Α-olefin-modified polyvinyl acetal resin composition, interlayer film for laminated glass, and laminated glass

Abstract

The present invention addresses the problem of providing an α-olefin-modified polyvinyl acetal resin composition with which it is possible to form a laminated glass that is excellent in terms of penetration resistance, end part peeling resistance, and wet heat resistance. The means for solving the problem is an α-olefin-modified polyvinyl acetal resin composition which contains an α-olefin-modified polyvinyl acetal resin and a compound that has a structure in which a hydrocarbon group having 6 or more carbon atoms and a polyoxyalkylene group are bonded to each other.

Description

α-olefin-modified polyvinyl acetal resin composition, interlayer film for laminated glass, and laminated glass

[0001] This patent application claims the benefit of Patent Application No. 2023-219053, filed in Japan on December 26, 2023, the contents of which are incorporated herein by reference. The present invention relates to an α-olefin-modified polyvinyl acetal resin composition, and in particular to an α-olefin-modified polyvinyl acetal resin composition used as an interlayer film for laminated glass.

[0002] Laminated glass is a composite glass in which an interlayer film for laminated glass made of a thermoplastic resin such as polyurethane, ethylene-vinyl acetate copolymer, or polyvinyl acetal resin is sandwiched between a plurality of glass plates.

[0003] Laminated glass is safe because it shatters little even if it is broken by an external impact, and is therefore widely used as windshields, side windows, and rear windows of vehicles such as automobiles, as well as window glass in aircraft and buildings.

[0004] Patent Document 1 describes an acetalized product of an ethylene-vinyl alcohol copolymer, in which the symmetry coefficient, which indicates the acetalization degree distribution, and the melting peak temperature / midpoint glass transition temperature ratio, which indicates the degree of crystallinity, are each adjusted to a specific range. It is said that a resin sheet containing the acetalized product of Patent Document 1 can improve self-supporting ability and creep resistance in high-temperature environments while maintaining high transparency and penetration resistance.

[0005] Patent Document 1 describes an interlayer film for laminated glass made of this resin sheet and laminated glass using the same. It also describes that a resin sheet containing a specific amount of a plasticizer with a specific SP value has excellent bleed-out resistance and provides excellent penetration resistance to the laminated glass.

[0006] International Publication No. 2022 / 220085

[0007] It has been found that when conventional α-olefin-modified polyvinyl acetal resin compositions are used as interlayer films for laminated glass, there is still room for improvement in the edge peel resistance of the laminated glass.

[0008] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide an α-olefin-modified polyvinyl acetal resin composition capable of forming laminated glass having excellent penetration resistance, edge peel resistance, and heat and humidity resistance.

[0009] The present invention provides the following aspects: [Aspect 1] An α-olefin-modified polyvinyl acetal resin composition comprising an α-olefin-modified polyvinyl acetal resin and a compound having a structure in which a hydrocarbon group having 6 or more carbon atoms and a polyoxyalkylene group are bonded together.

[0010] [Embodiment 2] The α-olefin-modified polyvinyl acetal resin composition of embodiment 1, wherein the compound comprises a polyoxyalkylene alkyl ether in which a hydrocarbon group having 6 or more carbon atoms and a polyoxyalkylene group are bonded via an ether bond.

[0011] [Aspect 3] The α-olefin-modified polyvinyl acetal resin composition of Aspect 1 or 2, wherein the compound is contained in an amount of 5 to 40 parts by mass, preferably 10 to 30 parts by mass, and more preferably 15 to 25 parts by mass, per 100 parts by mass of the α-olefin-modified polyvinyl acetal resin.

[0012] [Aspect 3-2] The α-olefin-modified polyvinyl acetal resin composition of Aspect 1 or 2, wherein the compound is contained in an amount of 8 to 25 parts by mass, preferably 10 to 22 parts by mass, more preferably 12 to 19 parts by mass, and even more preferably 14 to 17 parts by mass, per 100 parts by mass of the α-olefin-modified polyvinyl acetal resin.

[0013] [Aspect 4] The α-olefin-modified polyvinyl acetal resin composition of any one of Aspects 1 to 3 and Aspect 3-2, wherein the compound has a structure represented by the formula: Z-[O-(AO)n-H]x ... (I), wherein Z is a linear or branched alkyl group having 6 or more carbon atoms, x is an integer from 1 to 12, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is an integer from 1 to 30.

[0014] [Embodiment 5] The α-olefin-modified polyvinyl acetal resin composition of embodiment 4, wherein Z has 6 to 30 carbon atoms, preferably 8 to 22 carbon atoms, more preferably 10 to 20 carbon atoms, and even more preferably 12 to 14 carbon atoms.

[0015] [Aspect 6] The α-olefin-modified polyvinyl acetal resin composition of Aspect 4 or 5, wherein Z contains a branched alkyl group.

[0016] [Embodiment 7] The α-olefin-modified polyvinyl acetal resin composition of any one of Embodiments 4 to 6, wherein x is an integer of 1 to 6, preferably 1 to 3, and more preferably 1.

[0017] [Embodiment 8] The α-olefin-modified polyvinyl acetal resin composition of any one of Embodiments 4 to 7, wherein the AO has 2 carbon atoms.

[0018] [Aspect 9] The α-olefin-modified polyvinyl acetal resin composition of any one of Aspects 4 to 8, wherein n is an integer of 1 to 20, preferably 1 to 15, more preferably 2 to 9, and even more preferably 3 to 7.

[0019] [Aspect 10] The α-olefin-modified polyvinyl acetal resin composition of any one of Aspects 1 to 9 and Aspect 3-2, wherein the α-olefin comprises ethylene.

[0020] [Aspect 11] The α-olefin-modified polyvinyl acetal resin composition of any one of Aspects 1 to 10 and Aspect 3-2, wherein the α-olefin-modified polyvinyl acetal resin contains 5 to 80 mol %, preferably 20 to 60 mol %, more preferably 25 to 50 mol %, and even more preferably 30 to 46 mol % of α-olefin units.

[0021] [Embodiment 12] An interlayer film for laminated glass, comprising the α-olefin-modified polyvinyl acetal resin composition of any one of Embodiments 1 to 11 and Embodiment 3-2.

[0022] [Embodiment 13] A laminated glass having a plurality of glass plates and the interlayer film for laminated glass of embodiment 12 disposed between the plurality of glass plates.

[0023] According to the present invention, there is provided an α-olefin-modified polyvinyl acetal resin composition capable of forming laminated glass having excellent penetration resistance, edge peel resistance, and heat and humidity resistance.

[0024] Hereinafter, one embodiment of the present invention will be described in detail, but the scope of the present invention is not limited to the embodiment described here, and various modifications can be made without departing from the spirit of the present invention. Furthermore, when multiple upper and lower limit values ​​are specified for a specific parameter, any upper and lower limit values ​​can be combined to form a suitable numerical range.

[0025] (α-Olefin-Modified Polyvinyl Acetal Resin) The α-olefin-modified polyvinyl acetal resin composition of the present invention contains an α-olefin-modified polyvinyl acetal resin. The α-olefin-modified polyvinyl acetal resin refers to an acetalized product of an α-olefin-vinyl alcohol copolymer having α-olefin units in the main chain. The α-olefin-modified polyvinyl acetal resin can be obtained, for example, by subjecting a vinyl alcohol resin copolymerized with an α-olefin (hereinafter referred to as an α-olefin-vinyl alcohol copolymer) to an acetalization reaction with an aldehyde in the presence of an acidic catalyst. In this specification, the α-olefin-modified polyvinyl acetal resin composition may be referred to as a "resin composition," and the α-olefin-modified polyvinyl acetal resin may be referred to as a "modified polyvinyl acetal resin."

[0026] Examples of α-olefin vinyl alcohol copolymers include those obtained by copolymerizing an α-olefin with a vinyl ester monomer and saponifying the resulting copolymer. Examples of α-olefins include ethylene, propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and vinylcyclohexane. Among these, preferred α-olefins include ethylene.

[0027] As a method for copolymerizing an α-olefin with a vinyl ester monomer, a conventionally known method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. can be applied. As a polymerization initiator, an azo-based initiator, a peroxide-based initiator, a redox-based initiator, etc. can be appropriately selected depending on the polymerization method. As a saponification reaction, a conventionally known alcoholysis or hydrolysis using an alkali catalyst or an acid catalyst can be applied, and among these, a saponification reaction using methanol as a solvent and caustic soda (NaOH) as a catalyst is simple.

[0028] The degree of saponification of the α-olefin vinyl alcohol copolymer is not particularly limited, but is preferably 95 mol% or more, more preferably 98 mol% or more, even more preferably 99 mol% or more, and most preferably 99.9 mol% or more.

[0029] Examples of vinyl ester monomers that can be used as raw materials for α-olefin vinyl alcohol copolymers include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate, and vinyl benzoate, with vinyl acetate being particularly preferred.

[0030] The α-olefin unit content of the α-olefin-vinyl alcohol copolymer is, for example, 5 to 80 mol%, preferably 20 to 60 mol%, more preferably 25 to 50 mol%, and even more preferably 30 to 46 mol%. By satisfying this range, the α-olefin unit content of the modified polyvinyl acetal resin described below can be adjusted to a suitable range.

[0031] The melt mass flow rate (MFR) of the α-olefin vinyl alcohol copolymer at 190°C under a load of 2.16 kg is, for example, 0.1 to 50 g / 10 min, preferably 1 to 20 g / 10 min, and more preferably 5 to 10 g / 10 min. By ensuring that the MFR satisfies this range, the MFR of the modified polyvinyl acetal resin and resin composition described below can be adjusted to a suitable range. The MFR can be measured by a method in accordance with JIS K 7210-1:2014.

[0032] The method for producing the modified polyvinyl acetal resin of the present invention is not particularly limited, and the resin can be produced by a known production method, such as a method in which an aldehyde is added to an α-olefin vinyl alcohol copolymer solution under acidic conditions to cause an acetalization reaction, or a method in which an aldehyde is added to an α-olefin vinyl alcohol copolymer dispersion under acidic conditions to cause an acetalization reaction.

[0033] The reaction product obtained after the acetalization reaction is neutralized with an alkali, washed with water, and the solvent is removed to obtain the desired modified polyvinyl acetal resin.

[0034] The solvent for producing the modified polyvinyl acetal resin is not particularly limited, and examples thereof include water, alcohols, dimethyl sulfoxide, and mixed solvents of water and alcohols.

[0035] The dispersion medium for producing the modified polyvinyl acetal resin is not particularly limited, but examples thereof include water and alcohol.

[0036] The catalyst for the acetalization reaction is not particularly limited, and may be either an organic acid or an inorganic acid. Examples include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid, carbonic acid, etc. Inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid are particularly preferred because they are easy to wash off after the reaction.

[0037] The aldehyde used in the acetalization reaction is not particularly limited, and examples thereof include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, hexylaldehyde, benzaldehyde, isobutyraldehyde, 2-ethylhexylaldehyde, 2-methylbutyraldehyde, trimethylacetaldehyde, 2-methylpentylaldehyde, 2,2-dimethylbutyraldehyde, 2-ethylbutyraldehyde, 3,5,5-trimethylhexylaldehyde, 7-octenal, citral, citronellal, and acrolein. Examples of aldehydes that can be used include rhein, crotonaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, and 5-hydroxybenzaldehyde. In terms of heat resistance and optical properties, butyraldehyde, benzaldehyde, and isobutyraldehyde are preferred. These aldehydes may be used alone or in combination of two or more.

[0038] The alkali used to neutralize the reaction product is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, ammonia, sodium acetate, sodium carbonate, sodium hydrogen carbonate, and potassium carbonate.

[0039] The content of α-olefin units in the modified polyvinyl acetal resin of the present invention is, for example, 5 to 80 mol%, preferably 20 to 60 mol%, more preferably 25 to 50 mol%, even more preferably 30 to 46 mol%, and most preferably 35 to 42 mol%. If the content of α-olefin units is less than 5 mol%, the impact resistance and heat and humidity resistance of the modified polyvinyl acetal resin of the present invention are likely to decrease, while if it exceeds 80 mol%, the heat resistance is likely to be impaired.

[0040] The content of vinyl alcohol units in the modified polyvinyl acetal resin of the present invention is, for example, 20 to 70 mol%, preferably 25 to 55 mol%, more preferably 35 to 45 mol%, and even more preferably 38 to 43 mol%, based on all monomer units constituting the resin. If the proportion of vinyl alcohol units is less than 20 mol%, heat resistance and adhesiveness tend to deteriorate. On the other hand, if the proportion of vinyl alcohol units is 70 mol% or more, coloration tends to deteriorate.

[0041] The acetal units of the modified polyvinyl acetal resin of the present invention represent acetalized vinyl alcohol units, and are, for example, 5 to 50 mol%, preferably 10 to 35 mol%, more preferably 15 to 25 mol%, and even more preferably 18 to 22 mol%. If the acetal units are less than 5 mol%, the modified polyvinyl acetal resin of the present invention will have high crystallinity and will tend to have poor transparency. On the other hand, if the acetal units are 50 mol% or more, heat resistance and glass adhesion will tend to be impaired.

[0042] The modified polyvinyl acetal resin of the present invention has an MFR of, for example, 0.1 to 30 g / 10 min, preferably 5 to 25 g / 10 min, and more preferably 10 to 20 g / 10 min at 140°C and a load of 21.6 kg. When the MFR satisfies this range, the MFR of the resin composition described below can be adjusted to a suitable range.

[0043] (Compound Having a Structure in Which a Hydrocarbon Group Z Having 6 or More Carbon Atoms is Bonded to a Polyoxyalkylene Group) The resin composition of the present invention contains a compound having a structure in which a hydrocarbon group Z having 6 or more carbon atoms is bonded to a polyoxyalkylene group. The polyoxyalkylene group here has a structure represented by the formula -(AO)n- (wherein A is an alkylene group and n is an integer).

[0044] The number of carbon atoms in the alkylene A of the polyoxyalkylene group is, for example, 2 to 4, preferably 2. Specific examples of the alkylene A include ethylene, propylene, and butylene. Of these, the preferred alkylene A is ethylene. The average repeat number n of the oxyalkylene group AO is, for example, 1 to 30, preferably 1 to 20, more preferably 1 to 15, even more preferably 2 to 9, and most preferably 3 to 7. If n is outside the above range, the balance between hydrophilicity and hydrophobicity becomes poor, and the compatibility between the polyoxyalkylene alkyl ether and the modified polyvinyl acetal resin tends to decrease.

[0045] The hydrocarbon group is thought to exhibit affinity with the poly-α-olefin portion of the modified polyvinyl acetal resin, which has low polarity. The polyoxyalkylene group is thought to exhibit affinity with the acetal group and hydroxyl group of the modified polyvinyl acetal resin, which have high polarity. Furthermore, the bond between the hydrocarbon group and the polyoxyalkylene group is thought to cause the compound to exhibit excellent compatibility with the modified polyvinyl acetal resin. Compounds with such a structure exhibit the effect of plasticizing the modified polyvinyl acetal resin. Therefore, when the modified polyvinyl acetal resin composition contains the compound as a plasticizer, the penetration resistance of the interlayer film for laminated glass and the laminated glass is improved.

[0046] In a preferred embodiment, the compound includes a polyoxyalkylene alkyl ether in which a hydrocarbon group Z having 6 or more carbon atoms and a polyoxyalkylene group are bonded via an ether bond. That is, the polyoxyalkylene alkyl ether referred to here has a structure in which an alkylene oxide AO (wherein A is an alkylene group) is added to a monohydric or polyhydric alcohol Z[—OH]x (wherein Z is a hydrocarbon group and x is the valence of the alcohol).

[0047] In such cases, the valence number x of the alcohol is, for example, 1 to 12, preferably 1 to 6, more preferably 1 to 3, and particularly preferably 1. As x increases, hydrophilicity increases and compatibility with the resin tends to decrease.

[0048] The hydrocarbon group Z has 6 or more carbon atoms, preferably 6 to 30, more preferably 8 to 22, even more preferably 10 to 20, and most preferably 12 to 14. When the carbon number of Z is within the above range, the affinity with the polyolefin portion and butyral portion of the modified polyvinyl acetal resin is further improved. When Z is less than 6, hydrophilicity increases, and compatibility with the resin tends to decrease.

[0049] Examples of hydrocarbon groups include aliphatic, aromatic, and alicyclic groups. The hydrocarbon group may be saturated or unsaturated, but saturated hydrocarbon groups are preferred because they are less likely to be discolored and have better plasticizing properties. Examples of aliphatic hydrocarbon groups include linear or branched alkyl groups having a carbon number within the above range. Compounds having one of the above structures may be used, or two or more may be used in combination.

[0050] In one preferred form, the alcohol is a secondary alcohol, in which case the hydrocarbon group Z will comprise a branched alkyl group.

[0051] In a preferred embodiment, the polyoxyalkylene alkyl ether has a structure represented by the formula (I) above, wherein the symbols in the formula (I) have the same meanings as those in the main text above.

[0052] The compound is preferably contained in an amount of 5 to 40 parts by mass per 100 parts by mass of the modified polyvinyl acetal resin. If the content of the compound is less than 5 parts by mass, the penetration resistance of the laminated glass tends to decrease, while if it exceeds 40 parts by mass, the edge peel resistance of the laminated glass tends to decrease and bleeding out tends to occur more easily. The content of the compound is preferably 10 to 30 parts by mass, more preferably 15 to 25 parts by mass, per 100 parts by mass of the modified polyvinyl acetal resin.

[0053] In one embodiment, the content of the compound is preferably 8 to 25 parts by mass, more preferably 10 to 22 parts by mass, even more preferably 12 to 19 parts by mass, and particularly preferably 14 to 17 parts by mass, relative to 100 parts by mass of the α-olefin-modified polyvinyl acetal resin.

[0054] Furthermore, in one embodiment, for example, in applications in which penetration resistance is not important, the content of the compound may be 1 part by mass or more and less than 5 parts by mass relative to 100 parts by mass of the α-olefin-modified polyvinyl acetal resin.

[0055] (Other Components) The resin composition of the present invention may contain, in addition to the modified polyvinyl acetal resin and the compound, other thermoplastic resins. The other thermoplastic resins are not particularly limited, but examples thereof include (meth)acrylic resins, polyvinyl butyral resins, and ionomer resins.

[0056] When the resin composition contains the other thermoplastic resin, the content thereof is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the resin composition. If the content of the other thermoplastic resin in the resin composition exceeds 20% by mass, the transparency, impact resistance, and adhesion to substrates such as glass tend to be easily reduced.

[0057] The resin composition of the present invention may further contain additives such as a second plasticizer, an antioxidant, an ultraviolet absorber, an adhesion improver, an antiblocking agent, a silane coupling agent, a pigment, a dye, a functional inorganic compound, etc. If necessary, the plasticizer and various additives may be extracted or washed to reduce the content of these plasticizers and additives, and then the plasticizer and various additives may be added again.

[0058] When the resin composition contains the additives, the content thereof is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and most preferably 5% by mass or less, relative to the total mass of the resin composition. If the content of the various additives exceeds 20% by mass, problems such as insufficient self-supporting ability (heat resistance) under high-temperature conditions and bleeding during long-term use as an interlayer film for laminated glass tend to occur.

[0059] In particular, because the second plasticizer has a high effect of reducing the self-supporting ability (heat resistance) under high temperature conditions due to its properties, its content is preferably 0 to 1 mass %, more preferably 0 to 0.5 mass %, and even more preferably 0 to 0.1 mass %, relative to the total mass of the resin composition.

[0060] The second plasticizer is not particularly limited, and examples thereof include triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, di-(2-butoxyethyl)-adipate (DBEA), di-(2-butoxyethyl)-sebacate (DBES), di-(2-butoxyethyl)-azelate, di-(2-butoxyethyl)-glutaric acid ester, di-(2-butoxyethoxyethyl)-adipate (DBEEA), di-(2-butoxyethoxyethyl)-sebacate (DBEES), di-(2-butoxyethoxyethyl)-azelate, di-(2-butoxyethoxyethyl)-glutaric acid ester, di-(2-butoxyethoxyethyl)-adipate (DBEEA), di-(2-butoxyethoxyethyl)-sebacate (DBEES), di-(2-butoxyethoxyethyl)-azelate, di-(2-butoxyethoxyethyl)-glutaric acid ester, di-(2-hexoxyethyl)-glutaric acid ester, di-(2-hexoxyethyl)-adipate, di-(2-hexoxyethyl)-sebacic acid ester, di-(2-hexoxyethyl)-azelaic acid ester, di-(2-hexoxyethyl)-glutaric acid ester, di-(2-hexoxyethoxyethyl)-adipate, di-(2-hexoxyethoxyethyl)-sebacic acid ester, di-(2-hexoxyethoxyethyl)-azelaic acid ester, di-(2-hexoxyethoxyethyl)-glutaric acid ester, di-(2-butoxyethyl)-phthalic acid ester and / or di-(2-butoxyethoxyethyl)-phthalic acid ester. Among these, plasticizers having a sum of the number of carbon atoms and the number of oxygen atoms constituting the molecule of 28 or more are preferred. Examples include triethylene glycol-di-2-ethylhexanoate, tetraethylene glycol-di-2-ethylhexanoate, di-(2-butoxyethoxyethyl)-adipate, di-(2-butoxyethoxyethyl)-sebacate, etc. The above plasticizers may be used alone or in combination of two or more.

[0061] The resin composition may also contain an antioxidant. Examples of the antioxidant that can be used include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Among these, phenol-based antioxidants are preferred, and alkyl-substituted phenol-based antioxidants are particularly preferred.

[0062] Examples of the phenolic antioxidant include acrylate compounds such as 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate or 2,4-di-t-amyl-6-(1-(3,5-di-t-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, octadecyl-3-(3,5-)di-t-butyl-4-hydroxyphenyl)propionate, 2,2 '-Methylene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(4-methyl-6-t-butylphenol), 4,4'-butylidene-bis(6-t-butyl-m-cresol), 4,4'-thiobis(3-methyl-6-t-butylphenol), bis(3-cyclohexyl-2-hydroxy-5-methylphenyl)methane, 3,9-bis(2-(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetramethylphenol alkyl-substituted phenolic compounds such as oxaspiro[5,5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis(methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate)methane or triethylene glycol bis(3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate); 6-( and triazine group-containing phenolic compounds such as 4-hydroxy-3,5-di-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bis-octylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-t-butylanilino)-2,4-bis-octylthio-1,3,5-triazine, and 2-octylthio-4,6-bis-(3,5-di-t-butyl-4-oxyanilino)-1,3,5-triazine.

[0063] Examples of phosphorus-based antioxidants include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(2-t-butyl-4-methylphenyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and Examples of the phosphate groups include monophosphite compounds such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene, and diphosphite compounds such as 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis(phenyl-di-alkyl(C12 to C15) phosphite), 4,4'-isopropylidene-bis(diphenyl monoalkyl(C12 to C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl)butane, and tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene phosphite. Among these, monophosphite compounds are preferred.

[0064] Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, laurylstearyl 3,3'-thiodipropionate, pentaerythritol-tetrakis-(β-lauryl-thiopropionate), and 3,9-bis(2-dodecylthioethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane.

[0065] These antioxidants can be used alone or in combination of two or more. The amount of the antioxidant is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the modified polyvinyl acetal resin. These antioxidants may be added during production of the modified polyvinyl acetal resin of the present invention. Alternatively, they may be added to the resin composition during molding of the resin sheet of the present invention.

[0066] The resin composition may also contain an ultraviolet absorber. Examples of the ultraviolet inhibitors that can be used include benzotriazole-based ultraviolet absorbers such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α'dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, and 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole; Examples of the ultraviolet absorber include hindered amine ultraviolet absorbers such as lysyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate, and 4-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)-1-(2-(3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy)ethyl)-2,2,6,6-tetramethylpiperidine, and benzoate ultraviolet absorbers such as 2,4-di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate. The amount of these UV absorbers added is preferably 10 to 50,000 ppm, more preferably 100 to 10,000 ppm, by mass based on the modified polyvinyl acetal resin. These UV absorbers may be used alone or in combination of two or more. These UV absorbers may be added during production of the modified polyvinyl acetal resin of the present invention. Alternatively, they may be added to the resin composition during molding of the resin sheet of the present invention.

[0067] The resin composition may also contain an adhesion improver. Examples of adhesion improvers that can be used include those disclosed in WO 03 / 033583 A1. Alkali metal salts and / or alkaline earth metal salts of organic acids are preferred, with potassium acetate and / or magnesium acetate being particularly preferred. Other additives, such as silane coupling agents, may also be added. The optimal amount of adhesion improver varies depending on the additive used and the location where the resulting module or laminated glass will be used. However, it is generally preferable to adjust the adhesion strength of the resulting sheet to glass in the Pummel test (described in WO 03 / 033583 A1, etc.) to 3 to 10. When particularly high penetration resistance is required, it is preferable to adjust to 3 to 6, and when high glass shatter resistance is required, it is preferable to adjust to 7 to 10. When high glass shatter resistance is required, it is also useful to not add an adhesion improver.

[0068] Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldiethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyldiethoxysilane, and N-(2-aminoethyl)-3-aminopropyldiethoxysilane.

[0069] These silane coupling agents can be used alone or in combination of two or more. The amount of the silane coupling agent is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the modified polyvinyl acetal resin. These silane coupling agents may be added during the production of the modified polyvinyl acetal resin of the present invention. Alternatively, they may be added to the resin composition during molding of the resin sheet of the present invention.

[0070] (Resin Composition) The resin composition of the present invention can be produced by appropriately selecting the above-mentioned components and mixing them by a known and commonly used method.

[0071] The resin composition has an MFR at 140°C under a load of 21.6 kg of, for example, 1 to 50 g / 10 min, preferably 3 to 30 g / 10 min, and more preferably 10 to 20 g / 10 min. If the MFR is less than 1 g / 10 min, sufficient processability (fluidity) cannot be obtained within an appropriate molding temperature range during molding, necessitating an increase in molding temperature, and the resulting molded article tends to be easily discolored. If the MFR exceeds 50 g / 10 min, sufficient melt tension cannot be obtained within an appropriate molding temperature range during molding, and problems such as deterioration in film formation stability and the surface condition of the molded article tend to occur.

[0072] The resin composition of the present invention is not particularly limited in its applications, and can be used, for example, as a packaging material in various fields. Such packaging materials are used, for example, as containers with excellent oxygen barrier properties in the form of bags, tubes, cups, pouches, etc., for food, cosmetics, medical and chemical products, toiletries, vacuum insulation panels, etc., or as gas barrier films for food packaging, gasoline tanks, vacuum insulation panels, heat pipes, etc. The resin composition of the present invention is also useful as a fiber glue, a fiber treatment agent, a fiber processing agent, a sizing agent for textile products, a paper clear coating agent, a paper pigment coating agent, an internal sizing agent for paper, a paper processing agent such as a binder for overcoating thermal paper, a pressure-sensitive adhesive, an anti-fogging agent, a paint, a dispersant for organic and inorganic pigments, a polymeric dispersion stabilizer for emulsions, a polymeric dispersion stabilizer for PVC, an adhesive for paper, wood, plastics, etc., a binder for nonwoven fabrics, a binder for fibers, a binder for ceramics, a binder for electrodes, a binder for various building materials such as gypsum board and fiberboard, an additive for cement or mortar, a hot melt adhesive, an interlayer adhesive, a resin for 3D printers, etc. Furthermore, because the resin composition of the present invention has high transparency, it is also useful as an interlayer film for laminated glass, a protective film for glass surfaces, and various transparent containers for cosmetics, etc.

[0073] (Resin Sheet) The method for producing the resin sheet of the present invention is not particularly limited, and known methods can be used. Specifically, the resin composition may be molded into a sheet by extrusion molding, press molding, blow molding, injection molding, solution casting, or the like. A particularly preferred method involves feeding the resin composition and additives into an extruder, kneading and melting the mixture, discharging the mixture through a die, and then pulling it up with a take-up machine to form it into a plate. The resin temperature during extrusion is preferably 130 to 230°C, more preferably 140 to 220°C, and even more preferably 150 to 200°C. If the resin temperature is too high, the modified polyvinyl acetal resin will decompose, resulting in a high content of volatile substances. Conversely, if the temperature is too low, the content of volatile substances will also increase. To efficiently remove the volatile substances, it is preferable to remove them by reducing the pressure through a vent port of the extruder.

[0074] The resin sheet preferably has a surface irregularity to prevent adhesion between resin sheets and to improve degassing properties during the lamination process. Conventionally known methods can be used to provide the irregularities, including, for example, a method of providing a melt fracture structure by adjusting extrusion conditions, and a method of providing an embossed structure to an extruded sheet. Conventionally known methods can be used for the depth and shape of the embossment.

[0075] The thickness of the resin sheet is not particularly limited, but is preferably 0.10 to 3.0 mm, more preferably 0.40 to 2.8 mm, and even more preferably 0.70 to 2.6 mm. If the resin sheet is thinner than 0.10 mm, it tends to be difficult to meet the penetration resistance performance of the laminated glass, and if it is thicker than 3.0 mm, the cost of the sheet itself is high and the cycle time of the lamination process tends to be long, which is not preferable. The resin sheet may be used as a single molded sheet, or two or more molded sheets may be stacked and used to adjust the desired thickness.

[0076] The resin sheet containing the resin composition of the present invention has a haze of, for example, 1.1% or less, preferably 0.9% or less, more preferably 0.8% or less, and even more preferably 0.5% or less at a measurement temperature of 20°C and a thickness of 0.8 mm. When the haze is within the above range, the transparency is further improved. Since the smaller the haze, the higher the transparency of the resin sheet, the lower limit is not particularly limited and may be, for example, 0.01% or more. The haze of the resin sheet is measured using a haze meter in accordance with JIS K7136:2000.

[0077] The resin sheet containing the resin composition of the present invention has a storage modulus (E') of, for example, 5 to 100 MPa, preferably 7 to 50 MPa, and more preferably 10 to 30 MPa, measured at a temperature of 80°C and a frequency of 1 Hz. When the storage modulus (E') is within the above range, the sheet exhibits good self-supporting properties in high-temperature environments. The storage modulus (E') can be measured by a method conforming to JIS K 0129:2005. When the storage modulus is less than 5 MPa, creep resistance at high temperatures tends to be insufficient. Furthermore, when the storage modulus is greater than 100 MPa, the resin sheet tends to have high rigidity and insufficient penetration resistance.

[0078] For the resin sheet containing the resin composition of the present invention, a master curve was created at 50°C. ８ The long-term relaxation modulus after 10 seconds (about 10 years) may be preferably 0.5 MPa or more, more preferably 1.0 MPa or more, even more preferably 1.5 MPa or more, and particularly preferably 2.0 MPa or more. The upper limit of the long-term relaxation modulus is not particularly limited, but may be, for example, 20 MPa or less. When the long-term relaxation modulus is within the above range, creep resistance is further improved. The long-term relaxation modulus can be measured by the method described in the Examples. In one embodiment, the long-term relaxation modulus may be, for example, 1.0 to 20 MPa, preferably 1.5 to 10 MPa, and more preferably 2.0 to 5.0 MPa.

[0079] (Interlayer film for laminated glass) The resin sheet of the present invention is useful as an interlayer film for laminated glass. The interlayer film for laminated glass is particularly preferred as an interlayer film for laminated glass for structural materials, as it has excellent adhesion to substrates such as glass, transparency, and self-supporting ability. Furthermore, the resin sheet is not limited to interlayer films for laminated glass for structural materials, and is also suitable as an interlayer film for laminated glass for various applications such as mobile bodies such as automobiles, buildings, and solar cells, but is not limited to these applications.

[0080] (Laminated Glass) Laminated glass can be produced by inserting and laminating the resin sheet of the present invention between two or more sheets of glass made of inorganic glass or organic glass. There are no particular restrictions on the glass to be laminated with the interlayer film for laminated glass of the present invention, but in addition to inorganic glass such as float glass, tempered glass, wired glass, and heat-absorbing plate glass, conventionally known organic glass such as polymethyl methacrylate and polycarbonate can be used. There are no particular restrictions on the thickness of the glass, but it is preferably 1 to 10 mm, more preferably 2 to 6 mm.

[0081] The interlayer film used in the laminated glass of the present invention may be composed solely of a layer (x) containing the modified polyvinyl acetal resin or resin composition, or may be a multilayer film containing at least one layer (x). The multilayer film is not particularly limited, but examples thereof include a two-layer film in which a layer (x) and another layer are laminated, and a three-layer film in which another layer is disposed between two layers (x).

[0082] The other layers may include layers containing known resins. Examples of the resins include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, polytetrafluoroethylene, acrylic resin, polyamide, polyacetal, polycarbonate, and polyesters such as polyethylene terephthalate, polybutylene terephthalate, cyclic polyolefin, polyphenylene sulfide, polytetrafluoroethylene, polysulfone, polyethersulfone, polyarylate, liquid crystal polymer, and polyimide. The other layers may also contain additives such as plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, antiblocking agents, pigments, dyes, heat-shielding materials (e.g., inorganic or organic heat-shielding materials having infrared absorbing properties), and functional inorganic compounds, as needed.

[0083] The lamination method for obtaining the above-mentioned laminated glass can be a known method, such as a method using a vacuum laminator, a method using a vacuum bag, a method using a vacuum ring, a method using a nip roll, etc. Furthermore, a method in which the glass is subjected to an autoclave process after temporary bonding can also be additionally carried out.

[0084] When nip rolls are used, for example, a method may be used in which the resin composition is first temporarily bonded at a temperature equal to or lower than the flow initiation temperature thereof, and then temporarily bonded under conditions close to the flow initiation temperature thereof. Specifically, for example, the resin composition is heated to 30 to 70°C using an infrared heater or the like, degassed with rolls, and further heated to 50 to 120°C, and then pressure-bonded with rolls to bond or temporarily bond the resin composition.

[0085] The autoclave step, which is additionally performed after the temporary bonding, is carried out, for example, under a pressure of about 1 to 1.5 MPa at a temperature of 130 to 145° C. for about 2 hours, although this depends on the thickness and configuration of the module and the laminated glass.

[0086] The laminated glass of the present invention preferably has excellent transparency. For example, when a resin sheet having a thickness of 0.8 mm is used as an interlayer film of the laminated glass and the laminated glass is slowly cooled under the conditions described below, the haze is preferably 2% or less, more preferably 1.6% or less, and even more preferably 1.2% or less.

[0087] The laminated glass of the present invention preferably has excellent adhesive strength to glass. For example, the peel stress in a compressive shear strength test carried out by the method described below is preferably 20 to 40 MPa, more preferably 22 to 38 MPa, and even more preferably 24 to 36 MPa. If the peel stress is less than 20 MPa, the adhesive strength to glass is insufficient, and the glass tends to shatter when the glass breaks. If the peel stress exceeds 40 MPa, the adhesive strength to glass is too strong, and there is a risk of reduced penetration resistance when the glass breaks.

[0088] The laminated glass of the present invention has excellent transparency, impact resistance, and heat resistance, and can therefore be suitably used for building materials such as automobile windshields, automobile side glass, automobile sunroofs, automobile rear glass, glass for head-up displays, laminates for facades, exterior walls and roofs, panels, doors, windows, walls, roofs, sunroofs, sound insulation walls, display windows, balconies, and handrail walls, as well as partition glass components for conference rooms, solar panels, etc.

[0089] EXAMPLES The present invention will be specifically explained below with reference to examples and comparative examples, but the present invention is not limited to these.

[0090] Example 1 (1) Synthesis of Ethylene-Modified Polyvinyl Butyral Resin EVOH1 (MFR (190°C, 2.16 kg) 3.5 g / 10 min, ethylene unit content 38 mol%, saponification degree 99.98 mol%), an ethylene-vinyl alcohol copolymer (hereinafter referred to as "EVOH") synthesized by the method described in Japanese Patent No. 7,354,455, was dispersed in 377 parts by mass of water, and 20.0 parts by mass of isobutyraldehyde was added. The resulting dispersion was heated to 60°C with stirring. Stirring was continued for 2 hours, allowing the EVOH to be impregnated with isobutyraldehyde. Thereafter, 10 parts by mass of 1M hydrochloric acid was added to the dispersion at 60°C to carry out a butyralization reaction. Two hours after the first addition of hydrochloric acid, 40 parts by mass of 1M hydrochloric acid was added, and the butyralization reaction was carried out for an additional 4 hours. The butyralized product produced by butyralization was in a solid state.

[0091] Thereafter, 75 parts by mass of 1 M sodium hydroxide was added to the dispersion to neutralize it, thereby terminating the butyralization reaction. In order to neutralize the interior of the butyralized product, the dispersion was further stirred at 60°C for 8 hours. The neutralized butyralized product was collected by filtration, and 500 parts by mass of ion-exchanged water was added to the butyralized product, followed by stirring at 60°C for 6 hours, thereby washing the butyralized product.

[0092] The butyralized product was filtered, and 500 parts by mass of ion-exchanged water was added to the butyralized product. The mixture was stirred at 60°C for 6 hours to wash the butyralized product a second time. The washing water was filtered off, and the mixture was vacuum-dried at 60°C for 8 hours to obtain 113 parts by mass (yield 100%) of a pellet-shaped ethylene-modified polyvinyl butyral resin (PVB1). The MFR of the resin (PVB1) was measured at 190°C under a load of 2.16 kg using the method described above. The measurement results are shown in Table 1.

[0093] (2) Preparation of Resin Composition A polyethylene glycol alkyl ether ("SOFTANOL 30" (trade name) manufactured by Nippon Shokubai Co., Ltd.) was prepared, in which Z in formula (I) is 12 to 14, x is 1, the carbon number of AO is 2, and n is 3. 100 parts by mass of resin (PVB1) and 20 parts by mass of this polyethylene glycol alkyl ether were melt-kneaded for 5 minutes using a Labo Plastomill ("4M150" (trade name) manufactured by Toyo Seiki Seisaku-sho, Ltd.) at a chamber temperature of 160°C and a rotation speed of 60 rpm. The contents of the chamber were removed and cooled to obtain a resin composition. The MFR of the resulting resin composition was measured using the above-mentioned method at 140°C and a load of 21.6 kg. The measurement results are shown in Table 1.

[0094] (3) Production of Resin Sheet The obtained resin composition was heated at 180°C and subjected to a pressure of 50 kgf / cm using a release film (UPILEX (registered trademark)-S (manufactured by UBE Corporation)) having a maximum roughness height (Rz) of less than 100 nm. ２ The resin sheet was subjected to compression molding at a pressure of 50 MPa for 5 minutes to obtain a resin sheet having a thickness of 0.8 mm. The properties of the obtained resin sheet were measured as follows. The measurement results are shown in Table 1.

[0095] (Haze (Transparency)) A test piece measuring 20 mm in length and 5 mm in width was cut out from the resin sheet to obtain a test piece. The haze of the obtained test piece was measured by the above-described method using a haze meter ("HZ-1" (trade name) manufactured by Suga Test Instruments Co., Ltd.). A low haze value indicates that the resin sheet has excellent transparency. This measurement was performed while maintaining the temperature of the resin sheet at 20°C.

[0096] (Storage modulus at 80°C (self-supporting ability in a high-temperature environment)) A test piece measuring 20 mm in length and 5 mm in width was cut out from the resin sheet, and the storage modulus (E') was measured using a dynamic viscoelasticity measuring device (manufactured by UBM Co., Ltd.) at a measurement temperature of 80°C and a frequency of 1 Hz. A high value of the storage modulus indicates that the resin sheet has excellent self-supporting ability in a high-temperature environment.

[0097] (Long-term relaxation modulus (creep resistance)) After leaving the resin sheet to stand for one week or more in an atmosphere of 23°C and 50% RH, a test piece of 40 mm length x 5 mm width was cut out, and the long-term relaxation modulus was determined from a composite curve (master curve) at a reference temperature of 50°C obtained from dynamic viscoelasticity measurement and the time-temperature conversion law using a dynamic viscoelasticity measuring device manufactured by UBM Co., Ltd., and the value was used as an index of the strength of the resin sheet after a long period of time. A higher long-term relaxation modulus indicates a higher strength of the resin sheet after a long period of time.

[0098] Dynamic viscoelasticity was measured in accordance with JIS K 0129:2005, by performing tensile measurements at temperatures of 50 to 100°C and frequencies of 0.1, 0.5, 1, 5, 10, 50, and 100 Hz. From the storage modulus measurement results obtained, a master curve was created using the temperature-time conversion rule, with the reference temperature set to 50°C, and a frequency of 4.0 x 10 －７ Storage modulus (E'(t1)) in Hz and frequency 2.0 x 10 －７ The loss modulus (E''(t2)) at 50°C and 3.2 x 10 Hz was read, the Poisson's ratio was fixed at 0.5, and the loss modulus was calculated using the following formula (II). ８ The long-term relaxation modulus G(t) after 10 seconds was determined.

[0099] G(t)=E'(t1) / 3-0.4×E''(t2) / 3 (II) This series of calculations was performed using the calculation software "RheoStation" (trade name, manufactured by UBM Co., Ltd.) attached to a dynamic viscoelasticity measuring device manufactured by UBM Co., Ltd.

[0100] (Bleeding Resistance (Compatibility)) The resin sheet was kept at a temperature of 23° C. and a relative humidity of 50% for 30 days, after which a visual evaluation was carried out to evaluate the bleed-out resistance of the additive according to the following criteria.

[0101] Evaluation criteria A: No bleeding was observed B: Significant bleeding was observed

[0102] (4) Production of Laminated Glass The obtained resin sheet was sandwiched between two sheets of 2.7 mm thick float glass and placed in a vacuum laminator (1522N manufactured by Nisshinbo Mechatronics Inc.), and the pressure inside the vacuum laminator was reduced at 140°C for 1 minute. While maintaining the reduced pressure and temperature, the laminate was pressed at 30 kPa for 5 minutes to obtain a temporary bonded body. The obtained temporary bonded body was placed in an autoclave and treated at 140°C and 1.2 MPa for 30 minutes to obtain a laminated glass. The properties of the obtained laminated glass were measured as follows. The measurement results are shown in Table 1.

[0103] (Edge Peel Resistance) After leaving the laminated glass in an atmosphere of 85°C and 85% RH, the presence or absence of peeling between the interlayer film and the glass at the peripheral edge (edge) of the laminated glass was visually observed, and the edge peel resistance was evaluated based on the time until peeling occurred.

[0104] Evaluation criteria AA: No peeling for 2000 hours or more A: Peeling occurred in 1000 hours or more but less than 2000 hours B: Peeling occurred in 300 hours or more but less than 1000 hours C: Peeling occurred in less than 300 hours

[0105] (Haze (Transparency)) The haze at the center of the laminated glass was measured using a haze meter ("HZ-1" (trade name) manufactured by Suga Test Instruments Co., Ltd.) in the same manner as for the resin sheet. A low haze value indicates that the laminated glass has excellent transparency. The measurement was carried out while maintaining the temperature of the laminated glass at 20°C.

[0106] (Edge Whitening Distance) After the laminated glass was kept at a temperature of 85°C and a relative humidity of 85% for 1000 hours, the whitening state at the edge of the laminated glass was visually confirmed, and the whitening distance from the edge of the laminated glass was measured. A short edge whitening distance indicates that the laminated glass has excellent heat and humidity resistance.

[0107] Evaluation criteria A: Edge whitening distance less than 0.1 mm B: Edge whitening distance less than 1 mm C: Edge whitening distance 5 mm or more

[0108] (Ball Drop Test (Penetration Resistance)) The edges of the laminated glass were fixed to a support frame and held horizontally, and a 2.26 kg steel ball was dropped freely from a predetermined height onto the center of the laminated glass test piece. The height at which the steel ball did not penetrate half of the laminated glass was taken as the ball drop height, and the test was evaluated according to the following criteria. A result of the ball drop test of AA or A indicates that the laminated glass has superior penetration resistance. This test was carried out with the temperature of the laminated glass maintained at 23°C.

[0109] Evaluation criteria AA: 5m or more A: 3m or more but less than 5m B: 1.5m or more but less than 3m C: Less than 1.5m

[0110] Example 2 A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 1, except that a polyethylene glycol alkyl ether in which n is 5 ("LEOCOL SC-50" (trade name) manufactured by Lion Specialty Chemicals Co., Ltd.) was used instead of one in which n is 3 in formula (I), and the properties were tested. The results are shown in Table 1.

[0111] Example 3 A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 1, except that a polyethylene glycol alkyl ether in which n is 9 ("LEOCOL SC-90" (trade name) manufactured by Lion Specialty Chemicals Co., Ltd.) was used instead of one in which n is 3 in formula (I), and the properties were tested. The results are shown in Table 1.

[0112] Example 4 An ethylene-modified polyvinyl butyral resin (PVB2) was synthesized in the same manner as in Example 1, except that 28.0 parts by mass of isobutyraldehyde was used instead of 20.0 parts by mass of isobutyraldehyde. The property values ​​of the resin (PVB2) are shown in Table 1.

[0113] Resin compositions, resin sheets, and laminated glass were produced in the same manner as in Example 1, except that resin (PVB2) was used instead of resin (PVB1), and polyethylene glycol alkyl ether in which n is 5 in formula (I) instead of one in which n is 3 ("Leocol SC-50" manufactured by Lion Specialty Chemicals Co., Ltd.) was used, and their properties were tested. The results are shown in Table 1.

[0114] Example 5 An ethylene-modified polyvinyl butyral resin (PVB3) was synthesized in the same manner as in Example 1, except that 100 parts by mass of EVOH2 (MFR (190°C, 2.16 kg) 10 g / 10 min, ethylene unit content 44 mol%, saponification degree 99.98 mol%) synthesized by the method described in Japanese Patent No. 7,354,455 was used instead of 100 parts by mass of EVOH1 (MFR (190°C, 2.16 kg) 3.5 g / 10 min, ethylene unit content 38 mol%, saponification degree 99.98 mol%), and 18.0 parts by mass of isobutyraldehyde was used instead of 20.0 parts by mass of isobutyraldehyde. The property values ​​of the resin (PVB3) are shown in Table 1.

[0115] Resin compositions, resin sheets, and laminated glass were produced in the same manner as in Example 1, except that resin (PVB3) was used instead of resin (PVB1), and polyethylene glycol alkyl ether in which n is 5 ("Leocol SC-50" manufactured by Lion Specialty Chemicals Co., Ltd.) was used instead of polyethylene glycol alkyl ether in which n is 3 in formula (I), and the properties were tested. The results are shown in Table 1.

[0116]

[0117] Comparative Example 1 A polyvinyl butyral resin (PVB4) was synthesized in the same manner as in Example 1, except that 100 parts by mass of polyvinyl alcohol (MFR (190°C, 2.16 kg) 2 g / 10 min, saponification degree 97 mol%) was used instead of 100 parts by mass of EVOH1 (MFR (190°C, 2.16 kg) 3.5 g / 10 min, ethylene unit content 38 mol%, saponification degree 99.98 mol%), and 60.0 parts by mass of isobutyraldehyde was used instead of 20.0 parts by mass of isobutyraldehyde. The property values ​​of the resin (PVB4) are shown in Table 2.

[0118] Resin compositions, resin sheets, and laminated glass were produced in the same manner as in Example 1, except that resin (PVB4) was used instead of resin (PVB1), and polyethylene glycol alkyl ether in which n is 5 in formula (I) ("Leocol SC-50" manufactured by Lion Specialty Chemicals Co., Ltd.) was used instead of polyethylene glycol alkyl ether in which n is 3, and the properties were tested. The results are shown in Table 2.

[0119] Comparative Example 2 An ethylene-modified polyvinyl butyral resin (PVB5) was synthesized in the same manner as in Example 1, except that 100 parts by mass of EVOH2 (MFR (190°C, 2.16 kg) 10 g / 10 min, ethylene unit content 44 mol%, saponification degree 99.98 mol%) was used instead of 100 parts by mass of EVOH1 (MFR (190°C, 2.16 kg) 3.5 g / 10 min, ethylene unit content 38 mol%, saponification degree 99.98 mol%), and 25.0 parts by mass of isobutyraldehyde was used instead of 20.0 parts by mass of isobutyraldehyde. The property values ​​of the resin (PVB5) are shown in Table 2.

[0120] A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 1, except that resin (PVB5) was used instead of resin (PVB1), and di-(2-butoxyethyl)-adipate (DBEA, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of polyethylene glycol alkyl ether, and the properties were tested. The results are shown in Table 2.

[0121] Comparative Example 3 A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 1, except that resin (PVB3) was used instead of resin (PVB1), and polypropylene glycol (weight average molecular weight 400, PPG, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of polyethylene glycol alkyl ether, and the properties were tested. The results are shown in Table 2.

[0122] Comparative Example 4 A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 1, except that the resin (PVB3) was used instead of the resin (PVB1), and polyethylene glycol alkyl ether was not used, and the properties were tested. The results are shown in Table 2.

[0123]

[0124] In Comparative Example 1, the modified polyvinyl acetal resin was not α-olefin-modified, and the creep resistance of the resin sheet deteriorated, resulting in a large edge whitening distance of the laminated glass. In Comparative Examples 2 and 3, a conventionally known plasticizer was used, and edge peelability deteriorated. In Comparative Example 4, no plasticizer was used, and penetration resistance deteriorated.

[0125] Example 6 A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 1, except that the amount of polyethylene glycol alkyl ether added was changed to 15 parts by mass and the polyethylene glycol alkyl ether was changed to "Tergitol 15-S-3" manufactured by Dow Chemical Japan, Ltd., and the properties were tested. The results are shown in Table 3.

[0126] Example 7 A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 2, except that the amount of polyethylene glycol alkyl ether added was changed to 15 parts by mass and the polyethylene glycol alkyl ether was changed to "Tergitol 15-S-5" manufactured by Dow Chemical Japan, Ltd., and the properties were tested. The results are shown in Table 3.

[0127] Example 8 A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 3, except that the amount of polyethylene glycol alkyl ether added was changed to 15 parts by mass and the polyethylene glycol alkyl ether was changed to "Tergitol 15-S-9" manufactured by Dow Chemical Japan, Ltd., and the properties were tested. The results are shown in Table 3.

[0128] Example 9 A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 4, except that the amount of polyethylene glycol alkyl ether added was changed to 15 parts by mass and the polyethylene glycol alkyl ether was changed to "Tergitol 15-S-5" manufactured by Dow Chemical Japan, Ltd., and the properties were tested. The results are shown in Table 3.

[0129] Example 10: 100 parts by weight of EVOH1 was dispersed in 120 parts by weight of water and 195 parts by weight of 1-propanol. The solution was heated to 60°C with stirring and dissolved until homogeneous. After dissolution, 40 parts by weight of 1M hydrochloric acid was added, followed by 16.7 parts by weight of n-butylaldehyde, followed by dispersion. The temperature was maintained at 60°C to carry out the acetalization reaction. After 4 hours of reaction, 6.4 parts by weight of sodium carbonate was added to terminate the reaction. 500 parts by weight of 1-propanol was added to the reaction solution to homogenize it, and the mixture was then added dropwise to 2,000 parts by weight of water to precipitate the resin. The reaction was then filtered and washed three times, followed by vacuum drying at 60°C for 8 hours to obtain an ethylene-modified polyvinyl butyral resin (PVB6). The properties of the resin (PVB6) are shown in Table 3.

[0130] A resin composition, a resin sheet, and a laminated glass were produced in the same manner as in Example 1, except that resin (PVB6) was used instead of resin (PVB1), the amount of polyethylene glycol alkyl ether added was changed to 15 parts by mass, and the polyethylene glycol alkyl ether was changed to "Tergitol 15-S-5" manufactured by Dow Chemical Japan, Ltd., and the properties were tested. The results are shown in Table 3.

[0131]

Claims

1. An α-olefin-modified polyvinyl acetal resin composition comprising an α-olefin-modified polyvinyl acetal resin and a compound having a structure in which a hydrocarbon group having 6 or more carbon atoms and a polyoxyalkylene group are bonded.

2. The α-olefin-modified polyvinyl acetal resin composition according to claim 1, wherein the compound contains a polyoxyalkylene alkyl ether in which a hydrocarbon group having 6 or more carbon atoms and a polyoxyalkylene group are bonded by an ether bond.

3. The α-olefin-modified polyvinyl acetal resin composition according to claim 1, wherein the compound is contained in an amount of 5 to 40 parts by mass with respect to 100 parts by mass of the α-olefin-modified polyvinyl acetal resin.

4. The α-olefin-modified polyvinyl acetal resin composition according to claim 1, wherein the compound has a structure represented by the formula Z-[O-(AO)n-H]x... (I) [wherein, Z is a linear or branched alkyl group having 6 or more carbon atoms, x is an integer of 1 to 12, AO is an oxyalkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 30].

5. The α-olefin-modified polyvinyl acetal resin composition according to claim 4, wherein the carbon number of Z is 6 to 30.

6. The α-olefin-modified polyvinyl acetal resin composition according to claim 4, wherein Z contains a branched alkyl group.

7. The α-olefin-modified polyvinyl acetal resin composition according to claim 4, wherein x is an integer of 1 to 6.

8. The α-olefin-modified polyvinyl acetal resin composition according to claim 4, wherein the carbon number of AO is 2.

9. The α-olefin-modified polyvinyl acetal resin composition according to claim 4, wherein n is an integer of 1 to 20.

10. The α-olefin-modified polyvinyl acetal resin composition according to claim 1, wherein the α-olefin contains ethylene.

11. The α-olefin-modified polyvinyl acetal resin composition according to claim 1, wherein the α-olefin-modified polyvinyl acetal resin contains 5 to 80 mol% of α-olefin units.

12. An interlayer film for laminated glass comprising the α-olefin-modified polyvinyl acetal resin composition according to any one of claims 1 to 11.

13. A laminated glass having a plurality of glass plates and the interlayer film for laminated glass according to claim 12 disposed between the plurality of glass plates.