WO2015125689A1 - ポリビニルアセタール溶液からなる接着性改良剤 - Google Patents

ポリビニルアセタール溶液からなる接着性改良剤 Download PDF

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WO2015125689A1
WO2015125689A1 PCT/JP2015/053845 JP2015053845W WO2015125689A1 WO 2015125689 A1 WO2015125689 A1 WO 2015125689A1 JP 2015053845 W JP2015053845 W JP 2015053845W WO 2015125689 A1 WO2015125689 A1 WO 2015125689A1
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polyvinyl acetal
molecular weight
solution
vinyl
measured
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PCT/JP2015/053845
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English (en)
French (fr)
Japanese (ja)
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夕陽 島住
楠藤　健
徳地　一記
芳聡 浅沼
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株式会社クラレ
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2429/00—Presence of polyvinyl alcohol

Definitions

  • the present invention relates to an adhesion improver composed of a solution containing polyvinyl acetal, a molded body on which it is applied, and a laminate with an adherend.
  • Polyvinyl acetal resin is dissolved in various organic solvents and used in various adhesives, coating materials, paints, and the like. At this time, in consideration of handling properties in solution (solution viscosity, etc.), the use of a polyacetal resin having a low molecular weight as much as possible improves the initial adhesion, but the mechanical strength of the formed coating film after solvent volatilization and There is a problem that heat resistance is lowered. On the other hand, if a high molecular weight polyacetal resin is used to improve mechanical strength and heat resistance, the solution viscosity increases and handling becomes difficult, and a large amount of solvent needs to be used to reduce the viscosity. There is a problem.
  • Patent Document 1 discloses a saponification degree of 70 to 96 mol%.
  • a printing ink and a paint containing a polyvinyl butyral resin made from polyvinyl alcohol having a raw material are disclosed.
  • polyvinyl acetal resin is an adhesive.
  • an adhesive mainly composed of a polyvinyl acetal resin and a thermosetting resin such as a phenol resin, an epoxy resin, or a melamine resin has been widely used as an adhesive for printed circuit boards.
  • a printed circuit board is usually composed of a laminate composed of copper foil, phenol-impregnated paper, and an adhesive that bonds them, and the desired surface is obtained by etching the copper on the surface of the copper-clad laminate.
  • a printed circuit board on which a printed circuit is formed can be obtained.
  • adhesives that constitute printed circuit boards are required to have superior heat resistance compared to conventional adhesives, and in particular, improved adhesion strength of copper foil at high temperatures, that is, peeling strength of copper foil Improvement is strongly desired.
  • polyvinyl acetal is widely used as a binder for ceramic molding.
  • multilayer ceramic capacitors are required to have a large capacity and a small size.
  • the ceramic powder used in the ceramic green sheet has a fine particle size of 0.5 ⁇ m or less, and is coated on a peelable support in a thin film shape of 5 ⁇ m or less. Attempts have been made.
  • a multilayer ceramic capacitor an electrode layer is formed on a green sheet, and a green sheet with an electrode layer formed or a green sheet without an electrode layer is stacked to obtain a composite laminate.
  • resin products other than metal and glass are widely used for automobile exterior parts.
  • resin molded products are often used for bumpers, door mirror covers, moldings, spoilers, and the like.
  • an polyolefin resin material is used more and more than a urethane resin from the economical aspect.
  • Polyolefin resins are excellent in chemical resistance, water resistance, moldability, and the like.
  • a polyolefin resin material has low polarity and therefore has poor adhesion of a coating film.
  • the styrenic thermoplastic resin composition is also a material having low polarity, it is inferior in adhesiveness with a highly polar resin and is difficult to melt and bond. Therefore, in order to adhere a styrene thermoplastic resin or olefin thermoplastic resin to a highly polar resin, it is necessary to apply an adhesive or to treat the surface in advance.
  • Patent Document 2 by adding a specific molecular weight and molecular weight distribution to a polyvinyl acetal resin used for adhesives, coating materials, paints, etc., adhesive properties, heat resistance, inorganic dispersibility, solution physical properties, Polyvinyl acetal resins having excellent coating film properties are described. However, it does not mention the quality of the solution, such as the storage stability of the solution and foreign matters.
  • the object of the present invention is that the amount of foreign matter as a polyvinyl acetal solution is small, and the storage stability of the solution is excellent, and after application, it has excellent adhesion to an adherend and a coating film.
  • An object of the present invention is to provide an adhesion improver comprising a polyvinyl acetal solution having excellent stability after bonding. Furthermore, the objective of this invention is providing the molded object and laminated body which use this adhesive improvement agent.
  • An adhesion improver comprising a solution comprising polyvinyl acetal;
  • the polyvinyl acetal has an acetalization degree of 50 to 85 mol%, a vinyl ester monomer unit content of 0.1 to 20 mol%, a viscosity average polymerization degree of 200 to 5000, and heated at 230 ° C. for 3 hours.
  • the peak top molecular weight (A) measured with a differential refractive index detector and the peak top molecular weight measured with an absorptiometric detector (measurement wavelength 280 nm) ( B) is the following formula (1) (AB) / A ⁇ 0.60 (1) And having an absorbance at peak top molecular weight (B) of 0.50 ⁇ 10 ⁇ 3 to 1.00 ⁇ 10 ⁇ 2 .
  • hexafluoroisopropanol may be abbreviated as HFIP.
  • Sample concentration 1.00 mg / ml
  • Sample injection volume 100 ⁇ l
  • Absorbance detector cell length 10 mm It is.
  • 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.
  • An adhesion improver in which the polyvinyl acetal has a functional group selected from an amide group, an amino group, an ester group, a carbonyl group, and a vinyl group in the side chain is also a preferred embodiment of the present invention.
  • An adhesion improver in which the functional group of the polyvinyl acetal is an amide group or an amino group is also a preferred embodiment of the present invention.
  • a molded body obtained by applying the adhesive property improving agent on a substrate and forming a film is also a preferred embodiment of the present invention.
  • a molded body formed by irradiating plasma on at least a part of the coated polyvinyl acetal surface is also a preferred embodiment of the present invention.
  • a laminate formed by adhering an adherend to the molded body is also a preferred embodiment of the present invention.
  • the adhesion improver of the present invention has a small amount of foreign matter, excellent storage stability of the solution, and has excellent adhesion to the adherend after application, for adhesion stability after adhesion to the adherend. Excellent.
  • Example 1 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.
  • RI differential refractive index detector
  • UV absorptiometric detector
  • the polyvinyl acetal contained in the polyvinyl acetal solution constituting the adhesion improver 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.
  • the peak top molecular weight (B) measured with an absorptiometric detector (measurement wavelength: 280 nm) is expressed by the following formula (1) (AB) / A ⁇ 0.60 (1)
  • the absorbance at the peak top molecular weight (B) is 0.50 ⁇ 10 ⁇ 3 to 1.00 ⁇ 10 ⁇ 2 .
  • 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).
  • polyvinyl acetal detected by an absorptiometric detector is only one having absorption at a predetermined wavelength.
  • 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.
  • standard PMMA monodisperse PMMA
  • 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.
  • 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.
  • 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.
  • the polyvinyl acetal Before the GPC measurement, the polyvinyl acetal is heated at 230 ° C. for 3 hours.
  • polyvinyl acetal is heated by the following method.
  • the film has a thickness of 600 to 800 ⁇ m, preferably about 760 ⁇ m.
  • a 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 ⁇ l.
  • 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.
  • an appropriately diluted sample injection amount 100 ⁇ l
  • 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 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.
  • the molecular weight at the peak position in the chromatogram is defined as peak top molecular weight (A).
  • peak top molecular weight (A) the molecular weight at the peak position where the peak height is the highest is the peak top molecular weight (A).
  • 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.
  • the molecular weight at the peak position in the chromatogram is defined as peak top molecular weight (B).
  • peak top molecular weight (B) 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.
  • A peak top molecular weight measured with a differential refractive index detector
  • B 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).
  • the peak top molecular weight (A) is a value that serves as an index of the molecular weight of polyvinyl acetal.
  • the peak top molecular weight (B) is derived from a component present in polyvinyl acetal and having absorption at 280 nm.
  • (AB) / A becomes a positive value.
  • the low molecular weight component contains more components that absorb ultraviolet light having a wavelength of 280 nm.
  • foreign matter undissolved part
  • the adhesive strength is reduced.
  • (AB) / 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. . If the absorbance is less than 0.50 ⁇ 10 ⁇ 3 , foreign matter (undissolved content) in the solution produced using polyvinyl acetal may increase, and the adhesive strength decreases for the reasons described above. . On the other hand, when the absorbance exceeds 1.00 ⁇ 10 ⁇ 2 , polyvinyl acetal or a solution produced using the polyvinyl acetal may be easily colored, and the solution may be deteriorated due to poor appearance or resin deterioration. Storage stability and storage stability after bonding may be deteriorated.
  • 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 .
  • the polyvinyl acetal has a weight average molecular weight Mw ratio Mw / Mn of 2.8 to 12.0 determined by a differential refractive index detector in the GPC measurement. 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.
  • Mn is an average molecular weight that is strongly influenced by a low molecular weight component
  • 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.
  • Mw / Mn when Mw / Mn is less than 2.8, it indicates that the proportion of the low molecular weight component is small in the polyvinyl acetal.
  • Mw / Mn is more preferably 2.9 or more, and further preferably 3.1 or more.
  • Mw / Mn exceeds 12.0, it shows that the ratio of a low molecular weight component is large in polyvinyl acetal.
  • Mw / Mn exceeds 12.0, the mechanical properties of the coating film are deteriorated, which may cause cracks and the like.
  • Mw / Mn is more preferably 11.0 or less, and even more preferably 8.0 or less.
  • the degree of acetalization of polyvinyl acetal is 50 to 85 mol%, preferably 55 to 82 mol%, more preferably 60 to 78 mol%, and further preferably 65 to 75 mol%.
  • the degree of acetalization is less than 50 mol%, the water content after the production of polyvinyl acetal is increased, so that the cleaning efficiency is lowered, and deterioration of the resin due to contamination of impurities such as metal salts and acids remaining in the resin, Furthermore, the water content increases due to water absorption of the resin composition during storage, and there is a possibility that sufficient adhesiveness may not be exhibited.
  • the degree of acetalization exceeds 85 mol%, the efficiency of the acetalization reaction is remarkably lowered, the productivity is remarkably deteriorated, and the commercial property is lacking.
  • the degree of acetalization represents the ratio of the acetalized vinyl alcohol monomer unit to the total monomer units constituting the polyvinyl acetal.
  • 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 degree of polymerization of polyvinyl acetal is represented by the viscosity average degree of polymerization 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 [ ⁇ ] 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 ([ ⁇ ] ⁇ 10000 / 8.29) (1 / 0.62)
  • the viscosity average polymerization degree of the polyvinyl acetal is 200 to 5,000. When the viscosity average degree of polymerization is less than 200, it is difficult to produce polyvinyl acetal, and the mechanical properties of the coating film made of a solution using polyvinyl acetal are lowered, which may cause cracks and the like.
  • the viscosity average degree of polymerization is preferably 250 or more, more preferably 300 or more, and still more preferably 400 or more. On the other hand, when the viscosity average polymerization degree exceeds 5000, the solution viscosity becomes too high to be difficult to apply, and the adhesiveness may be lowered.
  • the viscosity average degree of polymerization is preferably 4500 or less, more preferably 4000 or less, further preferably 3500 or less, and particularly preferably 2500 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 to 13 mol%.
  • the content of the vinyl ester monomer unit is less than 0.1 mol%, polyvinyl acetal cannot be stably produced.
  • the content of the vinyl ester monomer unit exceeds 20 mol%, when deacetic acid occurs, the storage stability of the solution containing the polyvinyl acetal is lowered, and the mechanical properties are deteriorated due to resin deterioration. May decrease.
  • 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%.
  • Polyvinyl acetal is usually produced by acetalizing PVA.
  • the polyvinyl acetal may have at least one functional group selected from an amide group, an amino group, an ester group, a carbonyl group, and a vinyl group in the side chain.
  • the functional group is preferably an amide group or an amino group, and the content thereof is preferably 20 mol% or less, more preferably 10 mol% or less, more preferably 5 mol% relative to the number of monomer units of PVA before acetalization. % Or less is more preferable. When the content of the functional group is 20 mol% or more, it may be difficult to produce polyvinyl acetal.
  • the method for introducing a functional group into the side chain there is no particular limitation on the method for introducing a functional group into the side chain.
  • a method obtained by copolymerizing a comonomer having the functional group and vinyl acetate, and an aldehyde containing the functional group examples thereof include a method for acetalization and a method for reacting a hydroxyl group of a vinyl alcohol unit which has not been acetalized with a carboxylic acid.
  • 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.
  • vinyl acid examples include vinyl acid, and vinyl acetate is particularly preferable.
  • a carbonyl group-containing monomer As a comonomer used for the copolymerization with vinyl acetate and copolymerized to introduce the functional group, a carbonyl group-containing monomer, an amino group-containing monomer, a vinyl group-containing monomer, Examples thereof include N-vinylamide monomers and (meth) acrylamide monomers.
  • Examples of the carbonyl group-containing monomer include diacetone acrylamide.
  • amino group-containing monomers examples include allylamine, dimethylaminopropylmethacrylamide, N-isobutoxymethylmethacrylamide, dimethylaminoacrylamide, dimethylaminoethyl acrylate, acryloylmorpholine, and the like.
  • examples include methylol propane diallyl ether and pentaerythritol triallyl ether.
  • N-vinylamide monomers include N-vinyl-2-pyrrolidones and N-vinyl-2-caprolactams, N-vinylformamide, N-methyl-N-vinylformamide, N-vinylacetamide, N -Methyl-N-vinylacetamide and the like.
  • N-vinyl-2-pyrrolidones examples include N-vinyl-2-pyrrolidone, N-vinyl-3-propyl-2-pyrrolidone, N-vinyl-5,5-dimethyl-2-pyrrolidone, N-vinyl-3 , 5-dimethyl-2-pyrrolidone and the like.
  • (Meth) acrylamide monomers include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, t-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N- Such as methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, t-butyl (meth) acrylamide sulfonic acid, etc. ) Acrylamide derivatives and the like.
  • N-vinylacetamide, N-vinyl-2-caprolactam, and N-methoxymethylmethacrylamide are more preferable from the viewpoint of obtaining a homogeneous resin composition.
  • 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.
  • a thiol compound such as 2-mercaptoethanol, n-dodecyl mercaptan, mercaptoacetic acid, 3-mercaptopropionic acid, and saponifying the resulting polyvinyl ester.
  • Examples of methods for polymerizing vinyl esters include known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
  • a bulk polymerization method performed without a solvent or a solution polymerization method performed using a solvent such as alcohol is usually employed.
  • 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.
  • the reaction can be carried out by either a batch method or a continuous method.
  • the initiator used in the polymerization reaction include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy- 2,4-dimethylvaleronitrile) and other azo initiators; benzoyl peroxide, n-propyl peroxycarbonate, organic peroxide initiators such as peroxydicarbonate, and the like, as long as the effects of the present invention are not impaired.
  • organic peroxide initiators having a half-life of 10 to 110 minutes at 60 ° C. are preferred, and peroxydicarbonate is particularly preferred.
  • polymerization temperature for carrying out the polymerization reaction but a range of 5 ° C to 200 ° C is suitable.
  • a copolymerizable monomer can be copolymerized as necessary as long as the effects of the present invention are not impaired.
  • a monomer include ⁇ -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 acid 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; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether,
  • 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 method in an alcohol solvent.
  • an alkaline substance is usually used, and 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.
  • 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, and dimethylformamide. Of these solvents, methanol is preferably used. At this time, the water 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.
  • 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.
  • 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.
  • 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 vinyl ester from which a radical polymerization inhibitor contained in the raw material vinyl ester has been removed in advance is used for the polymerization.
  • Impurities include aldehydes such as acetaldehyde, crotonaldehyde, and acrolein; acetals 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.
  • the impurities contained in the solvent include those described above as the impurities contained in the raw material vinyl ester.
  • 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, 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.
  • an inhibitor 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.
  • 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.
  • 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 1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1-methoxy-1,3-butadiene, 2-methoxy-1,3-butadiene, 2-methoxy-1
  • Conjugated dienes from conjugated structures with three carbon-carbon double bonds such as 1,3,5-hexatriene, 2,4,6-octatriene-1-carboxylic acid, eleostearic acid, tung oil, cholecalciferol Conjugated triene: cyclooctatetraene, 2,4,6,8-decatetraene-1-carboxylic acid, retinol, retinoic acid, etc.
  • Carbon - include polyenes such as conjugated polyene consisting of carbon-carbon 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.
  • the residual monomer removal rate is 99% or more, more preferably 99.5% or more, still more preferably 99.8% or more.
  • the acetalization of PVA can be performed, for example, under the following reaction conditions, but is not limited thereto.
  • PVA is dissolved in water by heating to 80 to 100 ° C., and then gradually cooled over 10 to 60 minutes to obtain a 3 to 40% by mass aqueous solution of PVA.
  • 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.
  • polyvinyl acetal having reached a certain degree of acetalization is precipitated.
  • the temperature of the reaction solution is raised to 25 to 80 ° C.
  • aggregated particles made of polyvinyl acetal are generated in such a reaction or processing step, and coarse particles are easily formed.
  • coarse particles are generated, there is a risk of causing variation between batches.
  • 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.
  • the acid catalyst used in the acetalization reaction is not particularly limited, and any of organic acids and inorganic acids can be used.
  • acetic acid, p-toluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid and the like can be mentioned.
  • hydrochloric acid, sulfuric acid, and nitric acid are preferably used.
  • nitric acid when nitric acid is used, the reaction rate of the acetalization reaction is increased, and improvement in productivity can be expected.
  • the obtained polyvinyl acetal particles tend to be coarse and the variation between batches tends to increase. is there.
  • PVA produced using the above-described predetermined method is used as a raw material, the generation of coarse particles is suppressed.
  • the aldehyde used in the acetalization reaction is not particularly limited, and examples thereof include known aldehydes having a hydrocarbon group and alkyl acetals thereof.
  • aldehydes having a hydrocarbon group aliphatic aldehydes and alkyl acetals thereof include formaldehyde (including paraformaldehyde), acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, isovaleraldehyde, hexylaldehyde, 2-ethyl Butyraldehyde, pivalaldehyde, octyl aldehyde, 2-ethylhexyl aldehyde, nonyl aldehyde, decyl aldehyde, dodecyl aldehyde, etc.
  • alicyclic aldehydes and their alkyl acetals such as cyclopentane aldehyde, methyl cyclopentane aldehyde, dimethyl cyclopentane aldehyde , Cyclohexanealdehyde, methylcyclohexanealdehyde, dimethylcyclohexanealdehyde, cyclohexane Setaldehyde and the like are cyclic unsaturated aldehydes and alkyl acetals thereof, such as cyclopentene aldehyde and cyclohexene aldehyde, and aromatic and unsaturated bond-containing aldehydes and alkyl acetals thereof are benzaldehyde, methylbenzaldehyde, dimethylbenzaldehyde, methoxybenzaldehyde, and the like.
  • aldehydes having 1 to 8 carbon atoms are preferable, aldehydes having 4 to 6 carbon atoms are more preferable, and n-butyraldehyde is particularly preferably used.
  • polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.
  • an aldehyde used for acetalizing a polyvinyl alcohol resin an aldehyde having a functional group selected from an amide group, an amino group, an ester group, a carbonyl group, and a vinyl group or an alkyl acetal thereof may be used. .
  • an aldehyde having an amino group as a functional group is preferable.
  • aldehyde having an amino group as a functional group examples include aminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, aminopropionaldehyde, dimethylaminopropionaldehyde, aminobutyraldehyde, aminopentylaldehyde, aminobenzaldehyde, dimethylaminobenzaldehyde, ethylmethylaminobenzaldehyde, Examples include diethylaminobenzaldehyde, pyrrolidylacetaldehyde, piperidylacetaldehyde, pyridylacetaldehyde, and aminobutyraldehyde is more preferable from the viewpoint of productivity. Examples of the aldehyde having a vinyl group as a functional group include acrolein.
  • aldehyde having a carbonyl group as a functional group examples include glyoxylic acid and its metal salt or ammonium salt, 2-formylacetic acid and its metal salt or ammonium salt, 3-formylpropionic acid and its metal salt or ammonium salt, 5-formylpentane Acid and its metal salt or ammonium salt, 4-formylphenoxyacetic acid and its metal salt or ammonium salt, 2-carboxybenzaldehyde and its metal salt or ammonium salt, 4-carboxybenzaldehyde and its metal salt or ammonium salt, 2,4- Examples include dicarboxybenzaldehyde and its metal salt or ammonium salt.
  • aldehyde having an ester group as a functional group examples include methyl glyoxylate, ethyl glyoxylate, methyl formyl acetate, methyl formyl acetate, methyl 3-formylpropionate, ethyl 3-formylpropionate, methyl 5-formylpentanoate, 5- Examples include ethyl formylpentanoate.
  • heterocyclic aldehyde and its alkyl acetal an aldehyde having a hydroxyl group, an aldehyde having a sulfonic acid group, an aldehyde having a phosphoric acid group, a cyano group, a nitro group, or a quaternary ammonium salt may be used as long as the characteristics of the present invention are not impaired.
  • an aldehyde having a halogen atom may be used.
  • the solvent for dissolving the polyvinyl acetal resin is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, dipropyl ketone, and diisobutyl ketone; alcohols such as methanol, ethanol, isopropanol, and butanol; toluene, xylene, and the like.
  • Aromatic hydrocarbons methyl propionate, ethyl propionate, butyl propionate, methyl butanoate, ethyl butanoate, butyl butanoate, methyl pentanoate, ethyl pentanoate, butyl pentanoate, methyl hexanoate, ethyl hexanoate, Esters such as butyl hexanoate, 2-ethylhexyl acetate, 2-ethylhexyl butyrate; methyl cellosolve, ethyl cellosolve, butyl cellosolve, ⁇ -terpineol, butyl cellosolve acetate, butyl carbito Le acetate and the like.
  • These organic solvents may be used independently and 2 or more types may be used together, The ratio of the solvent to contain can be selected arbitrarily.
  • the method of applying the polyvinyl acetal solution to the base material is not particularly limited.
  • a method of applying the solution on the base material by an appropriate method such as a doctor blade method or a gravure printing method, roll coating, spray coating, dip Etc.
  • the drying method after the application of the polyvinyl acetal solution either natural drying or forced heating drying with hot air or the like can be applied.
  • the outside air temperature is low, the wettability to the base material is reduced, and the base material depends on the type of solvent. Decrease in wettability or decrease in wettability due to a decrease in the pressing force of coating may occur.
  • wetting in the solution state is not sufficiently achieved as described above, if it fails to wet, it may be overcoated after drying or in a half-thirsty state.
  • the drying temperature exceeds 180 ° C., the resin may be deteriorated or the adherend may be thermally deformed or thermally deteriorated.
  • the drying time is a characteristic that depends on the shape of the adherend and the characteristics of the dryer, and can be appropriately adjusted within a range that does not impair the physical properties.
  • the base material that forms the molded body obtained by coating and forming a polyvinyl acetal solution there are no particular limitations on the base material that forms the molded body obtained by coating and forming a polyvinyl acetal solution, and various plastics such as various ⁇ -olefin (co) polymers, cellulose resins, acrylic resins, and styrene resins.
  • Appropriate thin leaf bodies such as films and sheets, papers and cloths, nonwoven fabrics and metal foils, nets and foams, and laminates thereof can be used, and any of base materials in conventional adhesives can be used.
  • the base material may be a ceramic sheet, a gold-deposited film, glass or the like having a conductor layer or a magnetic layer and / or containing a conductive powder or magnetic powder. The thickness of the substrate can be appropriately determined.
  • the content of the polyvinyl acetal in the solution is not particularly limited, but is preferably 0.01 to 80 parts by mass with respect to 100 parts by mass of the solution. When the content of the polyvinyl acetal is within such a range, the amount of undissolved material is reduced, and an adhesive improver excellent in storage stability and coating property of the solution can be obtained.
  • the polyvinyl acetal solution is a plasticizer, an inorganic filler, a compatibilizer, a lubricant, a light stabilizer, a weathering agent, a processing aid, as long as it does not inhibit the effects of the invention.
  • Colorants such as pigments and pigments, flame retardants, antistatic agents, softeners, plasticizers, matting agents, fillers, silicone oil, antiblocking agents, UV absorbers, antioxidants, release agents, foaming agents, fragrances 1 type, or 2 or more types of other components may be contained.
  • Content of components other than the said polyvinyl acetal is 50 mass% or less, 20 mass% or less is preferable and 10 mass% or less is more preferable.
  • the above plasticizer is not particularly limited as long as it does not impair the effects of the present invention 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.
  • 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.
  • triethylene glycol-di-2-ethylhexanoate tetraethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-n-heptanoate, tetraethylene glycol-di-n-heptanoate
  • the reforming treatment of the molded body in which the adhesiveness improving agent of the present invention is applied and formed on at least a part of the surface of the substrate is subjected to plasma discharge on at least a part of the surface on which the adhesiveness improving agent is formed.
  • plasma discharge treatment corona discharge treatment or ultraviolet irradiation treatment, or atmospheric pressure plasma treatment.
  • these treatments can be carried out in accordance with ordinary methods.
  • a pressure of 1 to 100000 Pascals and argon, helium, and nitrogen are more preferred as the atmospheric gas.
  • the discharge frequency, discharge output, and processing time are preferably adjusted as appropriate depending on the shape and size of the processing apparatus. Usually, a frequency of 13.56 MHz, an output of 10 to 1000 watts, and a processing time of about 5 seconds to 10 minutes are preferable. is there.
  • corona discharge treatment is usually performed in the air due to the simplicity of the apparatus, but in order to improve the treatment effect and enhance the adhesion, an inert gas such as argon gas or a gas atmosphere such as oxygen or nitrogen
  • an inert gas such as argon gas or a gas atmosphere such as oxygen or nitrogen
  • the treatment may be carried out with the above, or the treatment may be carried out while blowing these gases in the vicinity of the electrodes.
  • this method is most preferably employed as a resin modification treatment method.
  • the frequency of the corona discharge treatment can be adjusted as appropriate, but is usually 5 kHz or more, particularly 20 to 30 kHz from the viewpoint of treatment effect and efficiency. If the frequency is lower than 5 kHz, it is difficult to perform a stable and uniform process and the power consumption is increased, which may increase the power cost and shorten the durability of the electrode.
  • the discharge output and processing time may be appropriately adjusted according to the material, shape, and size of the object to be processed, and the shape and size of the electrode. Usually, it is about 50 to 5000 watts and about 1 to 60 seconds. Is preferred.
  • a light source for ultraviolet irradiation treatment a mercury lamp, a halogen lamp, an excimer lamp, an excimer laser, or the like is used.
  • the treatment may be performed in air, but can also be performed in a nitrogen gas atmosphere.
  • the light source output and irradiation time are not particularly limited, and may be appropriately adjusted according to the type, characteristics, processing atmosphere, distance to the object to be processed, material of the object to be processed, shape, and the like.
  • atmospheric pressure plasma devices can be used for atmospheric pressure plasma.
  • a device that can generate low-temperature plasma by performing intermittent discharge while passing an inert gas at a pressure close to atmospheric pressure between electrodes covered with a dielectric is preferable, and any device can be used.
  • Various modifications can be selected according to the purpose of use.
  • the “pressure near atmospheric pressure” in the “atmospheric pressure plasma” in the present invention refers to a range of 70 kPa to 130 kPa, and preferably 90 kPa to 110 kPa.
  • any gas of nitrogen, oxygen, hydrogen, carbon dioxide, helium, and argon, or a mixed gas of two or more of these can be used. It is preferable to use inert gases such as He and Ar, or nitrogen gas (N2), and Ar or He is particularly preferable.
  • the shape, structure, use, etc. can be applied to an adherend made of an inorganic material or an organic material.
  • the adhesion is not particularly limited, and is useful for a wide range of applications. Further, it can be suitably used for automotive resin molded products such as bumpers, door mirror covers, moldings and spoilers, joint parts in buildings, multilayer ceramic capacitors, electronic components such as solar cell modules, miscellaneous goods, daily necessities and footwear.
  • the polymerization degree was measured using a part of the methanol solution of PVAc-1 obtained.
  • a 10% methanol solution of sodium hydroxide was added so that the molar ratio of sodium hydroxide to vinyl acetate monomer units in polyvinyl acetate was 0.1.
  • 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 to PVAc-11 Polyvinyl acetate (PVAc-2 to PVAc-20) was obtained in the same manner as PVAc-1, except that the conditions were changed to those described in Table 1.
  • “ND” means less than 1 ppm.
  • the degree of polymerization of each polyvinyl acetate obtained was determined in the same manner as PVAc-1. The results are shown in Table 1.
  • PVAc-A to H Polyvinyl acetate PVAc-A to H were obtained by the same method as PVAc-1, except that the conditions described in Table 2 were changed. The amount of modification of each comonomer was determined using a sample dissolved in DMSO-d6 or CDCl3 using a 500 MHz proton NMR measurement apparatus (JEOL GX-500).
  • 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 3.
  • the sodium acetate content of PVA-1 was determined by measuring the amount of sodium in the obtained ash using an ICP emission analyzer “IRIS AP” manufactured by Jarrel Ash. .
  • the content of sodium acetate was 0.7% (0.20% in terms of sodium).
  • PVA-2-7, comparative PVA-1-7 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 (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1. The results are shown in Table 3.
  • PVA-A1 to G comparative PVA-H1, -H2
  • 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 (sodium mass conversion) of the obtained PVA were measured in the same manner as PVA-1.
  • the results are shown in Table 4.
  • PVA analysis method Analysis of PVA was performed according to the method described in JIS K6726 unless otherwise specified.
  • the contents of N-vinylamide monomer units and acrylamide monomer units contained in PVA were determined using a 500 MHz proton NMR measurement apparatus (JEOL GX-500) for a sample dissolved in DMSO-d6.
  • 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 had a butyralization degree (acetalization degree) of 68.5 mol%, a vinyl acetate monomer unit content of 0.9 mol%, and a vinyl alcohol monomer unit content of 30. It was 9 mol%.
  • Table 5 The results are shown in Table 5.
  • GPC measurement was performed using “GPCmax” manufactured by VISCOTECH.
  • 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 column “GPC HFIP-806M” manufactured by Showa Denko KK was used.
  • OmniSEC (Version 4.7.0.406) attached to the apparatus was used as analysis software.
  • HFIP HFIP containing 20 mmol / l sodium trifluoroacetate was used as the mobile phase.
  • the mobile phase flow rate was 1.0 ml / min.
  • the sample injection amount was 100 ⁇ l, and measurement was performed at a GPC column temperature of 40 ° C.
  • the sample whose viscosity average polymerization degree of PVA mentioned later exceeds 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. ⁇ (mg / ml) is the concentration of the diluted sample.
  • Absorbance at a sample concentration of 1.00 mg / ml (1.00 / ⁇ ) ⁇ measured value of absorbance
  • PMMA polymethyl methacrylate
  • Agilent Technologies peak top molecular weight: 1944000, 790000, 467400, 271400, 144000, 79250, 35300, 13300, 7100, 1960, 1020, 690
  • a calibration curve for converting the elution volume into the PMMA molecular weight was prepared for each of the differential refractive index detector and the absorptiometric detector.
  • the analytical software was used to create each calibration curve. In this measurement, a column in a state where the peaks of the standard samples having both molecular weights of 1944000 and 271400 can be separated in the measurement of polymethyl methacrylate was used.
  • the peak intensity obtained from the differential refractive index detector is mV (millivolt), and the peak intensity obtained from the UV detector is represented by absorbance (abs unit: Absorbance unit).
  • Example preparation 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 ⁇ m. This was used for GPC measurement.
  • the sample prepared by the above method was dissolved in 20 mmol / l sodium trifluoroacetate-containing hexafluoroisopropanol (hereinafter abbreviated as “HFIP”) to prepare a 1.00 mg / ml solution of PVA.
  • HFIP sodium trifluoroacetate-containing hexafluoroisopropanol
  • 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.
  • Example 17 PVB-NH-1 Modified polyvinyl butyral was synthesized in the same manner as in Example 1 except that 21.5 g of 4-aminodiethyl acetal and 375 g of n-butyraldehyde were used. And it evaluated similarly to Example 1. FIG. The results are shown in Table 5.
  • Viscosity change rate is less than 5%
  • B Viscosity change rate is 5% or more and less than 10%
  • C Viscosity change rate is 10% or more
  • Viscosity change rate is 10% or more
  • Calculation formula Viscosity change rate (100 ⁇ viscosity after storage / initial viscosity) ⁇ 100 %]
  • Measurement of undissolved content (measurement of the number of particles having a diameter of 2 ⁇ m or more) Using the polyvinyl acetal resin obtained in Example 1, it was dissolved in a mixed solvent of toluene and ethanol in a weight ratio of 1: 1 to obtain a 2% by weight solution, and the particle size distribution of 5 ml of PVB solution was measured using a particle counter (PMS Corporation).
  • the ceramic slurry obtained above was coated on a release-treated polyester film so that the thickness after drying was about 10 ⁇ m, air-dried at room temperature for 1 hour, and then heated at 80 ° C. using a hot air dryer. For 3 hours, followed by drying at 120 ° C. for 2 hours to obtain a ceramic green sheet.
  • the obtained green sheet was used as a base material for an adhesion test.
  • A After storage for 50 days, the adhesiveness does not change compared to the adhesion state immediately after the adhesion, and the adhesion is strong.
  • B After storage for 50 days, the delamination site slightly increased as compared to the adhesion state immediately after the adhesion.
  • C After storage for 50 days, delamination was considerably increased as compared with the adhesion state immediately after the adhesion.
  • PET Adhesive Sample Using the polyvinyl acetal resin obtained in Example 1, the solution obtained in Example 1 was dried on polyethylene terephthalate (PET; “Bottle TR-8550” manufactured by Teijin Limited). It was applied with a bar coater so that the subsequent thickness was 0.5 ⁇ m. Then, it was dried at a temperature of 80 ° C. for 3 hours and then at a temperature of 120 ° C. for 2 hours using a hot air dryer to obtain a PET film on which a polyvinyl acetal resin was formed. Then, the sample which surface-modified using the atmospheric pressure plasma apparatus on the polyvinyl acetal surface on PET film was also produced.
  • PET polyethylene terephthalate

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