TW201546144A - Highly adhesive resin composition and molded article produced from same, and laminate - Google Patents

Abstract

A molded article which enables the production of a molded article having flexibility, excellent mechanical properties and excellent adhesivity to a polar polymer and also enables the production of a laminate, and which is highly stable after being adhered to an object of interest; and a laminate. A highly adhesive resin composition comprising: a polyvinyl acetal which 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 5000, and which has such a property that, when the polyvinyl acetal is heated at 230 DEG C for three hours and is then subjected to a gel permeation chromatographic measurement, the peak top molecular weight (A) as measured using a differential refractive index detector and the peak top molecular weight (B) as measured using an absorbance detector (a wavelength employed for measurement: 280 nm) satisfy the following formula (1): (A-B)/A < 0.60, wherein the absorbance at the peak top molecular weight (B) is 0.50 x 10-3 to 1.00 x 10-2; and a thermoplastic resin selected from polyester, polyamide, an [alpha]-olefin (co)polymer, a cellulose-type resin, an acrylic resin and a styrene-type resin.

Description

High-adhesive resin composition, formed body formed thereby, and laminate

The present invention relates to a resin composition having excellent adhesion of a polyvinyl acetal, and a molded body and a laminate thereof.

The polyvinyl acetal is obtained by using an acetalization reaction in water under acidic conditions using polyvinyl alcohol (hereinafter sometimes abbreviated as "PVA") and an aldehyde compound. Polyvinyl acetal has been proposed because it can obtain a tough film and has a special structure having both a hydrophilic hydroxyl group and a hydrophobic acetal group. Among them, polyethylene formaldehyde produced from PVA and formaldehyde, polyethylene acetal made from PVA and acetaldehyde, and polyvinyl butyral made from PVA and butyl aldehyde are also commercially important. . In particular, polyvinyl butyral is particularly important in commercial use because it is widely used in various adhesives or films.

On the other hand, resin products other than metal or glass are widely used on exterior parts of automobiles. For example, there are more and more cases in which a resin molded article is used for a bumper, a door mirror cover, a mold, a spoiler, and the like. As such a resin molded article, a large amount of a polyolefin-based resin material is used more and more in comparison with a urethane-based resin from the viewpoint of economy. Further, the polyolefin resin has excellent chemical resistance, water resistance, moldability, and the like. When these polyolefin-based resin materials are used, they are variously limited as compared with the case of metal coating. For example, since the polyolefin-based resin material has a low polarity, the adhesion of the coating film is inferior. Similarly, since the styrene-based thermoplastic resin composition is also a material having a relatively low polarity, the adhesion to the highly polar resin is poor, and it is difficult to carry out the melting. Therefore, when a styrene-based thermoplastic resin or an olefin-based thermoplastic resin is to be bonded to a highly polar resin, it is necessary to apply an adhesive or to pretreat the surface.

Further, as a method of improving the adhesion, Patent Document 1 or 2 discloses a thermoplastic composition in which the polyvinyl acetal is added to a low-polarity thermoplastic elastomer or a highly polar methacrylic resin. However, even in the thermoplastic composition described in Patent Document 1 or 2, sufficient adhesion strength cannot be obtained. Further, in Patent Document 3, the film is subjected to surface treatment using an atmospheric plasma device to improve the adhesion. However, only the adhesiveness is described, and the quality of the molded article is improved in terms of the mechanical properties of the obtained molded article. There is no mention.

[Advanced technical literature] [Patent Literature]

[Patent Document 1] International Publication No. 2009/081877

[Patent Document 2] International Publication No. 2008/050738

[Patent Document 3] International Publication No. 2011/046143

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition which is excellent in flexibility as a thermoplastic resin composition and which has excellent mechanical properties, and which has excellent adhesion to a polar polymer and excellent stability after adhesion to a coating body. Things. Further, an object of the present invention is to provide a molded body and a laminate using the thermoplastic resin composition.

The above problem is to provide a resin composition containing a polyvinyl acetal and a thermoplastic resin; in the polyvinyl acetal, the degree of acetalization is 50 to 85 mol%, and the content of the vinyl ester monomer unit is 0.1~ 20 mol %, viscosity average degree of polymerization 200-5000, and the absorption peak measured by differential refractive index detector when the polyethylene acetal heated at 230 ° C for 3 hours is measured by gel permeation chromatography The apex molecular weight (A) and the absorption peak top molecular weight (B) measured by an absorbance photodetector (measurement wavelength 280 nm) satisfy the following formula (1) (AB) / A < 0.60 (1), and the absorption peak tip molecular weight The absorbance in (B) is 0.50×10 ^-3 to 1.00×10 ^-2 ; the thermoplastic resin is selected from the group consisting of polyester, polyamine, α-olefin (co)polymer, cellulose resin, and acrylic resin. A styrene resin is a resin composition characterized by a resin composition.

However, for the aforementioned GPC measurement,

Mobile phase: 20 mmol/l hexafluoroisopropanol containing sodium trifluoroacetate (hereinafter will Hexafluoroisopropanol is abbreviated as HFIP

Sample concentration: 1.00mg/ml

Sample injection amount: 100μl

Pipe column: "GPC HFIP-806M" manufactured by Showa Denko Co., Ltd.

Column temperature: 40 ° C

Flow rate: 1ml/min

Container length of absorbance photodetector: 10mm

It is preferable that the ratio Mw/Mn of the weight average molecular weight Mw of the number average molecular weight Mn of the polyvinyl acetal obtained by the differential refractive index detector in the GPC measurement is 2.8 to 12.0.

The polyethylene acetal is a resin composition having a functional group selected from the group consisting of a mercaptoamine group, an amine group, an ester group, a carbonyl group, and a vinyl group in the side chain, and is also a preferred embodiment of the present invention. The aforementioned functional group is preferably a guanamine group or an amine group.

The resin composition in which the thermoplastic resin is a styrene resin or an α-olefin (co)polymer is also a preferred embodiment of the present invention.

A molded body formed of the above-mentioned resin composition or a molded body formed by irradiating at least a part of its surface with a plasma is also a preferred embodiment of the present invention.

A laminate obtained by coating or bonding a coated body to a molded body obtained by irradiating the above-mentioned plasma is also a preferred embodiment of the present invention.

The above-mentioned covering body has a functional group selected from the group consisting of a mercapto group, an ester group, a carbonate group, an acetal group, an ether group, a thioether group, a nitrile group, a hydroxyl group, a carbonyl group, a carboxyl group, an amine group, and a sulfonic acid group. The laminate of the polar polymer is also a preferred embodiment of the invention.

The foregoing polar polymer is selected from the group consisting of polyamine, polyester, polycarbonate, polyacetal, polyphenylene sulfide, ABS resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinyl acetal, polyvinyl acetate. At least one of the laminates of esters, poly(meth)acrylates, polyethers, polyketones, ionomers, polyurethanes, and polyureas is also a preferred embodiment of the invention.

The resin composition of the present invention has excellent flexibility and excellent mechanical properties, and does not require an adhesive, a primer or the like itself, and has excellent adhesion to a polar polymer, and is excellent in stability after adhesion to a coated body. Further, according to the present invention, a molded body and a laminate using the resin composition can be obtained.

Fig. 1 is a graph showing the relationship between the molecular weight and the value measured by a differential refractive index detector (RI), and the molecular weight and the absorbance photodetector (UV) for the polyvinyl acetal used in Example 1. The relationship between the absorbance measured at a wavelength of 280 nm) is shown.

[Formation of the Invention]

In the polyvinyl acetal contained in the resin composition of the present invention, the degree of acetalization is 50 to 85 mol%, the content of the vinyl ester monomer unit is 0.1 to 20 mol%, and the average degree of polymerization of the viscosity is Polyvinyl acetal of 200 to 5000, when the polyethylene acetal heated at 230 ° C for 3 hours is measured by GPC, the absorption peak peak molecular weight (A) measured by a differential refractive index detector is detected by absorbance luminosity The absorption peak peak molecular weight (B) measured by the apparatus (measuring wavelength 280 nm) is such that (E) (A)/A < 0.60 (1) is satisfied, and the absorbance in the top molecular weight (B) of the absorption peak is 0.50 × 10 ^-3 ~ 1.00 × 10 ^-2 .

However, for the aforementioned GPC measurement,

Mobile phase: 20mmol/l sodium trifluoroacetate containing HFIP

Sample concentration: 1.00mg/ml

Sample injection amount: 100μl

Pipe column: "GPC HFIP-806M" manufactured by Showa Denko Co., Ltd.

Column temperature: 40 ° C

Flow rate: 1ml/min

The container length of the absorbance photodetector: 10 mm.

In the GPC measurement in the present invention, a GPC device having a differential refractive index detector and an absorbance photodetector, which can simultaneously perform measurement by using these detectors, is used. In the absorbance photodetector, the absorbance at a wavelength of 280 nm can be measured. The container length (optical path length) was 10 mm in the container of the detection unit of the absorbance photodetector. The absorbance photodetector can be a person who measures the absorption of ultraviolet light of a specific wavelength, or can measure the absorption of ultraviolet light of a specific range of wavelengths by spectrometry. The polyvinyl acetal provided for the measurement can be separated from each molecular weight component by a GPC column. Differential refraction The signal intensity of the rate detector is approximately proportional to the concentration of the polyethylene acetal (mg/ml). On the other hand, the polyethylene acetal detected by the absorbance photodetector has an absorber at a predetermined wavelength. The respective concentrations of the respective molecular weight components of each of the polyvinyl acetals and the absorbance at a predetermined wavelength can be measured by the GPC measurement.

As a solvent and a mobile phase in which the polyvinyl acetal measured in the GPC measurement described above was used, HFIP containing sodium trifluoroacetate at a concentration of 20 mmol/l was used. HFIP is a soluble polyvinyl acetal and polymethyl methacrylate (hereinafter referred to as PMMA and abbreviation). Further, by adding sodium trifluoroacetate, adsorption of the polyvinyl acetal to the column packing can be prevented. The flow rate in the aforementioned GPC measurement was 1 ml/min, and the column temperature was 40 °C.

For the aforementioned GPC measurement, monodisperse PMMA (hereinafter referred to as standard PMMA) was used as a standard. Several types of standard PMMA having different molecular weights were determined, and a standard curve was formed from the GPC elution capacity and the molecular weight of the standard PMMA. For the present invention, a standard curve made using the detector in the measurement by a differential refractive index detector is used, and a standard curve formed by using the detector in the measurement by the absorbance photodetector is used. Using these standard curves, the molecular weight was converted from the GPC elution capacity, and the absorption peak top molecular weight (A) and the absorption peak tip molecular weight (B) were determined.

The polyvinyl acetal was heated at 230 ° C for 3 hours before the aforementioned GPC measurement. For the present invention, the polyvinyl acetal is heated by the following method. The difference from the hue of the sample after heat treatment can be clearly reflected in the difference in absorbance, and the powder of polyvinyl acetal is at a pressure of 2 MPa. After hot pressing at 230 ° C for 3 hours, a heated polyvinyl acetal (film) was obtained. The film thickness at this time is 600 to 800 μm, preferably about 760 μm.

The heated polyvinyl acetal was dissolved in the above solvent to obtain a measurement sample. The polyethylene acetal concentration of the measurement sample was set to 1.00 mg/ml, and the injection amount was set to 100 μl. However, when the average degree of polymerization of the polyvinyl acetal exceeds 2,400, the volume of the acetal is increased, so that the concentration of the polyvinyl acetal may not be reproducible when it is 1.00 mg/ml. At this time, a suitably diluted sample (injection amount of 100 μl) was used. The absorbance is proportional to the polyethylene acetal concentration. Therefore, the absorbance at a polyethylene acetal concentration of 1.00 mg/ml was determined using the diluted sample concentration and the measured absorbance.

Fig. 1 is a view showing the relationship between the molecular weight obtained by measuring GPC of polyvinyl acetal and the value measured by a differential refractive index detector, and the molecular weight and the absorbance photodetector (measurement wavelength: 280 nm) for the examples of the present invention to be described later. The relationship between absorbance. The GPC measurement in the present invention will be further described using Fig. 1 . In Fig. 1, the chromatogram shown by "RI" indicates the molecular weight (horizontal axis) of the polyvinyl acetal converted from the elution capacity, and the value measured by the differential refractive index detector is plotted. The molecular weight in the absorption peak position in the chromatogram of the present invention is taken as the absorption peak tip molecular weight (A). When a complex absorption peak is present in the chromatogram, the molecular weight in the absorption peak position having the highest absorption peak height is taken as the absorption peak tip molecular weight (A).

In Figure 1, the chromatogram shown by "UV" indicates self-dissolving The molecular weight (horizontal axis) of the polyvinyl acetal converted by the capacity, and the absorbance map measured by the absorbance photodetector (measurement wavelength: 280 nm). In the present invention, the molecular weight in the absorption peak position in the chromatogram is taken as the absorption peak tip molecular weight (B). Further, when there is a complex absorption peak in the chromatogram, the molecular weight in the absorption peak position having the highest absorption peak height is taken as the absorption peak tip molecular weight (B).

When the polyvinyl acetal is subjected to GPC measurement by the above method, the absorption peak peak molecular weight (A) measured by the differential refractive index detector and the absorption peak top molecular weight measured by the absorbance photodetector (measurement wavelength 280 nm) (B) ) is to satisfy the following formula (1).

(A-B)/A<0.60 (1)

The absorption peak tip molecular weight (A) is a value which is an index of the molecular weight of the polyvinyl acetal. On the other hand, the absorption peak top molecular weight (B) is a component having absorption at 280 nm existing in the polyvinyl acetal. Generally, it has a larger absorption peak tip molecular weight (A) than the absorption peak tip molecular weight (B), so (A-B)/A is a positive value. When the molecular weight (B) of the absorption peak is large, (A-B)/A becomes small, and if the molecular weight (B) of the absorption peak becomes small, (A-B)/A becomes large. That is, when (A-B)/A is large, it is shown that the low molecular weight component in the polyvinyl acetal contains many components of ultraviolet rays having a wavelength of 280 nm.

When (A-B)/A is 0.60 or more, as described above, a component which absorbs ultraviolet rays having a wavelength of 280 nm in the low molecular weight component increases. At this time, foreign matter (undissolved portion) in the molded body produced by using polyvinyl acetal may increase, that is, when there is an undissolved portion, it will be at the foreign matter interface. It becomes a starting point of fracture and failure, so that the mechanical properties and the subsequent strength are lowered. (A-B)/A is preferably less than 0.55, more preferably less than 0.50.

When the polyethylene acetal is subjected to GPC measurement by the above method, the absorbance (measuring wavelength 280 nm) in the molecular weight (B) of the absorption peak must be 0.50 × 10 ^-3 to 1.00 × 10 ^-2 . When the absorbance is less than 0.50 × 10 ^-3 , the foreign matter (undissolved portion) in the molded body produced by using the polyvinyl acetal may increase, and the mechanical properties and the subsequent strength are lowered by the above reasons. On the other hand, when the absorbance exceeds 1.00 × 10 ^-2 , the polyvinyl acetal or the molded article produced using the same may have a tendency to be easily colored, and there is a fear that the appearance is poor or the mechanical properties are lowered, and the resin is deteriorated. The preservation stability deteriorates. The absorbance is preferably 1.00 × 10 ^-3 to 8.00 × 10 ^{-3 , more} preferably 1.50 × 10 ^-3 to 6.50 × 10 ^-3 .

Further, in the polyvinyl acetal, the ratio Mw/Mn of the weight average molecular weight Mw of the number average molecular weight Mn of the polyvinyl acetal obtained by the differential refractive index detector in the GPC measurement is 2.8 to 12.0. It is better. Mw and Mn can be obtained from a chromatogram obtained by plotting the value measured by the differential refractive index detector for the molecular weight of the aforementioned polyvinyl acetal. Mw and Mn in the present invention are in terms of PMMA.

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

Therefore, when the Mw/Mn is less than 2.8 in the present invention, it means that the ratio of the low molecular weight component to the polyvinyl acetal is small. If the Mw/Mn is less than 2.8, there is a fear that the adhesion will decrease in the next step. When Mw/Mn is 2.9 or more, it is more preferable, and when it is 3.1 or more, it is more preferable. On the other hand, when Mw/Mn exceeds 12.0, the ratio of the low molecular weight component to the polyvinyl acetal is large. When Mw/Mn exceeds 12.0, there is a concern that the mechanical properties of the molded body are lowered. When Mw/Mn is 11.0 or less, it is more preferable, and when it is 8.0 or less, it is more preferable.

The degree of acetalization of the polyvinyl acetal is 50 to 85 mol%, preferably 55 to 82 mol%, preferably 60 to 78 mol%, more preferably 65 to 75 mol%. When the degree of acetalization is less than 50% by mole, the water content after the production of the polyvinyl acetal is increased, so that the cleaning efficiency is lowered, and impurities such as a metal salt or an acid remaining in the resin are mixed. The resin is deteriorated, and the water content is increased by the water absorption of the resin composition during storage, and the adhesion may not be sufficiently exhibited. On the other hand, when the degree of acetalization exceeds 85 mol%, the efficiency of the acetalization reaction is remarkably lowered, productivity is remarkably deteriorated, and commerciality is lacking.

Further, the degree of acetalization indicates the ratio of the acetalized vinyl alcohol monomer unit to the all monomer unit constituting the polyvinyl acetal. Among the vinyl alcohol monomer units in the PVA of the raw material, those which have not been acetalized remain in the polyvinyl acetal obtained as a vinyl alcohol monomer unit.

The viscosity average degree of polymerization of the polyvinyl acetal means the viscosity average degree of polymerization of the PVA of the raw material measured in accordance with JIS K6726. P750 is resaponified to a degree of saponification of 99.5 mol% or more. The ultimate viscosity [η] (L/g) measured in water at 30 ° C can be obtained by the following formula. The viscosity average degree of polymerization of PVA is substantially the same as the viscosity average degree of polymerization of the polyvinyl acetal obtained by acetalization.

P=([η]×10000/8.29)(1/0.62)

The polyvinyl acetal has a viscosity average degree of polymerization of 200 to 5,000. When the viscosity average degree of polymerization is less than 200, the production of the polyvinyl acetal becomes difficult, and the mechanical properties of the molded body formed by using the resin composition of the polyvinyl acetal are lowered. The average degree of polymerization of the viscosity 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 degree of polymerization exceeds 5,000, the resin viscosity during molding is too high to be formed, and the adhesion is lowered. The average degree of polymerization of the viscosity is preferably 4,500 or less, more preferably 4,000 or less, more preferably 3,500 or less, and most preferably 2,500 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%, preferably 0.5 to 15 mol%, more preferably 0.7 to 13 mol. ear%. When the content of the vinyl ester monomer unit is less than 0.1 mol%, the polyvinyl acetal cannot be produced stably. On the other hand, when the content of the vinyl ester monomer unit exceeds 20 mol%, the storage stability of the resin composition containing the polyvinyl acetal may be lowered to cause deterioration of the resin and a decrease in mechanical properties.

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

Polyvinyl acetal contained in the resin composition of the present invention It is generally produced by acetalizing PVA.

The polyvinyl acetal is one having at least one type of functional group selected from the group consisting of a guanamine group, an amine group, an ester group, a carbonyl group, and a vinyl group in the side chain. The functional group is preferably a mercapto group or an amine group, and the content is preferably 20 mol% or less, more preferably 10 mol% or less, based on the number of monomer units of PVA before acetalization. 5 mol% or less is better. When the content of the functional group is 20 mol% or more, the production of the polyvinyl acetal may become difficult.

The method of introducing a functional group into the side chain is not particularly limited. For example, in the production method described later, a method of copolymerizing a comonomer having the functional group and vinyl acetate, and a method of using the functional group described above may be mentioned. A method in which an aldehyde is acetalized, a method in which a hydroxyl group of a non-acetalized vinyl alcohol unit is reacted with a carboxylic acid, or the like.

Examples of the vinyl ester used in the production of the raw material PVA include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl phthalate, vinyl laurate, and vinyl stearate. Vinyl benzoate, vinyl pivalate and vinyl versatate, among which vinyl acetate is preferred.

Examples of the comonomer copolymerizable with the vinyl acetate in the above-mentioned copolymerization to introduce the aforementioned functional group include a carbonyl group-containing monomer, an amine group-containing monomer, a vinyl group-containing monomer, and N-ethylene. A quinone-based monomer, a (meth) acrylonitrile-based monomer, or the like.

Examples of the carbonyl group-containing monomer include diacetone acrylonitrile groups and the like.

As the amino group-containing monomer, allylamine and dimethyl group are mentioned. Aminopropyl methacryl fluorenyl group, dimethylaminopropyl propylene fluorenyl group, dimethylamino ethyl acrylate, acryl hydrazino morpholine, etc., as a vinyl group-containing monomer, trihydroxyl Methylpropane diallyl ether, pentaerythritol triallyl ether, and the like.

Examples of the N-vinylamine-based monomer include N-vinyl-2-pyrrolidone and N-vinyl-2-caprolactam, N-vinylformamide, and N- Methyl-N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, and the like.

Examples of the N-vinyl-2-pyrrolidone include N-vinyl-2-pyrrolidone, N-vinyl-3-propyl-2-pyrrolidone, and N-vinyl-5. 5-dimethyl-2-pyrrolidone, N-vinyl-3,5-dimethyl-2-pyrrolidone, and the like.

Examples of the (meth) acrylonitrile-based monomer include a (meth) acrylonitrile group, an N-methyl (meth) acryl fluorenyl group, an N-ethyl (meth) acryl fluorenyl group, and a t-butyl group. (meth)acryloyl fluorenyl, N-methylol (meth) propylene fluorenyl, N-methoxymethyl (meth) acrylonitrile, N-ethoxymethyl (meth) propylene hydride Base, Nn-butoxymethyl (meth) acrylonitrile, N-isobutoxymethyl (meth) acrylonitrile, t-butyl (meth) propylene sulfonic acid, etc. (methyl An acrylonitrile derivative or the like.

Among the above monomers, from the viewpoint of obtaining a homogeneous resin composition, N-vinylacetamide, N-vinyl-2-caprolactam, N-methoxymethylmethacryl oxime The base is better.

Further, the raw material PVA is a thiol compound such as a vinyl ester in 2-mercaptoethanol, n-dodecylmercaptan, thioglycolic acid or 3-mercaptopropionic acid. The polymerization is carried out in the presence of saponification of the obtained polyvinyl ester. By this method, PVA derived from a functional group of a thiol compound can be obtained at the terminal.

Examples of the method for polymerizing the vinyl ester include known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these methods, a bulk polymerization method in which no solvent is carried out or a solution polymerization method using a solvent such as an alcohol is generally employed. From the viewpoint of improving the effect of the present invention, a solution polymerization method in which a lower alcohol is co-polymerized is preferred. The lower alcohol is not particularly limited, and an alcohol having 3 or less carbon atoms such as methanol, ethanol, propanol or isopropanol is preferred, and methanol is generally used. When the polymerization reaction is carried out by a bulk polymerization method or a solution polymerization method, the reaction method can be carried out in any of a batch type and a continuous type. Examples of the initiator used in the polymerization reaction include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-. An azo initiator such as azobis(4-methoxy-2,4-dimethylvaleronitrile); benzammonium peroxide, n-propyl peroxycarbonate, peroxydicarbonate, etc. The organic peroxide-based initiator or the like is a known initiator which does not impair the effects of the present invention, and particularly preferably an organic peroxide-based initiator which has a half-life of 60 to 10 minutes and a period of 10 to 110 minutes. It is preferred to use peroxydicarbonate. The polymerization temperature at the time of carrying out the polymerization reaction is not particularly limited, but is preferably in the range of 5 ° C to 200 ° C.

When the vinyl ester is subjected to radical polymerization, the copolymerizable monomer may be copolymerized as necessary only insofar as the effects of the present invention are not impaired. Examples of such a monomer include α-olefins such as an exoethyl group, a propyl group, a 1-butene group, an isobutylene group, and a 1-hexene group; fumaric acid, maleic acid, itaconic acid, and Malay a carboxylic acid such as an acid anhydride or itaconic anhydride or a derivative thereof; an acrylic acid or a salt thereof; an acrylate such as methyl acrylate, ethyl acrylate, n-propyl acrylate or isopropyl acrylate; methacrylic acid or a salt thereof; Methyl acrylate such as methyl acrylate, ethyl methacrylate, n-propyl methacrylate or isopropyl methacrylate; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether Vinyl ethers such as isopropyl vinyl ether and n-butyl vinyl ether; ethylene glycol vinyl ether, 1,3-propane diol vinyl ether, 1,4-butanediol vinyl ether, etc. Hydroxy-containing vinyl ethers; allyl ethers such as allyl acetate, propyl allyl ether, butyl allyl ether, hexyl allyl ether; monomers having an alkyloxy group; Isopropenyl acetate, 3-buten-1-ol, 4-penten-1-ol, 5-hexen-1-ol, 7-octene-1-ol, 9-nonen-1-ol, a hydroxyl group-containing α-olefin such as 3-methyl-3-buten-1-ol; ethylene sulfonic acid, allyl sulfonic acid, methallyl sulfonic acid, 2-propenyl fluorenyl-2-methyl a monomer having a sulfonic acid group such as propane sulfonic acid; ethylene oxyethyl three Alkyl ammonium chloride, vinyloxybutyltrimethylammonium chloride, vinyloxyethyldimethylamine, vinyloxymethyldiethylamine, N-propylenemethylmethyltrimethylammonium chloride , N-propylene decylethyltrimethylammonium chloride, N-propylene dimethyl dimethylamine, allyl trimethyl ammonium chloride, methallyl trimethyl ammonium chloride, dimethyl a monomer having a cationic group such as allylamine or allylethylamine; vinyltrimethoxydecane, vinylmethyldimethoxydecane, vinyldimethylmethoxydecane, vinyltriethyl Oxydecane, vinylmethyldiethoxydecane, vinyl dimethyl ethoxy decane, 3-(methyl) propylene decyl propyl trimethoxy decane, 3-(methyl) propylene decyl propyl A monomer having a mercapto group, such as a triethoxysilane. Use of these monomers copolymerizable with vinyl esters The amount varies depending on the purpose and use thereof to be used, but is generally 20 mol% or less, preferably 10 mol% or less, based on all monomers used for copolymerization.

PVA can be obtained by saponification of the polyvinyl ester obtained by the above method in an alcohol solvent.

As the catalyst for the saponification reaction of the polyvinyl ester, a basic substance is generally used. Examples of the catalyst include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal alkoxides such as sodium methoxide. When the amount of the alkaline substance used is based on the vinyl ester monomer unit of the polyvinyl ester, the molar ratio is preferably in the range of 0.002 to 0.2, and particularly preferably in the range of 0.004 to 0.1. The saponification catalyst may be added all at once in the initial stage of the saponification reaction, or a part may be added at the beginning of the saponification reaction, and the remainder may be additionally added during the saponification reaction.

Examples of the solvent which can be used in the saponification reaction include methanol, methyl acetate, dimethyl hydrazine, diethyl hydrazine, dimethylformamide, and the like. Among these solvents, methanol is also preferred. At this time, the water content of methanol is preferably adjusted to 0.001 to 1% by mass, preferably adjusted to 0.003 to 0.9% by mass, and particularly preferably adjusted to 0.005 to 0.8% by mass.

The saponification reaction is preferably carried out at 5 to 80 ° C, preferably at a temperature of 20 to 70 ° C. The saponification reaction is preferably carried out for 5 minutes to 10 hours, more preferably 10 minutes to 5 hours. The saponification reaction can be carried out by any of a batch method and a continuous method. After the saponification reaction is completed, the remaining catalyst can be neutralized as necessary. Examples of the usable neutralizing agent include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate.

The basic substance containing the alkali metal added during the saponification reaction can be generally neutralized by an ester such as methyl acetate produced by a 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 produced. In the present invention, it is preferred that the raw material PVA contains an alkali metal salt of a carboxylic acid in an amount of 0.5% by mass or less based on the mass of the alkali metal. To obtain such a PVA, the PVA can be washed after saponification.

In the present invention, as a method for adjusting the respective values in the above range as determined by GPC measurement, for example, a method in which PVA produced by the following method is used as a raw material of polyvinyl acetal is mentioned.

A) A vinyl ester which previously removes a radical polymerization inhibiting agent contained in a raw material vinyl ester is used in the polymerization.

B) The total content of the impurities contained in the vinyl ester of the raw material is 1 to 1200 ppm, preferably 3 to 1100 ppm, more preferably 5 to 1000 ppm of the alkenyl ester is used for radical polymerization. Examples of the impurities include aldehydes such as acetaldehyde, crotonaldehyde, and acrolein; acetaldehyde dimethyl acetal, crotonaldehyde dimethyl acetal, and acrolein dimethyl aldehyde which are acetalized with an alcohol of a solvent. An acetal such as acetal; a ketone such as acetone; an ester such as methyl acetate or ethyl acetate; and the like.

C) In a series of steps of radically polymerizing the starting vinyl ester in an alcohol solvent and recovering and recycling the unreacted vinyl ester, the alcohol decomposition or hydrolysis of the vinyl ester is inhibited by the alcohol or a trace amount of water. Therefore, adding organic acid, specifically adding glycolic acid, glyceric acid, malic acid, citric acid, lactic acid, tartaric acid, salicylic acid and other hydroxycarboxylic acids; malonic acid, amber A polycarboxylic acid such as an acid, maleic acid, phthalic acid, oxalic acid or glutaric acid can suppress the formation of an aldehyde such as acetaldehyde by decomposition. The amount of the organic acid to be added is preferably from 1 to 500 ppm, more preferably from 3 to 300 ppm, still more preferably from 5 to 100 ppm, based on the raw material vinyl ester.

D) The solvent used for the polymerization is preferably used in an amount of from 1 to 1200 ppm, preferably from 3 to 1100 ppm, more preferably from 5 to 1,000 ppm. Examples of the impurities contained in the solvent include those described above as impurities contained in the vinyl ester of the raw material.

E) When the vinyl ester is subjected to radical polymerization, the solvent ratio to the vinyl ester is increased.

F) As a radical polymerization initiator used in radically polymerizing a vinyl ester, an organic peroxide is used. Examples of the organic peroxide include acetam peroxide, isobutyl peroxide, diisopropyl peroxycarbonate, diallyl peroxydicarbonate, and di-n-propyl peroxydicarbonate. Ester, dimyristyl peroxydicarbonate, bis(2-ethoxyethyl)peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, bis(methoxyisopropyl) Peroxydicarbonate, bis(4-tert-butylcyclohexyl)peroxydicarbonate, etc., particularly preferably a peroxydicarbonate having a half-life of 60 to 110 minutes and a period of 10 to 110 minutes.

G) After the radical polymerization of the vinyl ester, when the inhibiting agent is added to suppress the polymerization, a forbidden agent of 5 mol equivalent or less is added to the remaining undecomposed radical polymerization initiator. The type of the inhibiting agent is a compound having a conjugated double bond having a molecular weight of 1,000 or less, and examples thereof include a compound which can stabilize the radical and inhibit the polymerization reaction. Specific examples can be exemplified Pentadiene, 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, 1-ethoxyl -1,3-butadiene, 2-ethoxy-1,3-butadiene, 2-nitro-1,3-butadiene, chloroprene, 1-chloro-1,3-butene Diene, 1-bromo-1,3-butadiene, 2-bromo-1,3-butadiene, fulvene, cycloheptatrienone, basilene, hydrocelene, myrcene, farnesene, a conjugated diene composed of two conjugated structures of carbon-carbon double bonds such as cemblene, sorbic acid, sorbate, sorbate, and citric acid; 1,3,5-hexanetriene, 2,4 a conjugated triene formed by three conjugated structures of carbon-carbon double bonds such as 6-octatriene-1-carboxylic acid, tung oil, tung oil, and cholecalciferol; cyclooctatetraene, 2, 4 6, A polyene such as a conjugated polyene formed by a conjugated structure of four or more carbon-carbon double bonds such as 8-nonylene-1-carboxylic acid, retinol or retinoic acid. Further, any one having a stereoisomer such as 1,3-pentadiene, myrcene or farnesene may be used. Further, 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-benzene An aromatic compound such as 1,3-butadiene or 1,4-diphenyl-1,3-butadiene.

H) An alcohol solution of a polyvinyl ester which removes the residual vinyl ester as much as possible is used for the saponification reaction. The removal rate of the residual monomer is preferably 99% or more, preferably 99.5% or more, and more preferably 99.8% or more.

It is preferred that the PVA produced by suitably combining A) to H) is acetalized to obtain the polyethylene acetal.

The acetalization of PVA can be carried out, for example, according to the following reaction conditions, but is not limited thereto. After heating at 80 to 100 ° C to dissolve the PVA in water, it is slowly cooled after 10 to 60 minutes to obtain a 3 to 40% by mass aqueous solution of PVA. When the temperature is lowered to -10 to 30 ° C, an aldehyde and an acid catalyst are added to the aqueous solution, and the acetalization reaction is carried out for 30 to 300 minutes while maintaining a constant temperature. At this time, a polyvinyl acetal having a certain degree of acetalization is precipitated. Thereafter, the reaction solution was heated to 25 to 80 ° C over 30 to 300 minutes, and the temperature was maintained for 10 minutes to 24 hours (this temperature was taken as the reaction temperature at the time of progress). Next, in the reaction solution, if necessary, a neutralizing agent such as a base is added to neutralize the acid catalyst, and after washing with water and drying, a polyvinyl acetal is obtained.

Generally, aggregated particles made of polyvinyl acetal are produced in such a reaction or treatment step, and coarse particles are easily formed. When such a coarse particle is produced, it may become a cause of variation between batches. On the other hand, when PVA manufactured by the above-mentioned predetermined method is used as a raw material, generation of coarse particles is suppressed compared with the conventional product.

The acid catalyst used for the acetalization reaction is not particularly limited, and any of 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 Among them, hydrochloric acid, sulfuric acid and nitric acid are also preferred. When nitric acid is generally used, the reaction rate of the acetalization reaction is increased, and on the other hand, productivity is expected to be improved. On the other hand, the obtained polyvinyl acetal particles tend to be coarse, and the variation between batches tends to be large. On the other hand, when PVA manufactured by the above-described predetermined method is used as a raw material, generation of coarse particles is suppressed.

In the present invention, the aldehyde to be used in the acetalization reaction is not particularly limited, and examples thereof include a known aldehyde having a hydrocarbon group and an alkyl acetal. Among the aldehydes having a hydrocarbon group, examples of the aliphatic aldehyde and the alkyl acetal thereof include formaldehyde (containing paraformaldehyde), acetaldehyde, propionaldehyde, butyl aldehyde, valeraldehyde, isovaleraldehyde, hexyl aldehyde, 2-ethylbutyl aldehyde, neopentaldehyde, octyl aldehyde, 2-ethylhexyl aldehyde, mercapto aldehyde, mercapto aldehyde, dodecyl aldehyde, etc., as an alicyclic aldehyde and its alkyl acetal Examples thereof include cyclopentanal aldehyde, methylcyclopentanal aldehyde, dimethylcyclopentanal aldehyde, cyclohexane aldehyde, methylcyclohexane aldehyde, dimethylcyclohexane aldehyde, cyclohexane acetaldehyde, and the like. Examples of the cyclic unsaturated aldehyde and the alkyl acetal thereof include a cyclopentenal, a cyclohexenal, and the like, and an aromatic or an unsaturated aldehyde and an alkyl acetal thereof include benzaldehyde and A. Benzoaldehyde, dimethylbenzaldehyde, methoxybenzaldehyde, phenylacetaldehyde, phenylpropylaldehyde, anisaldehyde, naphthaldehyde, furfural, cinnamaldehyde, crotonaldehyde, acrolein, 7-octene -1-Alcohol or the like, as a heterocyclic aldehyde, an alkyl acetal furfural, methyl furfural or the like. Among the aldehydes, an aldehyde having 1 to 8 carbon atoms is preferably used, and an aldehyde having 4 to 6 carbon atoms is preferably used, and n-butylaldehyde is particularly preferred. In the present invention, a polyvinyl acetal obtained by using two or more kinds of aldehydes in combination can be used.

For the present invention, as a use of polyvinyl alcohol resin As the acetalized aldehyde, an aldehyde having an functional group selected from the group consisting of a mercaptoamine group, an amine group, an ester group, a carbonyl group, and a vinyl group, or an alkylacetal thereof can be used. Among them, an aldehyde having an amine group as a functional group is also preferred. Examples of the aldehyde having an amine group as a functional group include aminoacetaldehyde, dimethylaminoacetaldehyde, diethylaminoacetaldehyde, alanylpropionaldehyde, dimethylaminopropionaldehyde, and aminobutyl group. Aldehyde, aminopentyl aldehyde, aminobenzaldehyde, dimethylaminobenzaldehyde, ethylmethylaminobenzaldehyde, diethylaminobenzaldehyde, pyrrolidinylacetaldehyde, piperidinyl acetaldehyde Further, pyridyl acetaldehyde or the like, and aminobutyl aldehyde is preferred from the viewpoint of productivity. Examples of the aldehyde having a vinyl group as a functional group include acrolein and the like.

Examples of the aldehyde having a carbonyl group as a functional group include glyoxylic acid and a metal salt or ammonium salt thereof, 2-methyl thioglycolic acid and a metal salt or ammonium salt thereof, 3-methyl mercaptopropionic acid, and a metal salt or ammonium thereof. Salt, 5-methylmercaptoic acid and its metal or ammonium salt, 4-methyl phenoxy phenoxyacetic acid and its metal or ammonium salt, 2-carboxybenzaldehyde and its metal or ammonium salt, 4- Carboxybenzaldehyde and its metal or ammonium salts, 2,4-dicarboxybenzaldehyde and its metal or ammonium salts.

Examples of the aldehyde having an ester group as a functional group include methyl glyoxylate, ethyl glyoxylate, methyl mercaptoacetate, methyl mercaptoacetate, methyl 3-methylmercaptopropionate, and 3 - methyl mercaptopropionate, methyl 5-methylmercaptoate, ethyl 5-methylmercaptoate or the like.

Further, in the range which impairs the characteristics of the present invention, a heterocyclic aldehyde and an alkyl acetal thereof, an aldehyde having a hydroxyl group, an aldehyde having a sulfonic acid group, an aldehyde having a phosphoric acid group, having a cyano group, a nitro group or 4 may be used. An aldehyde such as an ammonium salt or an aldehyde having a halogen atom.

The content of the polyethylene acetal in the resin composition of the present invention is not particularly limited, and is preferably 0.01 to 80 parts by mass based on 100 parts by mass of the resin composition. When the content of the polyethylene acetal in the resin composition is within this range, it has excellent mechanical properties and good adhesion. When the content is less than 0.01 parts by mass, there is a fear that the adhesion force when the resin composition is insufficient may occur. The content is preferably 1 part by mass or more. On the other hand, when the content exceeds 80 parts by mass, the obtained molded body becomes hard and it is difficult to exhibit good mechanical properties. The content is preferably 50 parts by mass or less.

The polyester, polyamine, polyolefin, α-olefin (co)polymer, cellulose resin, acrylic resin, and styrene resin contained in the resin composition of the present invention are not particularly limited. A well-known person can be used. For example, a polyester resin such as polyethylene terephthalate, polybutylene terephthalate or polyethylene-2,6-naphthalate; nylon 6, nylon 12 may be mentioned. Poly-amide type resin; α-olefin (co)polymer such as polyethylene or polypropylene; and copolymer of α-olefin, ethylene-propylene copolymer rubber (EPR) and ethylene-extension Base-diene copolymer rubber (EPDM). Moreover, a typical example of the copolymer of ethylene and a monomer other than the α-olefin is an ethylene-vinyl acetate copolymer (EVA) or a saponified product thereof.

Further, examples thereof include cellulose resins such as cellulose, cellulose acetate, ethyl cellulose, and triacetyl cellulose; polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polypropyl ( Methyl) acrylate, polyisopropyl (meth) acrylate, poly-n-butyl (meth) acrylate, poly-sec-butyl (A) Acrylic resin such as acrylate or poly-tert-butyl (meth) acrylate; block copolymerization of polymer blocks composed of polystyrene, aromatic vinyl compound and conjugated diene compound a styrene resin such as a substance or a hydride thereof; a resin such as these and a copolymer thereof.

Among them, polyolefin resin such as polyethylene or polypropylene or polyethylene terephthalate or polybutylene terephthalate is considered in consideration of transparency and secondary workability. A polyester resin such as an ester or a polyethylene-2,6-naphthalate is preferable. Further, when moisture resistance is taken into consideration, an olefin resin such as polyethylene or polypropylene is preferred, and polypropylene is particularly preferred. . Further, as the copolymer with the α-olefin, an ethylene-vinyl acetate copolymer (EVA) of a copolymer of ethylene and a monomer other than the α-olefin is also preferable.

Examples of the polypropylene include a propyl homopolymer, an ethylene group other than a propyl group and a propyl group, 1-butene, 1-pentene, 1-hexene, and 4-methyl-1-pentene. A random or block copolymer of an α-olefin, further including a mixture of these polymers, wherein a propyl homopolymer, a propyl-ethylene random copolymer, and a propyl-ethylene-1 are also used. A butene random terpolymer is preferred.

Further, in the above polypropylene, other resins and copolymers can be used to the extent that the effects of the present invention are not inhibited. The copolymerizable monomer is not particularly limited, and examples thereof include a copolymer of ethylene and vinyl acetate, an acrylate, and an acrylic monomer, or a mixture of two or more of these polymers.

Moreover, as the thermoplastic resin to be used in the present invention, one type of the above-mentioned resins may be used alone, or two or more types may be used in combination.

Further from the point of view of connectivity, if the thermoplastic tree When the compatibility between the fat and the polyvinyl acetal is lowered, the thermoplastic resin to be used may be a thermoplastic resin containing a polar functional group, and these may be used in combination. Since the thermoplastic resin containing a polar functional group has good compatibility with the polyvinyl acetal, it has excellent mechanical properties of the resin composition and excellent adhesion to the covering.

In addition to the thermoplastic resin and the polyvinyl acetal, the resin composition of the present invention may contain a softener for rubber, if necessary, for the purpose of imparting formability and flexibility. As such a softening agent, a softener for mineral oil-based rubber called a processing oil or an extended oil is mentioned, for example. This is a mixture of three aromatic rings, a cycloalkane ring and a paraffin. Among the total carbon numbers, the carbon number of the paraffin chain is 50% by mass or more, and the carbon number of the cycloalkane ring is 30~. 45 mass% is called a cycloalkane system, and the aromatic carbon number is more than 30%, and it is called an aromatic system. In general, 5 to 500 parts by mass of a rubber softener can be added to 100 parts by mass of the thermoplastic resin.

Further, the resin composition of the present invention may contain a plasticizer, an inorganic filler, a compatibilizing agent, a lubricant, a light stabilizer, a weathering agent, and a processing aid, if necessary, in addition to the above-described components, without departing from the effects of the invention. Coloring agents such as pigments and pigments, flame retardants, antistatic agents, softeners, plasticizers, matting agents, fillers, eucalyptus oils, anti-blocking agents, ultraviolet absorbers, antioxidants, release agents, adhesion promoters, One or two or more kinds of other components such as a foaming agent and a fragrance. The content of the component other than the polyvinyl acetal is 50% by mass or less, preferably 20% by mass or less, and preferably 10% by mass or less.

The above plasticizer does not impair the effect of the present invention, and The compatibility of the olefin acetal is not a problem and is not particularly limited. The plasticizer is not particularly limited as long as it does not impair the effects of the present invention and does not cause compatibility with the polyvinyl acetal. As the plasticizer, a mono- or diester of an oligomeric alkanediol having a hydroxyl group at both terminals, a diester of a dicarboxylic acid and an alcohol, or the like can be used. These can be used individually or in combination of 2 or more types. Specific examples thereof include triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-n-heptanoate, and tetraethylene a tri- or tetraethylene glycol such as an alcohol-di-n-heptanoate or a mono- or di-ester of an oligoalkylene glycol having a hydroxyl group at both terminals; a dioctyl phthalate, a dibutyl phthalate An ester of a dicarboxylic acid such as phthalic acid ester, dioctyl adipic acid or dibutyl adipate with an alcohol.

The method for producing the resin composition of the present invention is not particularly limited, and may be any method which can uniformly mix the above-mentioned components used in the resin composition of the present invention, and it can be produced by any method, and a melt kneading method is generally used. The melt-kneading can be carried out, for example, by using a melt-kneading device such as a uniaxial extruder, a 2-axis extruder, a kneader, a batch mixer, a roll mixer, an internal mixer, or the like, and generally can be carried out at a temperature of 100 ° C to 270 ° C. The resin composition of the present invention is obtained by melt-kneading.

Since the resin composition of the present invention has hot meltability and excellent moldability, various molded articles, sheets, and films can be produced. As the molding method at this time, various molding methods generally used for the thermoplastic resin can be used, and for example, any molding method such as injection molding, extrusion molding, press molding, blow molding, calender molding, or tape casting can be employed. Further, in the formation of a film or a sheet, a general T-die method, a rolling method, an inflation method, a conveyor belt method, or the like can be used.

A preferred embodiment of the molded article of the resin composition of the present invention is a laminate obtained by coating or bonding a molded article formed of the resin composition to a coated body. The coating body has, for example, a functional group selected from the group consisting of a mercaptoamine group, an ester group, a carbonate group, an acetal group, an ether group, a thioether group, a nitrile group, a hydroxyl group, a carbonyl group, a carboxyl group, an amine group, and a sulfonic acid group. A polar polymer based. These functional genes have an interaction with the polyvinyl acetal contained in the resin composition of the present invention, and thus have good adhesion to the resin composition of the present invention. The styrene resin or the α-olefin (co)polymer generally has a poor adhesion to a polar polymer, and the resin composition of the present invention is excellent in adhesion to a polar polymer for the above reasons, and Then the stability is also excellent. Therefore, the resin composition of the present invention can be applied in combination with the above polar polymer.

Preferred examples of the polar polymer include polyamine, polyester, polycarbonate, polyacetal, polyphenylene sulfide, and ABS resin (acrylonitrile-butadiene-styrene copolymer), and polyethylene. Alcohols, ethylene-vinyl alcohol copolymers, polyvinyl acetals, polyvinyl acetates, poly(meth)acrylates, polyethers, polyketones, ionomers, polyurethanes, and polyureas.

The method for producing the molded article of the resin composition of the present invention and the polar polymer is not particularly limited. For example, a molding method such as an injection molding method, an extrusion molding method, a pressure molding method, or a melt injection molding method can be given. Further, the solution may be melt-coated or applied to one of the preformed molded articles. Others may also be formed by two-color molding or insert molding.

A solvent-based paint, an aqueous paint, and a solvent-free paint can be used for the application of the molded body formed by the resin composition of the present invention. Examples of the solvent-based coating material include an alkyd resin coating material, an amine alkyd resin coating material, a vinyl resin coating material, a room temperature drying type acrylic resin coating material, a barbecue drying type acrylic resin coating material, and a tar epoxy type. Epoxy resin coating, painting. Enamel-type epoxy resin coating, one-liquid urethane resin coating, multi-liquid urethane resin coating, unsaturated polyester resin coating, chlorinated rubber coating. Moreover, examples of the water-based paint include an emulsion paint and a water-soluble resin paint. Further, examples of the solventless coating material include powder coating materials and road marking paints.

In the production of the laminate, at least a part of the surface of the molded body is preferably treated by plasma discharge treatment, corona discharge treatment or ultraviolet irradiation treatment, or atmospheric piezoelectric slurry treatment. These treatments can be carried out according to the usual method, but the conditions of the plasma discharge treatment are preferably from 1 to 100,000 Pascal, and the ambient gas is preferably argon, helium or nitrogen. The number of discharge frequencies, the discharge power, and the processing time may be appropriately adjusted according to the shape or size of the processing device, and generally the frequency is 13.56 MHz, the output is 10 to 1000 watts, and the processing time is 5 seconds to 10 minutes. .

Further, the corona discharge treatment is generally carried out in the air because the apparatus is light, and it is possible to improve the treatment effect and improve the adhesion. The inert gas such as argon gas or a gas atmosphere such as oxygen or nitrogen can be used. The gas is treated while blowing under the electrode. Particularly when the corona discharge treatment is performed in nitrogen gas, the treatment effect can be improved and the running cost can be suppressed to a lower level, and the advantage is that the treatment of ozone generated by corona discharge treatment in air is not required, and the present invention This method is adopted as a resin reforming method as the best method.

Although the frequency of the corona discharge treatment can be appropriately adjusted, it is generally 5 kHz or more from the viewpoint of processing effect and efficiency, and particularly preferably 20 to 30 kHz. When it is lower than 5 kHz, it is difficult to uniformly process it under stable conditions, and the power consumption is also increased, so that the power cost is increased and the electrode durability is also shortened.

Further, the discharge power and the processing time are preferably adjusted in accordance with the material, shape, size, or electrode shape of the material to be processed, and are generally preferably 50 to 5,000 watts, preferably 1 to 60 seconds.

Atmospheric piezoelectric pastes can be used in a variety of atmospheric piezoelectric slurry devices. For example, it is preferable to carry out intermittent discharge under an inert gas under pressure of atmospheric pressure between electrodes covered with a dielectric body, and it is preferable to use a device capable of generating low-temperature plasma, and any device can be used, and various modifications can be selected in accordance with the purpose of use. . The "pressure in the vicinity of atmospheric pressure" in the "atmospheric piezoelectric slurry" of the present invention means a range of 70 kPa or more and 130 kPa or less, preferably 90 kPa or more and 110 kPa or less.

As the discharge gas used in the generation of the atmospheric piezoelectric slurry, any one of nitrogen, oxygen, hydrogen, carbon dioxide, helium, and argon, or a mixture of two or more thereof may be used. It is preferable to use a noble gas such as He or Ar as an inert gas or nitrogen (N ₂ ), and a rare gas of Ar or He is preferable.

The shape, structure, use, and the like of the molded article and laminate formed of the resin composition of the present invention are not particularly limited, and are useful for a wide range of applications. Moreover, it can also be applied to a resin molded article for a bumper or a door mirror cover, a mold, a spoiler, or the like, or a joint in a building. Electronic components such as ministry and solar cell modules, groceries, daily necessities, and exhibits.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples and comparative examples. The "parts" and "%" in the following examples and comparative examples are all based on quality unless otherwise specified. "Polymerity" means "viscosity average degree of polymerization". Further, the present invention is not limited by the related embodiments. Further, the synthesis of the resin and the preparation of the test piece and the measurement or evaluation of each physical property in the examples and the comparative examples were carried out as follows.

[Synthesis of Polyvinyl Acetate] PVAc-1

It was placed in a 6 L separable flask equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a reflux tube, and deoxygenated in advance, and charged with vinyl acetate (VAM) containing 500 ppm of acetaldehyde (AA) and 50 ppm of acetaldehyde dimethyl acetal (DMA). 2555 g; a tartaric acid 1% methanol solution containing acetaldehyde dimethyl acetal 50 ppm, acetaldehyde content of less than 1 ppm of methanol (MeOH) 945 g, and vinyl acetate content of tartaric acid of 20 ppm. The temperature inside the flask was adjusted to 60 ° C while blowing nitrogen gas into the flask. The ethylene glycol/water solution at -10 ° C was circulated in a reflux tube. A 0.55 mass% methanol solution of di-n-propyl peroxydicarbonate was prepared, and 18.6 mL of the solution was added to the flask to start polymerization. The amount of di n-propyl peroxydicarbonate added at this time was 0.081 g. A methanol solution of di-n-propylperoxydicarbonate was successively added to the end of the polymerization at a rate of 20.9 mL/hour. In the polymerization, the inside of the flask The temperature was maintained at 60 °C. Four hours after the start of the polymerization, 0.0141 g of sorbic acid (corresponding to 3 n-propyl peroxydicarbonate remaining unresolved in the polymerization liquid) was added at a time when the solid content concentration of the polymerization liquid was 25.1%. After 1200 g of methanol of the molar equivalent), the polymerization solution was cooled to stop the polymerization. The polymerization rate of vinyl acetate at the time of stopping the polymerization was 35.0%. After cooling the polymerization solution to room temperature, the inside of the flask was depressurized by using a water aspirator, and vinyl acetate and methanol were distilled off to precipitate polyvinyl acetate. After adding 3000 g of methanol to the precipitated polyvinyl acetate, the polyvinyl acetate was dissolved while heating at 30 ° C, and the inside of the flask was again decompressed using a water aspirator, and then vinyl acetate and methanol were distilled off. Polyvinyl acetate is precipitated. After the polyvinyl acetate was dissolved in methanol, the operation of precipitating was repeated twice more. Methanol was added to the precipitated polyvinyl acetate to obtain a 40% by mass methanol solution of polyvinyl acetate (PVAc-1) having a vinyl acetate removal rate of 99.8%.

The degree of polymerization was determined using a portion of the obtained PVAc-1 methanol solution. In a methanol solution of PVAc-1, a molar ratio of sodium hydroxide to a monomer of vinyl acetate in polyvinyl acetate was set to 0.1, and a 10% methanol solution of sodium hydroxide was added. The gel was pulverized at the time of gel formation, and Soxhlet extraction was carried out for 3 days with methanol. The obtained polyvinyl alcohol was dried to provide a viscosity average degree of polymerization. The degree of polymerization was 1700.

PVAc-2~PVAc-11

Except for the conditions described in Table 1, by using with PVAc-1 In the same manner, polyvinyl acetate (PVAc-2~PVAc-11) was obtained. Further, "ND" in Table 1 indicates that it is less than 1 ppm. The degree of polymerization of each of the obtained polyvinyl acetates was determined in the same manner as in PVAc-1.

The results are shown in Table 1.

PVAc-A~H

Polyvinyl acetate PVAc-A~H was obtained by the same method as PVAc-1 except that the conditions described in Table 2 were changed. The amount of denaturation of each comonomer was determined by using a 500 MHz proton NMR measuring apparatus (JEOL GX-500) in a sample dissolved in DMSO-d6 or CDCl ₃ .

[Synthesis of polyvinyl alcohol] PVA-1

For a 40% by mass methanol solution of polyvinyl acetate of PVAc-1, the total solid content concentration (saponification concentration) is 30% by mass, and the vinyl acetate monomer unit in methanol and polyvinyl acetate is desired. The molar ratio of sodium hydroxide was 0.020, and an 8% methanol solution of sodium hydroxide was added thereto with stirring, and the saponification reaction was started at 40 °C. As the saponification reaction proceeds, the gel is pulverized at the point of time when the gelation is formed, and the pulverized gel is transferred to a vessel at 40 ° C, and immersed in methanol/acetic acid at a time point of 60 minutes from the start of the saponification reaction. Base/water (25/70/5 mass ratio) solution and neutralized. The obtained swelling gel was centrifuged, and twice the mass of methanol was added to the mass of the swelling gel, and immersed. After standing for 30 minutes, the operation of centrifuging was repeated four times, dried at 60 ° C for 1 hour, and dried at 100 ° C. PVA-1 was obtained after 2 hours.

The degree of polymerization and the degree of saponification of PVA-1 were determined in accordance with the method described in JIS K6726. The degree of polymerization was 1700 and the degree of saponification was 99.1% by mole. These physical property data are shown in Table 3.

After ashing PVA-1, the ICP luminescence analyzer "IRIS AP" manufactured by Jarreer Gray Co., Ltd. was used, and the sodium content of PVA-1 was determined by measuring the amount of sodium in the obtained ash. The content of sodium acetate was 0.7% (0.20% in terms of sodium). These physical property data are shown in Table 3.

PVA-2~7, compare 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 degree of polymerization of the obtained PVA, the degree of saponification, and the content of sodium acetate (calculated as the mass of sodium) were measured in the same manner as in PVA-1. These results are shown in Table 3.

PVA-A1~G, compare 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 degree of polymerization, the degree of saponification, and the content of sodium acetate (calculated as the mass of sodium) of the obtained PVA were measured in the same manner as in PVA-1. These results are shown in Table 4.

(Analysis method of PVA)

The analysis of PVA was carried out in accordance with the method described in JIS K6726 unless otherwise specified. The content of the N-vinylguanamine monomer unit and the acrylonitrile monomer unit contained in the PVA was determined by using a 500 MHz proton NMR measuring device (JEOL GX-500) for the sample dissolved in DMSO-d6. .

[Synthesis of Polyethylene Acetal] <PVB-1-1>

In a 10 liter glass container equipped with a reflux condenser, a thermometer, and a crucible stirring blade, 8100 g of ion-exchanged water and 660 g of PVA-1 (7.5% PVA) were charged, and the contents were heated to 95 ° C to completely dissolve the PVA. . Next, the content was stirred at 120 rpm, and after slowly cooling to 10 ° C over about 30 minutes, n-butyl aldehyde was added to the above container. 384 g and 540 mL of 20% hydrochloric acid were subjected to a butyralization reaction for 150 minutes. Thereafter, the temperature was raised to 60 ° C over 60 minutes, and after maintaining at 60 ° C for 120 minutes, it was cooled to room temperature. After the precipitated resin was washed with ion-exchanged water, an excess amount of the aqueous sodium hydroxide solution was added and neutralized. Then, the resin was washed again with ion-exchanged water, and dried to obtain polyvinyl butyral.

(Analysis method of polyethylene acetal)

The butyralization degree (acetalization degree) of the polyvinyl butyral, the content of the vinyl acetate monomer unit, and the content of the vinyl alcohol monomer unit are measured in accordance with JIS K6728. The degree of butyralization (degree of acetalization) of the obtained polyvinyl butyral was 68.2 mol%, the content of the vinyl acetate monomer unit was 0.9 mol%, and the content of the vinyl alcohol monomer unit was 30.9% by mole. Thereafter, in the synthesis example, the amount of denaturation of the amino acetal in the vinyl acetal polymer was determined by using a 500 MHz proton NMR measuring apparatus (JEOL GX-500) in a sample dissolved in DMSO-d6. The results are shown in Table 5.

[GPC measurement of PVB] (measuring device)

GPC measurement was performed using "GPCmax" manufactured by VISCOTECH. "TDA305" manufactured by VISCOTECH is used as the differential refractive index detector. As a UV-visible absorbance photodetector, "UV Detector 2600" manufactured by VISCOTECH is used. The detection path of the container for the absorbance photodetector has an optical path length of 10 mm. GPC pipe column is manufactured by Showa Denko Co., Ltd. "GPC HFIP-806M". In addition, the analysis software uses the accessory OmniSEC (Version 4.7.0.406).

(measurement conditions)

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

Further, a sample having a viscosity average degree of polymerization of PVA of more than 2,400, which will be described later, was subjected to GPC measurement using a suitably diluted sample (100 μl). The absorbance at a sample concentration of 1.00 mg/ml was calculated from the measured value by the following formula. α (mg/ml) is the diluted sample concentration.

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

(made of the standard curve)

As a standard, polymethyl methacrylate (hereinafter abbreviated as "PMMA") manufactured by Agilent Technologies was measured (absorbent peak top molecular weight: 1944000, 790,000, 467,400, 271,400, 144,000, 79,250, 35,300, 13,300, 7,100, 1,960, 1020). 690) For each of the differential refractive index detector and the absorbance photodetector, a standard curve for converting the elution capacity into the PMMA molecular weight is prepared. The standard curve is used to use the aforementioned analysis software. Further, the measurement of the polymethyl methacrylate for the measurement was carried out by using a column in which the absorption peaks of the two kinds of molecular weights of 1944000 and 271400 were separated from each other.

Further, with the present device, the absorption peak intensity obtained by the differential refractive index detector indicates mV (millivolt), and the absorption peak intensity obtained by the UV Detector indicates absorbance (abs unit).

(Preparation of sample)

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

The sample prepared according to the above method was dissolved in 20 mmol/l of hexafluoroisopropanol containing sodium trifluoroacetate (hereinafter abbreviated as "HFIP") to prepare a 1.00 mg/ml solution of PVA. This solution was filtered through a 0.45 μm polytetrafluoroethylene ethyl filter and used for 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 by the differential refractive index detector, and the relationship between the molecular weight and the absorbance measured by the absorbance photodetector (measurement wavelength: 280 nm). The molecular weight at this time is the one converted from the standard curve by the dissolution capacity (molecular weight in terms of PMMA). The absorption peak peak molecular weight (A) measured by the differential refractive index detector obtained in Fig. 1 was 90,000, and the absorption peak tip molecular weight (B) measured by the absorbance photodetector (280 nm) was 68900. The value obtained by bringing the obtained value into the following formula (AB)/A was 0.23. The absorbance (b) in the molecular weight (B) of the absorption peak was 2.21 × 10 ^-3 . The ratio Mw/Mn of the weight average molecular weight Mw of the number average molecular weight Mn obtained from the chromatogram (RI) in Fig. 1 was 3.4. These results are shown in Table 5.

<PVB-1-2~PVB-7>

The polyvinyl butyral was synthesized in the same manner as in the case of changing the raw material PVA to those shown in Table 5. The evaluation of the same obtained polyvinyl acetal (GPC measurement) was continued. The results are shown in Table 5.

<PVB-A1~F>

The raw material PVA was changed to the same as in Table 5, and polyvinyl butyral was synthesized in the same manner. The evaluation of the same obtained polyvinyl acetal (GPC measurement) was continued.

<PVB-NH-1>

The denatured polyvinyl butyral was synthesized and evaluated in the same manner except that the diethyl acetal of 4-aminobutyl aldehyde was 21.5 g and the amount of n-butyl aldehyde was changed to 375 g. The results are shown in Table 5.

<Compare PVB-1~H2>

The polyvinyl butyral was synthesized in the same manner except that the raw material PVA was changed to those shown in Table 5. The evaluation of the same obtained polyvinyl acetal (GPC measurement) was continued.

<Example 1> (1) Production of resin composition and polar resin sheet

The polyvinyl acetal shown in Table 6 was used, and the polypropylene emulsifier was added to the polyethylene acetal to be 20% by mass in total, and the batch mixer "Labo Plastomill 20R20C" manufactured by Toyo Seiki Co., Ltd. was used. Melt kneading was carried out for 5 minutes at 230 ° C at a number of revolutions of 100 rpm. The obtained kneaded material was subjected to a compression press molding machine "NF-37" manufactured by Shinto Metal Industry Co., Ltd., and a metal frame was coated with a "Teflon (registered trademark)" as a spacer at a load of 100 kgf/cm ² at 230 ° C. After 5 minutes of compression press molding, a resin composition sheet having a thickness of 1 mm was obtained.

Further, the following polypropylene was used, and the following rubber softener for 50 phr of polypropylene was added and used for the above treatment.

[Polypropylene]

Polypropylene "NovatecPP MA3" made by Japan Jukai Co., Ltd.

[softener for rubber]

Wax-based processing oil "Diana Process PW-90" manufactured by Idemitsu Kosan Co., Ltd.

(2) Tensile strength and tensile elongation determination

The sheet prepared by the above method (1) was perforated to prepare a JIS No. 3 dumbbell test piece. Using the dumbbell test piece, "Autograph AG-5000B" manufactured by Shimadzu Corporation was used, and tensile strength and tensile elongation at break were measured in accordance with JIS K6251 at 500 mm/min.

Tensile breaking strength test

A: The breaking strength is 5 MPa or more.

B: breaking strength 1~ less than 5MPa

C: breaking strength is less than 1MPa

Tensile fracture extension test

A: The elongation at break is 200% or more.

B: The elongation at break is 100%~ less than 200%

C: the elongation at break is less than 100%

(3) Preparation of the adhesion test sample

An atmospheric piezoelectric slurry device was used on the surface of a sheet of 50 mm × 25 mm × 1 mm obtained by the sheet produced by the above method (1), and a gas mixture of a flow rate of 11 kV was used at a flow rate of 11 kV using a nitrogen gas of 150 L/min. The sample was moved at a speed of 10 mm/sec and the distance between the electrodes was 2 mm. The plasma treatment was continued, and the fluororesin sheet was further masked to make a polar polymer sheet (50 mm × 25 mm ×) as described in Table 6 without atmospheric piezoelectric slurry treatment. The end face of 1 mm) was only a portion of 25 mm × 25 mm, and then a sheet of the resin composition was placed. This was sandwiched between the metal plates of the compression molding machine, and hot pressed under the conditions shown below to obtain a laminate bonded to the resin composition sheet and the polar polymer sheet. At the same time, it is also made without plasma treatment.

Pressurizing temperature 180~260°C

Pressure 2Mpa

Time 10 minutes

The polar polymer with the resin composition is used as The next one.

[PET] polyethylene terephthalate "Bottle TR-8550" made by Teijin Co., Ltd.

[PA6] Polyamide "UBE Nylon 1013B" manufactured by Ube Industries Co., Ltd.

[ABS] ABS "Psycho rack EX-111" by Ube Cycon Co., Ltd.

[POM] Polyplastic Excipient Co., Ltd. Polyoxymethyl Methyl "DURACON M90-44"

(4) Determination of the strength

For the laminate produced above, "Autograph AG-5000B" manufactured by Shimadzu Corporation was used, and the peeling strength test was performed under the conditions of a peeling angle of 180° and a tensile speed of 50 mm/min in accordance with JIS K6854-2. The continuation was evaluated by the following three stages using a functional test that was considered to be the subject.

A: Inter-layer peeling was not confirmed at all, and strongly followed, showing very good adhesion.

(larger than 10N/25mm)

B: A part of the interlayer peeling was confirmed, but showed good adhesion.

(1N/25mm~10N/25mm)

C: The peeling between the layers was confirmed, and it was judged that the adhesion was poor.

(not up to 1N/mm)

(5) Next evaluation method of stability

The test piece prepared in the same manner as the test piece evaluated in the above (4) was stored in a dark place under an environmental condition (normal temperature) at a temperature of 25 ° C and a humidity of 60% RH for a certain period of time, and the adhesion was carried out in the same manner as (4). test.

A: After the storage for 50 days, the subsequent strengths of the subsequent ones are compared, and the subsequent properties are not changed, or the adhesion reduction rate is less than 5%.

B: After the storage for 50 days, the subsequent strength after the comparison is compared, and the rate of decrease in adhesion is less than 20%.

C: After the storage for 50 days, the subsequent strength after the subsequent comparison was compared, and the rate of decrease in adhesion was 20% or more.

The results are shown in Table 6.

<Examples 2 to 23>

The same evaluation as in Example 1 was carried out except that the raw material PVB was changed to those shown in Table 6. The results are shown in Table 6.

In the example of the ethylene-vinyl acetate copolymer (EVA) (the content of the vinyl acetate is 28% by mass), the batch mixer "Labo Plastomill 20R20C" manufactured by Toyo Seiki Seisakusho Co., Ltd. is used as the thermoplastic resin. The ethylene acetal PVB was melted and kneaded in an amount of 20% by mass in a total amount of 150 rpm at 100 ° C for 5 minutes. The obtained kneaded material was subjected to a compression press molding machine "NF-37" manufactured by Shinto Metal Industry Co., Ltd., and a fluororesin coated metal frame was used as a spacer, and subjected to compression at a load of 150 ° C, 100 kgf / cm ² for 5 minutes. After molding, a sheet of a resin composition having a thickness of 1 mm was obtained.

<Example 24>

The same operation as in Example 1 was carried out, except that the softener for rubber was not used, and evaluated. The results are shown in Table 6.

<Comparative Examples 1 to 14>

The same operation as in Example 1 was carried out and evaluated except that the polyvinyl acetal and the composition shown in Table 6 were changed.

(6) Smear test

The surface of the 50 mm × 50 mm × 1 mm sheet obtained from the sheet produced by the above method (1) was subjected to plasma treatment using an atmospheric piezoelectric slurry apparatus, and the urethane coating-based metallic coating was continuously applied (manufactured by Bee Chemical Co., Ltd., Japan) Product name: R-212) to a thickness of 20 μm, dried at 80 ° C for 30 minutes, After leaving at room temperature for 48 hours, a test piece was obtained. The obtained test piece was cut into a square-shaped cut of 2 mm intervals, and the cellophane adhesive tape (JIS Z1522) was fully pressed on the test piece, and the coated film was pulled open at about 30 degrees with the surface of the coated film to calculate the peeled coated film. number.

A: The stripper is 0 in 100 pieces.

B: Those who have not reached 11

C: 11 or more

When the resin compositions of Examples 1 to 24 were used, the obtained molded article exhibited excellent mechanical properties and good adhesion to the polar resin or spreadability. Further, by irradiating the atmospheric piezoelectric slurry to the resin or the molded body, it is possible to exhibit better adhesion or spreadability, and then the stability is also very good. On the other hand, when a resin composition which did not satisfy the conditions specified in the present invention (Comparative Examples 1 to 14) was used, all the properties were shown to be reduced.

Claims (10)

A resin composition characterized by comprising a polyvinyl acetal and a thermoplastic resin, wherein the polyvinyl acetal has a degree of acetalization of 50 to 85 mol%, and the vinyl ester monomer unit has a content of 0.1 to 20 Mohr%, viscosity average polymerization degree: 200 to 5000, when the polyethylene acetal heated at 230 ° C for 3 hours was subjected to gel permeation chromatography, the absorption peak peak molecular weight measured by the differential refractive index detector (A) The absorption peak peak molecular weight (B) measured by the absorbance photodetector (measurement wavelength 280 nm) satisfies the following formula (1) (AB) / A < 0.60 (1), and the absorption peak tip molecular weight (B) The absorbance is 0.50×10 ^-3 to 1.00×10 ^-2 ; the thermoplastic resin is selected from the group consisting of polyester, polyamine, α-olefin (co)polymer, cellulose resin, acrylic resin, and styrene. Resin. The resin composition of claim 1, wherein the weight average molecular weight Mw of the number average molecular weight Mn of the polyvinyl acetal obtained by the differential refractive index detector is determined by the differential refractive index detector. The ratio Mw/Mn is 2.8 to 12.0. The resin composition of claim 1 or 2, wherein the polyvinyl acetal is a functional group having a functional group selected from the group consisting of a mercaptoamine group, an amine group, an ester group, a carbonyl group, and a vinyl group in the side chain. The resin composition of claim 3, wherein the aforementioned functional group having a polyvinyl acetal is an amidino group or an amine group. The resin composition according to any one of claims 1 to 4, wherein the aforementioned The thermoplastic resin is a styrene resin or an α-olefin (co)polymer. A molded body characterized by being a resin composition as claimed in any one of claims 1 to 5. A molded body according to claim 6, which is irradiated with plasma at least a part of the surface. A laminate characterized by being applied or bonded to a molded article according to claim 7. The laminate of claim 8, wherein the coating system has a structure selected from the group consisting of a mercapto group, an ester group, a carbonate group, an acetal group, an ether group, a thioether group, a nitrile group, a hydroxyl group, a carbonyl group, a carboxyl group, an amine group, and A polar polymer of a functional group in which a sulfonic acid group is grouped. The laminate of claim 9, wherein the polar polymer is selected from the group consisting of polyamine, polyester, polycarbonate, polyacetal, polyphenylene sulfide, ABS resin, polyvinyl alcohol, ethylene-vinyl alcohol copolymer At least one of a group of polyvinyl acetal, polyvinyl acetate, poly(meth) acrylate, polyether, polyketone, ionomer, polyurethane, and polyurea.