° C. for 2 hours to obtain Comparative PVA-23.

  The degree of polymerization, the degree of saponification, and the content of sodium acetate of Comparative PVA-23 were measured in the same manner as PVA-1. The degree of polymerization was 300, the degree of saponification was 60.2 mol%, and the sodium acetate content was 1.3% (0.36% in terms of sodium). The results are shown in Table 8.

PVA-21, comparative PVA-24 and 25
Each PVA was synthesized in the same manner as PVA-1 except that the conditions shown in Table 9 were changed. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 9.

PVA-22, comparative PVA-26 and 27
Each PVA was synthesized in the same manner as PVA-1 except that the conditions were changed to those shown in Table 10. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 10.

Comparative PVA-28-30
Each PVA was synthesized in the same manner as PVA-1, except that the conditions were changed to those shown in Table 11. The polymerization degree, saponification degree, and sodium acetate content (in terms of sodium mass) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 11.

Example 1
A 10-liter glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-1 (PVA concentration 7.5%), and the content was raised to 95 ° C. Warm to completely dissolve the PVA. Next, the contents are gradually cooled to 10 ° C. over about 30 minutes while stirring at 120 rpm, and then 384 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 150 minutes. It was. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, the resin was washed again with ion-exchanged water and dried to obtain polyvinyl butyral (PVB-1).

(Composition of polyvinyl butyral)
The degree of butyralization (degree of acetalization) of polyvinyl butyral, the content of vinyl acetate monomer units, and the content of vinyl alcohol monomer units were measured according to JIS K6728. The resulting polyvinyl butyral has a butyralization degree (acetalization degree) of 68.2 mol%, a vinyl acetate monomer unit content of 0.9 mol%, and a vinyl alcohol monomer unit content of 30. It was 9 mol%. The results are also shown in Table 12.

[GPC measurement of PVB]
(measuring device)
GPC measurement was performed using “GPCmax” manufactured by VISCOTECH. As a differential refractive index detector, “TDA305” manufactured by VISCOTECH was used. “UV Detector 2600” manufactured by VISCOTECH was used as an ultraviolet-visible absorption detector. The optical path length of the detection cell of the absorptiometric detector is 10 mm. “GPC HFIP-806M” manufactured by Showa Denko KK was used for the GPC column. Moreover, OmniSEC (Version 4.7.0.406) attached to the apparatus was used as analysis software.

(Measurement condition)
As the mobile phase, HFIP containing 20 mmol / l sodium trifluoroacetate was used. The mobile phase flow rate was 1.0 ml / min. The sample injection amount was 100 μl, and measurement was performed at a GPC column temperature of 40 ° C.

In addition, the sample in which the viscosity average polymerization degree of PVA exceeded 2400 performed GPC measurement using the sample (100 microliters) diluted suitably. The absorbance at a sample concentration of 1.00 mg / ml was calculated from the measured value according to the following formula. α (mg / ml) is the concentration of the diluted sample.

Absorbance at a sample concentration of 1.00 mg / ml = (1.00 / α) × measured value of absorbance

(Create a calibration curve)
As a standard, PMMA (peak top molecular weight: 1944000, 790000, 467400, 271400, 144000, 79250, 35300, 13300, 7100, 1960, 1020, 690) manufactured by Agilent Technologies was measured, and a differential refractive index detector and absorbance were measured. A calibration curve for converting the elution volume into the PMMA molecular weight was prepared for each detector. The analytical software was used to create each calibration curve. In this measurement, a column in a state where the peaks of standard samples having both molecular weights of 1944000 and 271400 can be separated in the PMMA measurement is used.

  In this apparatus, the peak intensity obtained from the differential refractive index detector is expressed in mV (millivolt), and the peak intensity obtained from the absorptiometric detector is expressed in absorbance (abs unit: Absorbance unit).

(Sample preparation)
The sample prepared by the above method was dissolved in HFIP containing 20 mmol / l sodium trifluoroacetate to prepare a 1.00 mg / ml solution of PVB. The solution was filtered through a 0.45 μm polytetrafluoroethylene filter and used for measurement.

  The obtained powdery PVB-1 was hot-pressed at a pressure of 2 MPa and 230 ° C. for 3 hours to obtain a heated polyvinyl acetal (film). At this time, the thickness of the film was 760 μm. This was used for GPC measurement.

The obtained sample was subjected to GPC measurement by the above method. FIG. 1 is a graph showing the relationship between the molecular weight and the value measured with a differential refractive index detector, and the relationship between the molecular weight and the absorbance measured with an absorptiometric detector (measurement wavelength 280 nm). The molecular weight at this time is one converted from the elution volume using a calibration curve (PMMA equivalent molecular weight). The peak top molecular weight (A) measured with the differential refractive index detector obtained from FIG. 1 was 90000, and the peak top molecular weight (B) measured with the absorptiometric detector (280 nm) was 68900. The obtained value is expressed by the following formula (AB) / A
The value obtained by substituting for was 0.23. The absorbance (b) at the peak top molecular weight (B) was 2.21 × 10 ⁻³ . The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn obtained from the chromatogram (RI) in FIG. 1 was 3.4. These results are also shown in Table 12.

(Preparation of radical polymerizable resin composition)
50 g of polyvinyl acetal (PVB-1) is dissolved in 100 g of methyl ethyl ketone (MEK), 50 g of 2-hydroxyethyl acrylate (HEA) is added to the resulting solution, and 0.1 g of azobisisobutyronitrile (AIBN) is used as a polymerization initiator. Was added to obtain a radical polymerizable resin composition.

  Radical polymerization was started by heating the radical polymerizable resin composition to 70 ° C. under a nitrogen stream. Six hours after the start of polymerization, the reaction solution was cooled to room temperature to terminate the polymerization, and a resin composition was obtained.

(Resin composition film formation)
This resin composition was applied to a polyethylene terephthalate film and dried at 80 ° C. for 3 hours to obtain a film of the resin composition.

(Compatibility evaluation)
By measuring the transparency of the film of the obtained resin composition, the compatibility between the polyvinyl acetal component and the polymer component obtained by polymerizing the radical polymerizable monomer was evaluated. The evaluation of transparency was performed by measuring the haze of the film of the resin composition in accordance with JIS K7105. The evaluation criteria are as follows.
Evaluation A: Haze less than 1.0% Evaluation B: Haze 1.0% or more and less than 3.0% Evaluation C: Haze 3.0% or more The haze of the film of the resin composition of the present invention is JIS K7361-1. Based on the prescribed measurement method, it is automatically measured as haze measured using a turbidimeter “NDH-1001DP” manufactured by Nippon Denshoku Industries Co., Ltd. = (Diffuse light / total transmitted light) × 100 (%). .

(Carbon residue)
The carbon residue of the resin composition film was evaluated by baking in a platinum pan using TA INSTRUMENTS Q5000IR and measuring the resin portion residue ratio. The evaluation criteria are as follows.
Evaluation A: Resin residue ≦ 0.02 wt%
Evaluation B: 0.02 wt% <residue of resin portion ≦ 0.05 wt%
Evaluation C: 0.05 wt% <resin residue ≦ 0.10 wt%
<Measurement conditions>
Temperature increase rate: 10 ° C./min Atmosphere: in nitrogen (100 ml / min)
Measurement start temperature: 30 ° C
Measurement end temperature: 450 ° C

Examples 2-8
Polyvinyl butyral was synthesized in the same manner as in Example 1 except that the raw material PVA was changed to that shown in Table 12. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Example 9
Polyvinyl butyral was synthesized in the same manner as in Example 1 except that the amount of n-butyraldehyde added was changed to 320 g. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Example 10
Polyvinyl butyral was synthesized in the same manner as in Example 1 except that the amount of n-butyraldehyde added was changed to 362 g. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Example 11
Polyvinyl butyral was synthesized in the same manner as in Example 1 except that the amount of n-butyraldehyde added was changed to 449 g. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Comparative Example 1
Polyvinyl butyral was synthesized in the same manner as in Example 1 except that the amount of n-butyraldehyde added was changed to 271 g. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Comparative Example 2
A 10-liter glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-1 (PVA concentration 7.5%), and the content was raised to 95 ° C. Warm to completely dissolve the PVA. Next, the contents are gradually cooled to 10 ° C. over about 30 minutes while stirring at 120 rpm, and then 740 g of n-butyraldehyde and 810 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 150 minutes. It was. Thereafter, the temperature was raised to 80 ° C. over 90 minutes, kept at 80 ° C. for 16 hours, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, the resin was washed again with ion-exchanged water and then dried to obtain polyvinyl butyral. Using the obtained polyvinyl butyral, a radical polymerizable resin composition and a resin composition were prepared in the same manner as in Example 1, and then a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Comparative Examples 3-7
Polyvinyl butyral was synthesized in the same manner as in Example 1 except that the raw material PVA was changed to that shown in Table 12. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Comparative Example 8
Polyvinyl butyral was synthesized in the same manner as in Example 9 except that the raw material PVA was changed to comparative PVA-1 and the addition amount of n-butyraldehyde was changed to 271 g. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Comparative Example 9
Polyvinyl butyral was synthesized in the same manner as in Example 9 except that the raw material PVA was changed to comparative PVA-1. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Comparative Example 10
Polyvinyl butyral was synthesized in the same manner as in Example 1211 except that the raw material PVA was changed to comparative PVA-1. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Comparative Example 11
Polyvinyl butyral was synthesized in the same manner as in Comparative Example 8 except that the raw material PVA was changed to Comparative PVA-2. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Comparative Example 12
Polyvinyl butyral was synthesized in the same manner as in Example 9 except that the raw material PVA was changed to comparative PVA-2. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

Comparative Example 13
Polyvinyl butyral was synthesized in the same manner as in Example 11 except that the raw material PVA was changed to comparative PVA-2. And after using the obtained polyvinyl butyral to prepare a radical polymerizable resin composition and a resin composition in the same manner as in Example 1, a film was formed and evaluated in the same manner as in Example 1. The results are shown in Table 12.

  Table 12 shows the evaluation results of the radical polymerizable resin composition containing polyvinyl acetal using a completely saponified PVA having a polymerization degree of 1700 as a raw material. A film obtained by drying a resin composition obtained by polymerizing a radical polymerizable resin composition satisfying the conditions specified in the present invention is obtained by polymerizing a polyvinyl acetal component and a radical polymerizable monomer. The compatibility with the polymer component was good, and the amount of carbon residue was small (Examples 1 to 11). On the other hand, the film obtained by drying the resin composition obtained by polymerizing the radical polymerizable resin composition that does not satisfy the conditions specified in the present invention had insufficient performance (Comparative Example). 1-13).

Example 12
A 10-liter glass container equipped with a reflux condenser, thermometer, and squid-type stirring blade is charged with 8100 g of ion-exchanged water and 660 g of PVA-9 (PVA concentration 7.5%), and the contents are heated to 95 ° C. Thus, the PVA was completely dissolved. Next, the contents were gradually cooled to 1 ° C. over about 30 minutes while stirring at 120 rpm, and then 422 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to the vessel, and a butyralization reaction was performed for 120 minutes. It was. Thereafter, the temperature was raised to 45 ° C. over 60 minutes, held at 45 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral.

  The composition of the obtained polyvinyl butyral was measured in the same manner as in Example 1. The degree of butyralization (degree of acetalization) was 68.1 mol%, the content of vinyl acetate monomer units was 1.1 mol%, and the content of vinyl alcohol monomer units was 30.8 mol%. It was. Next, the polyvinyl butyral obtained in the same manner as in Example 1 was evaluated (GPC measurement) and the compatibility was evaluated to measure the amount of carbon residue. The results are shown in Table 13.

Comparative Examples 14-16
Polyvinyl butyral was synthesized in the same manner as in Example 12 except that the raw material PVA was changed to that shown in Table 13. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, the resin composition obtained by polymerizing this was dried to form a film. Evaluation similar to Example 1 was performed. The results are shown in Table 13.

  Table 13 shows a film obtained by drying a resin composition obtained by polymerizing a radically polymerizable resin composition containing polyvinyl acetal using a fully saponified PVA having a polymerization degree of 300 or 150 as a raw material, The compatibility between the polyvinyl acetal component and the polymer component obtained by polymerizing the radical polymerizable monomer was good, and the amount of carbon residue was small (Example 12). On the other hand, the film obtained by drying the resin composition obtained by polymerizing the radical polymerizable resin composition that does not satisfy the conditions specified in the present invention had insufficient performance (Comparative Example). 14 and 15). Moreover, when the degree of polymerization was smaller than the lower limit specified in the present invention, any performance was insufficient (Comparative Example 16).

Example 13
A 10-liter glass container equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-10 (PVA concentration 7.5%), and the contents were raised to 95 ° C. Warm to completely dissolve the PVA. Next, after gradually cooling to 5 ° C. over about 30 minutes with stirring at 120 rpm, 402 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to carry out a butyralization reaction for 120 minutes. Thereafter, the temperature was raised to 50 ° C. over 60 minutes, held at 50 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral.

  The composition of the obtained polyvinyl butyral was measured in the same manner as in Example 1. The resulting polyvinyl butyral has a butyralization degree (acetalization degree) of 68.5 mol%, a vinyl acetate monomer unit content of 1.5 mol%, and a vinyl alcohol monomer unit content of 30. 0.0 mol%. Next, the polyvinyl butyral obtained in the same manner as in Example 1 was evaluated (GPC measurement) and the compatibility was evaluated to measure the amount of carbon residue. The results are shown in Table 14.

Comparative Examples 17 and 18
Polyvinyl butyral was synthesized in the same manner as in Example 13 except that the raw material PVA was changed to that shown in Table 14. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, the resin composition obtained by polymerizing this was dried to form a film. Evaluation similar to Example 1 was performed. The results are shown in Table 14.

  Table 14 shows the evaluation results of the radical polymerizable resin composition containing polyvinyl acetal using a fully saponified PVA having a polymerization degree of 500 as a raw material. A film obtained by drying a resin composition obtained by polymerizing a radical polymerizable resin composition satisfying the conditions specified in the present invention is obtained by polymerizing a polyvinyl acetal component and a radical polymerizable monomer. The compatibility with the polymer component was good, and the amount of carbon residue was small (Example 13). On the other hand, the film obtained by drying the resin composition obtained by polymerizing the radical polymerizable resin composition that does not satisfy the conditions specified in the present invention had insufficient performance (Comparative Example). 17 and 18).

Example 14
Into a 10-liter glass container equipped with a reflux condenser, thermometer, and squid type stirring blade, 8234 g of ion-exchanged water and 526 g of PVA-11 were charged (PVA concentration 6.0%), and the content was raised to 95 ° C. Warm to dissolve completely. Next, the contents are gradually cooled to 15 ° C. over about 30 minutes while stirring at 120 rpm, and then 307 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 120 minutes. It was. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral. The resulting polyvinyl butyral has a butyralization degree (acetalization degree) of 68.2 mol%, a vinyl acetate monomer unit content of 1.3 mol%, and a vinyl alcohol monomer unit content of 30. It was 5 mol%.

  The composition of the obtained polyvinyl butyral was measured in the same manner as in Example 1. The degree of butyralization (degree of acetalization) was 68.2 mol%, the content of vinyl acetate monomer units was 1.3 mol%, and the content of vinyl alcohol monomer units was 30.5 mol%. It was. Next, the polyvinyl butyral obtained in the same manner as in Example 1 was evaluated (GPC measurement) and the compatibility was evaluated to measure the amount of carbon residue. The evaluation results are shown in Table 15.

Comparative Examples 19 and 20
Polyvinyl butyral was synthesized in the same manner as in Example 14 except that the raw material PVA was changed to that shown in Table 15. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 15.

  Table 15 shows the evaluation results of the radical polymerizable resin composition containing polyvinyl acetal using a fully saponified PVA having a polymerization degree of 2400 as a raw material. A film obtained by drying a resin composition obtained by polymerizing a radical polymerizable resin composition satisfying the conditions specified in the present invention is obtained by polymerizing a polyvinyl acetal component and a radical polymerizable monomer. The compatibility with the polymer component was good, and the amount of carbon residue was small (Example 14). On the other hand, the film obtained by drying the resin composition obtained by polymerizing the radical polymerizable resin composition that does not satisfy the conditions specified in the present invention had insufficient performance (Comparative Example). 19 and 20).

Comparative Example 21
A 10-liter glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8322 g of ion-exchanged water and 438 g of comparative PVA-13 (PVA concentration: 5.0%), and the contents were adjusted to 95 ° C. The PVA was completely dissolved by raising the temperature. Next, the contents are gradually cooled to 20 ° C. over about 30 minutes while stirring at 120 rpm, and then 256 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 120 minutes. It was. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral.

  The composition of the obtained polyvinyl butyral was measured in the same manner as in Example 1. The degree of butyralization (degree of acetalization) was 68.1 mol%, the content of vinyl acetate monomer units was 1.5 mol%, and the content of vinyl alcohol monomer units was 30.4 mol%. It was. Next, the polyvinyl butyral obtained in the same manner as in Example 1 was evaluated (GPC measurement) and the compatibility was evaluated to measure the amount of carbon residue. The evaluation results are shown in Table 16.

Comparative Examples 22 and 23
Polyvinyl butyral was synthesized in the same manner as in Comparative Example 21 except that the raw material PVA was changed to that shown in Table 16. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 16.

  Table 16 shows the evaluation results of the radical polymerizable resin composition containing polyvinyl acetal using a fully saponified PVA having a polymerization degree of 3600 as a raw material. When the degree of polymerization is larger than the upper limit specified in the present invention (Comparative Examples 21 to 23), the film obtained by drying the composition obtained by polymerizing the radical polymerizable resin composition is free from the polymerization with the polyvinyl acetal component. The performance of either the compatibility with the polymer component obtained or the amount of carbon residue was insufficient.

Example 16
A 10 liter glass container equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-13 (PVA concentration 7.5%), and the contents were raised to 95 ° C. Warm to dissolve completely. Next, the contents are gradually cooled to 15 ° C. over about 30 minutes while stirring at 120 rpm. Then, 432 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 90 minutes. It was. Thereafter, the temperature was raised to 45 ° C. over 30 minutes, held at 45 ° C. for 180 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral.

  The composition of the obtained polyvinyl butyral was measured in the same manner as in Example 1. The degree of butyralization (degree of acetalization) was 74.1 mol%, the content of vinyl acetate monomer units was 8.1 mol%, and the content of vinyl alcohol monomer units was 17.8 mol%. It was. Next, the polyvinyl butyral obtained in the same manner as in Example 1 was evaluated (GPC measurement) and the compatibility was evaluated to measure the amount of carbon residue. The results are shown in Table 13. The results are shown in Table 17.

Examples 17-22
Polyvinyl butyral was synthesized in the same manner as in Example 16 except that the raw material PVA was changed to that shown in Table 17. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Example 23
Polyvinyl butyral was synthesized in the same manner as in Example 16 except that the amount of n-butyraldehyde added was changed to 269 g. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Example 24
Polyvinyl butyral was synthesized in the same manner as in Example 16 except that the amount of n-butyraldehyde added was changed to 307 g. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Example 25
Polyvinyl butyral was synthesized in the same manner as in Example 16 except that the amount of n-butyraldehyde added was changed to 458 g. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Comparative Example 24
Polyvinyl butyral was synthesized in the same manner as in Example 16 except that the addition amount of n-butyraldehyde was changed to 225 g. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Comparative Example 25
A 10 liter glass container equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-13 (PVA concentration 7.5%), and the contents were raised to 95 ° C. Warm to dissolve completely. Next, the contents are gradually cooled to 15 ° C. over about 30 minutes while stirring at 120 rpm, 837 g of n-butyraldehyde and 810 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 90 minutes. It was. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, kept at 60 ° C. for 24 hours, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral. Using the obtained polyvinyl butyral, a radical polymerizable resin composition was prepared in the same manner as in Example 1, and then the resin composition obtained by polymerizing this was dried to form a film obtained. Evaluation similar to Example 1 was performed. The results are shown in Table 17.

Comparative Examples 26-29
Polyvinyl butyral was synthesized in the same manner as in Example 16 except that the raw material PVA was changed to that shown in Table 17. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Comparative Example 30
Polyvinyl butyral was synthesized in the same manner as in Example 16 except that the raw material PVA was changed to comparative PVA-16 and the amount of n-butyraldehyde added was changed to 225 g. Using the obtained polyvinyl butyral, a radical polymerizable resin composition was prepared in the same manner as in Example 1, and then the resin composition obtained by polymerizing this was dried to form a film obtained. Evaluation similar to Example 1 was performed. The results are shown in Table 17.

Comparative Example 31
Polyvinyl butyral was synthesized in the same manner as in Example 23 except that the raw material PVA was changed to Comparative PVA-16. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Comparative Example 32
Polyvinyl butyral was synthesized in the same manner as in Example 25 except that the raw material PVA was changed to Comparative PVA-16. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Comparative Example 33
Polyvinyl butyral was synthesized in the same manner as in Example 16 except that the raw material PVA was changed to Comparative PVA-17 and the addition amount of n-butyraldehyde was changed to 225 g. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Comparative Example 34
Polyvinyl butyral was synthesized in the same manner as in Example 23 except that the raw material PVA was changed to Comparative PVA-17. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

Comparative Example 35
Polyvinyl butyral was synthesized in the same manner as in Example 25 except that the raw material PVA was changed to Comparative PVA-17. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 17.

  Table 17 shows the evaluation results of the radical polymerizable resin composition containing polyvinyl acetal using a partially saponified PVA having a polymerization degree of 1700 (saponification degree: about 88 mol%) as a raw material. A film obtained by drying a resin composition obtained by polymerizing a radical polymerizable resin composition that satisfies the conditions specified in the present invention is obtained by polymerizing a polyvinyl acetal component and a radical polymerization monomer. Thus, the compatibility with the polymer component obtained was good and the amount of carbon residue was small (Examples 16 to 25). On the other hand, a film obtained by drying a resin composition obtained by polymerizing a radical polymerizable resin composition that does not satisfy the conditions specified in the present invention has insufficient performance. (Comparative Examples 24-35).

Example 26
A 10-liter glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8100 g of ion-exchanged water and 660 g of PVA-20 (PVA concentration 7.5%), and the contents were raised to 95 ° C. Warm to completely dissolve the PVA. Next, the contents were gradually cooled to 1 ° C. over about 60 minutes while stirring at 120 rpm, and then 468 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to the vessel, and a butyralization reaction was performed for 90 minutes. It was. Thereafter, the temperature was raised to 25 ° C. over 30 minutes, held at 25 ° C. for 180 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral.

  The composition of the obtained polyvinyl butyral was measured in the same manner as in Example 1. The degree of butyralization (degree of acetalization) was 73.2 mol%, the content of vinyl acetate monomer units was 8.0 mol%, and the content of vinyl alcohol monomer units was 18.8 mol%. It was. Next, the polyvinyl butyral obtained in the same manner as in Example 1 was evaluated (GPC measurement) and the compatibility was evaluated to measure the amount of carbon residue. The evaluation results are shown in Table 18.

Comparative Examples 36 and 37
Polyvinyl butyral was synthesized in the same manner as in Example 26 except that the raw material PVA was changed to that shown in Table 18. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 18.

Comparative Example 38
Polyvinyl butyral was synthesized in the same manner as in Example 26 except that the raw material PVA was changed to Comparative PVA-23. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 18.

  Table 18 shows the evaluation results of the radical polymerizable resin composition containing polyvinyl acetal using partially saponified PVA having a polymerization degree of 300 as a raw material. A film obtained by drying a resin composition obtained by polymerizing a radical polymerizable resin composition satisfying the conditions specified in the present invention comprises a polyvinyl acetal component and a radical polymerizable monomer. The compatibility with the polymer component obtained by polymerization was good and the amount of carbon residue was small (Example 26). On the other hand, the film obtained by drying the resin composition obtained by polymerizing the radical polymerizable resin composition that does not satisfy the conditions specified in the present invention had insufficient performance (Comparative Example). 36-38).

Example 27
A 10 L liter glass container equipped with a reflux condenser, thermometer and squid type stirring blade was charged with 8100 g of ion exchange water and 660 g of PVA-21 (PVA concentration 7.5%), and the contents were raised to 95 ° C. Warm to completely dissolve the PVA. Next, the contents were gradually cooled to 5 ° C. over about 60 minutes while stirring at 120 rpm, and then 450 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid were added to the vessel, and a butyralization reaction was performed for 90 minutes. It was. Thereafter, the temperature was raised to 30 ° C. over 30 minutes, held at 30 ° C. for 180 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral.

  The composition of the obtained polyvinyl butyral was measured in the same manner as in Example 1. The degree of butyralization (degree of acetalization) was 74.3 mol%, the content of vinyl acetate monomer units was 7.9 mol%, and the content of vinyl alcohol monomer units was 17.8 mol%. It was. Next, the polyvinyl butyral obtained in the same manner as in Example 1 was evaluated (GPC measurement) and the compatibility was evaluated to measure the amount of carbon residue. The results are shown in Table 19.

Comparative Examples 39 and 40
Polyvinyl butyral was synthesized in the same manner as in Example 27 except that the raw material PVA was changed to that shown in Table 19. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 19.

  Table 19 shows the evaluation results of the radical polymerizable resin composition containing polyvinyl acetal using a partially saponified PVA having a polymerization degree of 500 (saponification degree of about 88 mol%) as a raw material. A film obtained by drying a resin composition obtained by polymerizing a radical polymerizable resin composition satisfying the conditions specified in the present invention is obtained by polymerizing a polyvinyl acetal component and a radical polymerizable monomer. The compatibility with the polymer component was good, and the amount of carbon residue was small (Example 27). On the other hand, the film obtained by drying the resin composition obtained by polymerizing the radical polymerizable resin composition that does not satisfy the conditions specified in the present invention had insufficient performance (Comparative Example). 39 and 40).

Example 28
A 10L liter glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8234g of ion-exchanged water and 526g of PVA-22 (PVA concentration 6.0%), and the contents were raised to 95 ° C. Warm to completely dissolve the PVA. Next, the contents are gradually cooled to 15 ° C. over about 60 minutes while stirring at 120 rpm, and then 344 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 90 minutes. It was. Thereafter, the temperature was raised to 45 ° C. over 30 minutes, held at 45 ° C. for 180 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral.

  The composition of the obtained polyvinyl butyral was measured in the same manner as in Example 1. The degree of butyralization (degree of acetalization) was 74.6 mol%, the content of vinyl acetate monomer units was 8.3 mol%, and the content of vinyl alcohol monomer units was 17.1 mol%. It was. Next, the polyvinyl butyral obtained in the same manner as in Example 1 was evaluated (GPC measurement) and the compatibility was evaluated to measure the amount of carbon residue. The results are shown in Table 20.

Comparative Examples 41 and 42
Polyvinyl butyral was synthesized in the same manner as in Example 28 except that the raw material PVA was changed to that shown in Table 20. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 20.

  Table 20 shows the evaluation results of the radical polymerizable resin composition containing polyvinyl acetal using a partially saponified PVA having a polymerization degree of 2400 (saponification degree of about 88 mol%) as a raw material. A film obtained by drying a resin composition obtained by polymerizing a radical polymerizable resin composition satisfying the conditions specified in the present invention is obtained by polymerizing a polyvinyl acetal component and a radical polymerizable monomer. The compatibility with the polymer component was good, and the amount of carbon residue was small (Example 28). On the other hand, the film obtained by drying the resin composition obtained by polymerizing the radical polymerizable resin composition that does not satisfy the conditions specified in the present invention had insufficient performance (Comparative Example). 41 and 42).

Comparative Example 43
A 10-liter glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 8234 g of ion-exchanged water and 438 g of comparative PVA-28 (PVA concentration: 5.0%), and the content was adjusted to 95 ° C. The PVA was completely dissolved by raising the temperature. Next, the contents are gradually cooled to 15 ° C. over about 60 minutes while stirring at 120 rpm, and then 265 g of n-butyraldehyde and 540 mL of 20% hydrochloric acid are added to the vessel, and a butyralization reaction is performed for 90 minutes. It was. Thereafter, the temperature was raised to 45 ° C. over 30 minutes, held at 45 ° C. for 180 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water and then neutralized by adding an excessive amount of aqueous sodium hydroxide solution. Subsequently, it was rewashed with ion-exchanged water and dried to obtain polyvinyl butyral.

  The composition of the obtained polyvinyl butyral was measured in the same manner as in Example 1. The degree of butyralization (average degree of acetalization) of polyvinyl butyral is 73.2 mol%, the content of vinyl acetate monomer units is 8.1 mol%, and the content of vinyl alcohol monomer units is 18.7. Mol%. Next, the polyvinyl butyral obtained in the same manner as in Example 1 was evaluated (GPC measurement) and the compatibility was evaluated to measure the amount of carbon residue. The results are shown in Table 21.

Comparative Examples 44 and 45
Polyvinyl butyral was synthesized in the same manner as in Comparative Example 43 except that the raw material PVA was changed to that shown in Table 21. Then, using the obtained polyvinyl butyral, after preparing a radical polymerizable resin composition in the same manner as in Example 1, a film obtained by drying the resin composition obtained by polymerizing this was formed. The same evaluation as in Example 1 was performed. The results are shown in Table 21.

  Table 21 shows the evaluation results of the radical polymerizable resin composition containing polyvinyl acetal using partially saponified PVA having a polymerization degree of 3600 (saponification degree of about 88 mol%) as a raw material. A film obtained by drying a resin composition obtained by polymerizing a radical polymerizable resin composition that does not satisfy the conditions specified in the present invention is obtained by polymerizing a polyvinyl acetal component and a radical polymerizable monomer. Any of the compatibility with the obtained polymer component and the amount of carbon residue was insufficient (Comparative Examples 43 to 45).

  As shown from the above results, the film obtained by drying the resin composition obtained by polymerizing the radical polymerizable resin composition satisfying the conditions specified in the present invention is composed of the polyvinyl acetal component and the radical polymerizable monomer. The compatibility with the polymer component obtained by polymerizing the monomer was good and the amount of carbon residue was small. On the other hand, the film obtained by drying a resin composition obtained by polymerizing a radically polymerizable resin composition that does not satisfy the conditions defined in the present invention clearly has insufficient performance.

Claims (6)

The degree of acetalization is 50 to 85 mol%, the content of vinyl ester monomer units is 0.1 to 20 mol%, the viscosity average polymerization degree is 200 to 3000, and the following formulas (1) and (2) are satisfied. Containing polyvinyl acetal, a radical polymerizable monomer and a radical polymerization initiator,
Content of the said radically polymerizable monomer is 5-500 mass parts with respect to 100 mass parts of polyvinyl acetals, The radically polymerizable resin composition characterized by the above-mentioned.
(AB) / A <0.60 (1)
0.50 × 10 ⁻³ ≦ b ≦ 1.00 × 10 ⁻² (2)
A: Peak top molecular weight measured with a differential refractive index detector when the polyvinyl acetal heated at 230 ° C. for 3 hours was measured by gel permeation chromatography B: The polyvinyl acetal heated at 230 ° C. for 3 hours Peak top molecular weight (B) measured with an absorptiometric detector (measurement wavelength 280 nm) when measured by gel permeation chromatography
b: Absorbance at peak top molecular weight (B)   The radically polymerizable resin composition according to claim 1, wherein the radically polymerizable monomer contains (meth) acrylate.   The ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the polyvinyl acetal obtained by a differential refractive index detector in the gel permeation chromatography measurement is 2.8 to 12.0. 2. The radical polymerizable resin composition according to 2.   The radical polymerizable resin composition according to claim 1, wherein the polyvinyl acetal is polyvinyl butyral.   The resin composition obtained by radical-polymerizing the radically polymerizable resin composition in any one of Claims 1-4.   A ceramic molding binder or a conductive paste binder comprising the resin composition according to claim 5.

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