WO2023145776A1 - Polymer film and laminated glass - Google Patents

Abstract

A polymer film wherein, when irradiation is performed with UV light that has a wavelength of 365 nm, a peak is detected at an electron spin nuclear magnetic resonance (ESR), and four such peaks are not detected, or if four peaks are detected, the intensity ratios of the peaks at irradiation intensities of 60% and 20%, relative to at an irradiation intensity of 100%, are each 0.6 to 1.4.

Description

Polymer film and laminated glass

The present invention relates to a polymer film and a laminated glass having a polymer film.

Laminated glass is safe because it does not scatter glass fragments even if it is damaged by an external impact, so it is widely used for the window glass of various vehicles such as automobiles and the window glass of buildings. Laminated glass is widely known in which an interlayer film for laminated glass containing a resin component such as polyvinyl acetal resin is interposed between a pair of glasses to integrate them.

It is known that polymer films used in environments exposed to sunlight, such as interlayer films for laminated glass, are generally mixed with UV absorbers. In addition, it is widely known that various polymer films are blended with antioxidants for the purpose of improving durability. Furthermore, polymer films such as interlayer films for laminated glass are blended with various additives according to their purpose. An interlayer film for laminated glass containing fullerene is disclosed.

JP-A-2004-75433

However, polymer films containing conventional UV absorbers and antioxidants may not be able to sufficiently prevent deterioration due to UV exposure, and further deterioration prevention is required to improve durability. . Moreover, although Patent Document 1 indicates that the fullerene improves the heat shielding property, it does not indicate a compounding that can prevent deterioration of the polymer film due to the fullerene.

Therefore, an object of the present invention is to provide a polymer film that is sufficiently prevented from deterioration and has excellent durability even when used in an environment exposed to ultraviolet rays.

As a result of intensive studies, the present inventors found that the durability of polymer films is excellent when the radical peak in electron spin nuclear magnetic resonance (ESR) at the time of ultraviolet irradiation satisfies predetermined conditions. completed. That is, the present invention provides the following [1] to [17].
[1] When irradiated with ultraviolet rays having a wavelength of 365 nm, a peak in electron spin nuclear magnetic resonance (ESR) is detected, and four peaks are not detected, or even if four peaks are detected, the irradiation intensity is 100%. On the other hand, a polymer film having a peak intensity ratio of 0.6 or more and 1.4 or less when the irradiation intensity is 60% and 20%.
[2] The above [1], comprising at least one resin selected from the group consisting of polyvinyl acetal resins, olefin resins, ionomer resins, ethylene-vinyl acetate copolymer resins, polyurethane resins, and acrylic resins. polymer film.
[3] The polymer film according to [1] or [2] above, which contains a polyvinyl acetal resin.
[4] The polymer film according to any one of [1] to [3] above, which contains a carbon material.
[5] The polymer film according to [4] above, wherein the content of the carbon material is 0.005% by mass or more and 0.1% by mass or less.
[6] The polymer film according to [4] or [5] above, wherein the carbon material is a fullerene.
[7] The polymer film according to [6] above, wherein the fullerenes include hydrogenated fullerenes.
[8] The polymer film according to any one of [1] to [7] above, containing at least one selected from the group consisting of antioxidants and light stabilizers.
[9] The polymer film according to [8] above, wherein the content of the antioxidant is 0.01% by mass or more and 2% by mass or less based on the total amount of the polymer film.
[10] The polymer film of [8] or [9] above, wherein the light stabilizer is a hindered amine light stabilizer.
[11] Any one of [8] to [10] above, wherein the content of the light stabilizer in the polymer film is 0.001% by mass or more and 0.5% by mass or less based on the total amount of the polymer film. 2. The polymer film according to item 1.
[12] The polymer film as described in any one of [8] to [11] above, wherein the weight ratio of the light stabilizer to the antioxidant is 1:20 to 1:1.
[13] Any one of the above [1] to [12], containing a carbon material and an antioxidant, and wherein the mass ratio of the carbon material and the antioxidant is 1:40 to 1:1. The polymer film described in .
[14] The polymer film of any one of [1] to [13] above, which contains an ultraviolet absorber.
[15] The polymer film of [14] above, wherein the ultraviolet absorber is a compound having a benzotriazole skeleton.
[16] The polymer film according to [14] or [15] above, wherein the content of the ultraviolet absorber is 0.01% by mass or more and 2% by mass or less based on the total amount of the polymer film.
[17] A first laminated glass member, a second laminated glass member, and the polymer film according to any one of [1] to [16] above, wherein the first laminated glass member and A laminated glass, wherein the polymer film is arranged between the second laminated glass member.

According to the present invention, it is possible to provide a polymer film that is sufficiently prevented from being deteriorated and has excellent durability even when used in an environment exposed to ultraviolet rays.

The ESR spectrum of Example 3 is shown. An example of the ESR spectrum of Example 5 is shown.

The present invention will be described in more detail below.
<Polymer film>
When the polymer film of the present invention is irradiated with ultraviolet rays having a wavelength of 365 nm, a peak is detected in electron spin nuclear magnetic resonance (ESR). Even if the irradiation intensity is 100%, the intensity ratios of the peaks when the irradiation intensity is 60% and 20% are both 0.6 or more and 1.4 or less.
The peak in the electron spin nuclear magnetic resonance (ESR) is the peak of radicals (radical peak) generated when irradiated with ultraviolet rays. In the present invention, the radical peak satisfies the above requirements, so that the polymer film has excellent durability even when used in an environment exposed to ultraviolet rays.

When four peaks are detected in ESR, the peaks are considered to be peaks derived from radicals for trapping peroxy radicals, for example, peaks derived from antioxidants. When four peaks are detected, the peak height is considered to represent the radical scavenging performance, and the closer the intensity ratio is to 1, the more constant it is regardless of the irradiation intensity of ultraviolet rays, for example, even when the irradiation intensity is high. It is considered that the radical scavenging performance of Therefore, when four peaks are detected, the intensity ratio of the peaks at irradiation intensities of 60% and 20% with respect to the irradiation intensity of 100% is 0.6 or more and 1.4 or less. is less likely to deteriorate when exposed to UV light.

On the other hand, when four ESR peaks are not detected, the detected peaks are considered to be peaks derived from radicals for trapping alkyl radicals, and are considered peaks derived from compounds other than antioxidants. In other words, when four peaks are not detected, it is considered that the alkyl radicals are appropriately captured, and a certain radical capturing performance is exhibited regardless of the intensity ratio of the peaks. difficult to proceed.
In general, when a polymer is exposed to ultraviolet rays, protons are abstracted by the ultraviolet rays to generate alkyl radicals, which then react with oxygen to generate peroxy radicals. While the peroxy radical extracts more protons, it itself becomes hydroperoxide, and deterioration progresses. In other words, it can be said that the capture of alkyl radicals that occurs when four peaks are not detected suppresses the degradation reaction on the upstream side in the degradation scheme. performance is expected to be demonstrated.

In addition, "4 peaks are detected" means that at least 4 peaks are detected, and 5 or more peaks may be detected, but typically 4 peaks are detected. be done. Also, "4 peaks are not detected" means that 1 to 3 peaks are detected, but typically 2 peaks are detected. Although the number of detected peaks does not change depending on the irradiation intensity, it is preferable to detect the number of peaks when the irradiation intensity is 100%. The number of detected peaks means the number of peak divisions.

In addition, as shown in FIG. 1, the peaks in electron spin nuclear magnetic resonance (ESR) appear symmetrically on the plus side and the minus side. It is assumed that the peak of is detected. A pair of peaks has continuous waveforms on the plus side and the minus side, and the intensity difference between the peaks is 0.04 or more.
Therefore, the ESR spectrum shown in FIG. 1 has four peaks detected. Also, the ESR spectrum shown in FIG. 2 has two peaks detected.
Furthermore, the "peak intensity ratio" is the ratio of the maximum height of the peak when the irradiation intensity is 60% or 20% to the maximum height of the peak when the irradiation intensity is 100%. , the maximum height M of the peak at 100% irradiation intensity. The maximum height M of the peak is obtained by reading the maximum height of the peak on the positive side.

When four peaks are detected, the intensity ratio of the peak when the irradiation intensity is 60% to the irradiation intensity of 100% (also referred to as “relative peak height”) may be 0.6 or more and 1.4 or less. , preferably 0.7 to 1.3, more preferably 0.8 to 1.2, still more preferably 0.85 to 1.15, from the viewpoint of further improving durability.
In addition, when four peaks are detected, the intensity ratio of the peaks when the irradiation intensity is 20% to the irradiation intensity of 100% may be 0.6 or more and 1.4 or less, but from the viewpoint of further improving durability. Therefore, it is preferably 0.65 or more and 1.3 or less, more preferably 0.7 or more and 1.2 or less, and still more preferably 0.78 or more and 1.1 or less.

When four peaks are not detected, the intensity ratio of the peak when the irradiation intensity is 60% to the irradiation intensity of 100% is not particularly limited, and is, for example, 0.2 or more and 5 or less, but preferably 0.2 or more and 2 or less. , more preferably 0.5 or more and 1.5 or less.
Further, when four peaks are not detected, the intensity ratio of the peaks when the irradiation intensity is 20% to the irradiation intensity of 100% is not particularly limited. It is 2 or more and 2 or less, more preferably 0.25 or more and 1 or less.

In order for the radical peak to satisfy the above requirements, the polymer film should contain a durability improver. As the durability improver, compounds having radical scavenging properties are preferable, and specific examples thereof include antioxidants, light stabilizers, carbon materials, and the like, which will be described later. In the present invention, one or a combination of two or more of these may be appropriately adjusted so that the radical peak satisfies the above requirements.

[resin]
The polymeric film of the present invention contains a resin as a polymeric material (polymer). The resin may be either a thermosetting resin or a thermoplastic resin, but a thermoplastic resin is preferred. Also, the resin may be an elastomer. By containing a thermoplastic resin, the polymer film can easily function as an adhesive film, and when used as an interlayer film for laminated glass, for example, the adhesiveness to laminated glass members is improved.

Examples of resins include, but are not limited to, polyvinyl acetal resins, olefin resins, ionomer resins, ethylene-vinyl acetate copolymer (EVA) resins, polyurethane resins, and acrylic resins. By using these resins, it becomes easier to ensure adhesion to other members such as laminated glass members. These resins are typically thermoplastic resins. Among the above resins, polyvinyl acetal resins are preferable, and polyvinyl butyral resins are particularly preferable, because they exhibit excellent adhesiveness to inorganic glass when used in combination with a plasticizer.
Polymer film WHEREIN: The said resin may be used individually by 1 type, and may be used together 2 or more types.

(polyvinyl acetal resin)
The polyvinyl acetal resin is not particularly limited as long as it is a polyvinyl acetal resin obtained by acetalizing polyvinyl alcohol (PVA) with an aldehyde.
Although the above aldehyde is not particularly limited, aldehydes having 1 to 10 carbon atoms are generally preferably used. The aldehyde having 1 to 10 carbon atoms is not particularly limited, and examples thereof include n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde and n-nonylaldehyde. , n-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. These aldehydes may be used alone or in combination of two or more.
Among the above, n-butyraldehyde, n-hexylaldehyde and n-valeraldehyde are preferred, and n-butyraldehyde is more preferred. Therefore, polyvinyl butyral resin is suitable for polyvinyl acetal resin.

Polyvinyl alcohol (PVA) is obtained, for example, by saponifying a polyvinyl ester such as polyvinyl acetate. The degree of saponification of polyvinyl alcohol is generally 70-99.9 mol %. Polyvinyl acetal resin may be used individually by 1 type, and may use 2 or more types together.
The average degree of polymerization of PVA is preferably 200 or higher, more preferably 500 or higher, still more preferably 1000 or higher, and even more preferably 1500 or higher. When the average degree of polymerization is equal to or higher than the above lower limit, the penetration resistance of the laminated glass becomes high when used for the laminated glass. Also, the average degree of polymerization of PVA is preferably 5,000 or less, more preferably 4,000 or less, even more preferably 3,500 or less, and still more preferably 2,500 or less.
The average degree of polymerization of polyvinyl alcohol is determined by a method conforming to JIS K6726 "Polyvinyl alcohol test method".

The hydroxyl group content of the polyvinyl acetal resin is preferably 15 mol % or more and preferably 38 mol % or less. When the hydroxyl group content is 15 mol % or more, the adhesiveness tends to be good, and when used in laminated glass, the penetration resistance of the laminated glass tends to be improved. Also, by setting the hydroxyl group content to 38 mol % or less, the laminated glass is prevented from becoming too hard. The amount of hydroxyl groups is more preferably 20 mol % or more, still more preferably 25 mol % or more, from the viewpoint of adhesion to glass members such as laminated glass members. Moreover, the amount of hydroxyl groups is more preferably 35% or less, and still more preferably 33 mol% or less.
When polyvinyl butyral resin is used as polyvinyl acetal resin, the amount of hydroxyl groups is 15 mol % or more, preferably 38 mol % or less, more preferably 20 mol % or more, and still more preferably 25 mol % or more, from the same viewpoint. It is mol % or more, more preferably 35 mol % or less, still more preferably 33 mol % or less.
The amount of hydroxyl groups in the polyvinyl acetal resin is the molar fraction obtained by dividing the amount of ethylene groups to which hydroxyl groups are bonded by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of ethylene groups to which the hydroxyl groups are bonded can be measured according to, for example, JIS K6728 "Polyvinyl butyral test method".

The degree of acetalization of the polyvinyl acetal resin is preferably 47 mol % or more and preferably 85 mol % or less. The degree of acetalization is more preferably 55 mol % or more, still more preferably 60 mol % or more, and more preferably 80 mol % or less, still more preferably 75 mol % or less.
The degree of acetalization means the degree of butyralization when the acetal group is a butyral group and the polyvinyl acetal resin (A) is a polyvinyl butyral resin.

The degree of acetalization is the total amount of ethylene groups in the main chain minus the amount of ethylene groups to which hydroxyl groups are bonded and the amount of ethylene groups to which acetyl groups are bonded. It is a value showing the mole fraction obtained by dividing by the percentage. The degree of acetalization (degree of butyralization) may be calculated, for example, from the results measured by a method conforming to JIS K6728 "Polyvinyl butyral test method".

The degree of acetylation of the polyvinyl acetal resin is preferably 30 mol % or less, more preferably 20 mol % or less, even more preferably 10 mol % or less, and even more preferably 2 mol % or less. When the degree of acetylation is equal to or less than the upper limit, the moisture resistance of the polymer film is enhanced. Although the degree of acetylation is not particularly limited, it is preferably 0.01 mol % or more, more preferably 0.1 mol % or more.
The degree of acetylation is the molar fraction obtained by dividing the amount of ethylene groups to which acetyl groups are bonded by the total amount of ethylene groups in the main chain, expressed as a percentage. The amount of ethylene groups to which the acetyl groups are bonded can be measured according to, for example, JIS K6728 "Polyvinyl butyral test method".

(olefin resin)
Examples of olefin resins include polymers or copolymers of olefins such as ethylene, propylene, 1-butene, 4-methylpentene-1, 1-hexene, 1-octene, 1-decene, and 1-dodecene. Specific examples include polyethylene resin, polypropylene resin, polybutene resin, poly(4-methylpentene-1) resin, and the like.

(ionomer resin)
The ionomer resin is not particularly limited, and various ionomer resins can be used. Specific examples include ethylene-based ionomers, styrene-based ionomers, perfluorocarbon-based ionomers, telechelic ionomers, polyurethane ionomers, and the like. Among these, ethylene-based ionomers are preferable from the viewpoint of improving the mechanical strength, durability, transparency, etc. of laminated glass and from the viewpoint of excellent adhesion to laminated glass members.

As the ethylene ionomer, an ethylene/unsaturated carboxylic acid copolymer ionomer is preferably used because of its excellent transparency and toughness. The ethylene/unsaturated carboxylic acid copolymer is a copolymer having at least structural units derived from ethylene and structural units derived from unsaturated carboxylic acid, and may have structural units derived from other monomers.
Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, etc. Acrylic acid and methacrylic acid are preferred, and methacrylic acid is particularly preferred. Other monomers include acrylic acid esters, methacrylic acid esters, 1-butene, and the like.
The ethylene/unsaturated carboxylic acid copolymer preferably has 75 to 99 mol% of ethylene-derived structural units when the total structural units of the copolymer are 100 mol%, and unsaturated carboxylic acid-derived It preferably has 1 to 25 mol % of structural units.
The ionomer of the ethylene/unsaturated carboxylic acid copolymer is an ionomer resin obtained by neutralizing or crosslinking at least part of the carboxyl groups of the ethylene/unsaturated carboxylic acid copolymer with metal ions. The degree of neutralization of carboxyl groups is usually 1-90%, preferably 5-85%.

Ion sources for ionomer resins include alkali metals such as lithium, sodium, potassium, rubidium and cesium, and polyvalent metals such as magnesium, calcium and zinc, with sodium and zinc being preferred.

The method for producing the ionomer resin is not particularly limited, and it can be produced by a conventionally known production method. For example, when an ionomer of an ethylene/unsaturated carboxylic acid copolymer is used as the ionomer resin, for example, ethylene and an unsaturated carboxylic acid are subjected to radical copolymerization at high temperature and high pressure to form an ethylene/unsaturated carboxylic acid. to produce a copolymer; By reacting the ethylene/unsaturated carboxylic acid copolymer with the metal compound containing the ion source, an ionomer of the ethylene/unsaturated carboxylic acid copolymer can be produced.

(Ethylene-vinyl acetate copolymer (EVA) resin)
The ethylene-vinyl acetate copolymer resin may be a non-crosslinked ethylene-vinyl acetate copolymer resin or a high-temperature crosslinked ethylene-vinyl acetate copolymer resin. As the ethylene-vinyl acetate copolymer resin, ethylene-vinyl acetate modified resins such as ethylene-vinyl acetate copolymer saponified products and ethylene-vinyl acetate hydrolysates can also be used.
The ethylene-vinyl acetate copolymer resin preferably has a vinyl acetate content of 10 to 50% by mass, more preferably 10 to 50% by mass, as measured according to JIS K 6730 "Ethylene-vinyl acetate resin test method" or JIS K 6924-2:1997. is 20 to 40% by mass. By setting the vinyl acetate content to these lower limit values or more, the adhesiveness to other members such as laminated glass members is enhanced, and the penetration resistance of the laminated glass tends to be improved. Also, by setting the vinyl acetate content to these upper limits or less, the breaking strength of the polymer film is increased, and the impact resistance of the laminated glass is improved.

(polyurethane resin)
Examples of polyurethane resins include polyurethanes obtained by reacting an isocyanate compound with a diol compound, polyurethanes obtained by reacting an isocyanate compound with a diol compound, and a chain extender such as polyamine. Moreover, the polyurethane resin may contain a sulfur atom. In that case, part or all of the diols may be selected from polythiols and sulfur-containing polyols. Polyurethane resin can improve adhesion to organic glass. Therefore, it is preferably used when the laminated glass member is made of organic glass.

(acrylic resin)
Examples of acrylic resins include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl methacrylate, sec-butyl (meth)acrylate, t-butyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid 2 - Ethylhexyl, n-octyl (meth)acrylate, lauryl (meth)acrylate, n-tridecyl (meth)acrylate, myristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, ( meth)allyl acrylate, vinyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-naphthyl (meth)acrylate, 2,4,6-trichlorophenyl (meth)acrylate, 2,4,6-tribromophenyl (meth)acrylate, isobornyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate , polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, tetrahydrofluoryl (meth)acrylate, 2,3-dibromopropyl (meth)acrylate, 2-chloroethyl (meth)acrylate , 2,2,2-trifluoroethyl (meth)acrylate, hexafluoroisopropyl (meth)acrylate, glycidyl (meth)acrylate, 3-trimethoxysilylpropyl (meth)acrylate, (meth)acrylic acid 2 -Diethylaminoethyl, 2-dimethylaminoethyl (meth)acrylate, t-butylaminoethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate ) acrylate, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, neopentyl di(meth)acrylate, dimethyloltricyclodecane di(meth)acrylate Acrylic, bifunctional epoxy (meth)acrylate, caprolactone-modified (meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, trimethylolpropane triacrylate, etc. (Meth)acrylic monomers such as trimethylolpropane tetra(meth)acrylate, (meth)acrylonitrile, (meth)acrylamide, dimethyl(meth)acrylamide, diethylaminoethyl (meth)acrylate, and polyethylene glycol di(meth)acrylate polymer. These (meth)acrylic monomers may be used alone, or two or more of them may be used in combination to form a copolymer. (Meth)acrylic monomers, itaconic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyllauryllactam, styrene, and other (meth) ) It may be a copolymer with a monomer other than an acrylic monomer. In the present invention, (meth)acryl means either one or both of acrylic and methacryl.

[Antioxidant/light stabilizer]
The polymer film preferably contains at least one of an antioxidant and a light stabilizer, more preferably contains at least an antioxidant, and preferably contains both an antioxidant and a light stabilizer. More preferred. When the polymer film contains an antioxidant, it becomes easier to capture peroxy radicals, making it easier to detect four radical peaks. On the other hand, if a light stabilizer is contained, alkyl radicals are likely to be captured, and four radical peaks are not detected, and two peaks are likely to be detected.

(Antioxidant)
Antioxidants include phenol compounds, phosphoric compounds, sulfur compounds, and the like. Antioxidants prevent oxidative deterioration of the polymer film and improve durability. Among the above antioxidants, phenolic compounds are suitable.

Phenolic compounds include, for example, 2,6-di-t-butyl-p-cresol (BHT), butylated hydroxyanisole (BHA), 2,6-di-t-butyl-4-ethylphenol, stearyl-β -(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis-(4-methyl-6-butylphenol), 2,2'-methylenebis-(4-ethyl-6- t-butylphenol), 4,4′-butylidene-bis-(3-methyl-6-t-butylphenol), 1,1,3-tris-(2-methyl-hydroxy-5-t-butylphenyl)butane, tetrakis[methylene-3-(3′,5′-butyl-4-hydroxyphenyl)propionate]methane, 1,3,3-tris-(2-methyl-4-hydroxy-5-t-butylphenol)butane, 1 , 3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene and bis(3,3′-t-butylphenol)butyric acid glycol ester and pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate].

Examples of the phosphoric acid compound include trisnonylphenyl phosphite, tridecyl phosphite, 2-ethyl-2-butylpropylene-4,6-tri-tert-butylphenol phosphite, 9,10-dihydro-9-oxa- 10-phosphaphenanthrene, tetra(tridecyl)isopropylidenediphenol diphosphite, tris[2-tert-butyl-4-(3-tert-hydroxy-5-methylphenylthio)-5-methylphenyl]phosph fight and the like.

Examples of the above sulfur compounds include dialkylthiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and pentaerythritol tetra(β-dodecylmercaptopropionate), etc. β-alkylmercaptopropionate esters of polyols and the like are included.
An antioxidant may be used individually by 1 type, and may use 2 or more types together.

The content of the antioxidant in the polymer film is preferably 0.01% by mass or more and 2% by mass or less based on the total amount of the polymer film. By making it 0.01% by mass or more, peroxy radicals can be appropriately captured even in an environment exposed to ultraviolet rays, oxidative deterioration of the resin film can be appropriately prevented, and durability can be enhanced. Moreover, by making it 2 mass % or less, it becomes easy to exhibit the effect commensurate with the content. The content of the antioxidant is more preferably 0.03% by mass or more and 1.5% by mass or less, still more preferably 0.05% by mass or more and 1.0% by mass or less, and 0.07% by mass or more and 0 0.5% by mass or less is even more preferable.

(light stabilizer)
The light stabilizers (HALS) are preferably hindered amine light stabilizers. Hindered amine light stabilizers, for example, scavenge alkyl radicals to prevent deterioration of polymer films due to irradiation with ultraviolet rays contained in sunlight.
Examples of the hindered amine light stabilizer include hindered amine light stabilizers in which an alkyl group, an alkoxy group, or a hydrogen atom is bonded to the nitrogen atom of the piperidine structure. From the viewpoint of further suppressing deterioration, hindered amine light stabilizers in which an alkyl group or an alkoxy group is bonded to the nitrogen atom of the piperidine structure are preferred. The hindered amine light stabilizer is preferably a hindered amine light stabilizer in which an alkyl group is bonded to the nitrogen atom of the piperidine structure, and is a hindered amine light stabilizer in which an alkoxy group is bonded to the nitrogen atom of the piperidine structure. is also preferred.
Only one kind of light stabilizer may be used, or two or more kinds thereof may be used in combination.

Examples of the hindered amine light stabilizer having an alkyl group bonded to the nitrogen atom of the piperidine structure include "Tinuvin 765" and "Tinuvin 622SF" manufactured by BASF, and "ADEKA STAB LA-52" manufactured by ADEKA.
Further, as hindered amine light stabilizers in which an alkoxy group is bonded to the nitrogen atom of the piperidine structure, BASF's "TinuvinXT-850FF" and "TinuvinXT-855FF", and ADEKA's "ADEKA STAB LA-81", etc. mentioned.
Examples of the hindered amine light stabilizer in which a hydrogen atom is bonded to the nitrogen atom of the piperidine structure include "Tinuvin 770DF" manufactured by BASF and "Hostavin N24" manufactured by Clariant.

The content of the light stabilizer in the polymer film is preferably 0.001% by mass or more and 0.5% by mass or less based on the total amount of the polymer film. By making it 0.001% by mass or more, alkyl radicals are easily captured, four radical peaks are not detected and two peaks are easily detected, and deterioration of the polymer film due to ultraviolet rays etc. It can be prevented and durability can be improved. Moreover, by making it 0.5 mass % or less, it becomes easy to exhibit the effect commensurate with the content.
The content of the light stabilizer is more preferably 0.003% by mass or more and 0.4% by mass or less, further preferably 0.005% by mass or more and 0.2% by mass or less, and 0.007% by mass or more. 0.1% by mass or less is even more preferable.

[Carbon material]
The polymer film of the invention preferably contains a carbon material. The carbon material traps radicals such as peroxy radicals and alkyl radicals, making it easier for the peaks detected in the ESR of the polymer film to satisfy the above requirements. The carbon material may be any material that can capture radicals such as peroxy radicals and alkyl radicals, but fullerenes are preferred. Fullerenes trap both peroxy radicals and alkyl radicals, making it easier for peaks detected in ESR to satisfy the above requirements. Moreover, even if the polymer film is used in an environment where it is exposed to ultraviolet rays, the durability is likely to be improved.

Fullerenes include fullerenes and fullerene derivatives. Fullerene consists of carbon atoms and has a closed shell structure. A closed-shell structure is typically a combination of a 5-membered ring and a 6-membered ring. Specific examples of fullerene include _C60 , _C70 , _C76 , _C78 , _C84 , _C90 , _C96 , _C180 , _C240 , _C320 , etc. Among these, _C60 is preferred.

Fullerene derivatives are those in which the carbon atoms of the above-mentioned fullerenes are modified _with inorganic atoms or atoms forming a part of an organic compound. is preferred. In the present invention, by using hydrogenated fullerene, the above-described relative peak height tends to approach 1, and the durability of the polymer film under ultraviolet exposure environment is further improved. Furthermore, the use of hydrogenated fullerene makes it possible to increase the transparency of the polymer film, and also makes it easier to suppress tinting due to the carbon material.
Fullerenes may be used individually by 1 type, and may use 2 or more types together. For example, when hydrogenated fullerene is used, hydrogenated fullerene may be used alone as fullerenes, or hydrogenated fullerene and other fullerenes such as fullerene may be used in combination.

The content of the carbon material in the polymer film is preferably 0.005% by mass or more and 0.1% by mass or less based on the total amount of the polymer film. When the content is 0.005% by mass or more, radicals such as alkyl radicals and peroxy radicals are properly captured by the carbon material, and the peak detected in the ESR of the polymer film easily satisfies the above requirements. Moreover, it becomes easy to improve the durability at the time of ultraviolet exposure.
On the other hand, by setting the content to 0.1% by mass or less, it becomes easier to exhibit an effect commensurate with the content. In addition, the transparency of the polymer film can be increased, and it is possible to prevent the carbon material from imparting a tint.
From the above viewpoints, the content of the carbon material in the polymer film is more preferably 0.006% by mass or more and 0.07% by mass or less, further preferably 0.007% by mass or more and 0.04% by mass or less. 01% by mass or more and 0.025% by mass or less is even more preferable.

In the polymer film of the present invention, carbon materials such as fullerenes are preferably used in combination with one or both of an antioxidant and a light stabilizer, more preferably in combination with at least an antioxidant. The combined use of a carbon material such as fullerenes and at least one of an antioxidant and a light stabilizer makes it easier for the peak detected in ESR to satisfy the above requirements. In addition, the function of scavenging radicals of antioxidants and light stabilizers is enhanced, and the durability of the polymer film under an environment exposed to ultraviolet rays can be further improved.

When the carbon material and the antioxidant are used together in the polymer film, the mass ratio of the carbon material and the antioxidant contained in the polymer film is preferably 1:40 to 1:1. When the mass ratio of the carbon material and the antioxidant is within the above range, the function of scavenging radicals is further enhanced by the carbon material and the antioxidant. It also makes it easier for the peaks detected in the ESR to satisfy the above requirements. From these viewpoints, the mass ratio of the carbon material and the antioxidant in the polymer film is more preferably 1:30 to 1:2, more preferably 1:20 to 1:4, and more preferably 1:15 to 1:5. More preferred.

In the polymer film, it is also preferable to use a light stabilizer and an antioxidant in combination as described above. :20 to 1:1 is preferred. When the mass ratio of the light stabilizer and the antioxidant is within the above range, the function of scavenging peroxy radicals and alkyl radicals is enhanced in a well-balanced manner, making it easier to improve durability when exposed to ultraviolet rays. Also, two peaks detected in ESR are likely to be detected instead of being detected four.
From these viewpoints, the mass ratio of the light stabilizer and the antioxidant in the polymer film is more preferably 1:18 to 1:2, more preferably 1:15 to 1:3, and 1:12 to 1:4. Even more preferable.

In the polymer film, as described above, the carbon material and the light stabilizer may be used together. When these are used together, the mass ratio of the carbon material and light stabilizer contained in the polymer film is preferably 1:20 to 10:1. When the mass ratio of the light stabilizer and the carbon material is within the above range, the carbon material and the light stabilizer further enhance the function of trapping alkyl. The weight ratio of the carbon material to the light stabilizer in the polymer film is more preferably 1:10 to 5:1, more preferably 1:5 to 2:1, even more preferably 1:3 to 1:1.

In the polymer film, as described above, it is also preferable to use a carbon material, an antioxidant, and a light stabilizer in combination. When these are used together, the mass ratio of the carbon material, antioxidant and light stabilizer contained in the polymer film is preferably 1:1:1 to 1:40:10, and 1:2:1 to 1:1:1. 20:10 is more preferred, 1:3:1 to 1:15:5 is more preferred, and 1:4:1 to 1:15:3 is even more preferred.

(Ultraviolet absorber)
The polymer film preferably contains an ultraviolet absorber. The UV absorber absorbs UV rays contained in sunlight or the like, reduces the amount of UV rays that directly irradiate the polymer in the polymer film, and further improves the durability under an UV exposure environment.
Examples of UV absorbers include compounds having a malonate skeleton, compounds having an anilide oxalate skeleton, compounds having a benzotriazole skeleton, compounds having a benzophenone skeleton, compounds having a triazine skeleton, compounds having a benzoate skeleton, and hindered amines. A compound or the like having a skeleton can be used. Among these, compounds having a benzotriazole skeleton (benzotriazole compounds) are preferred.

（式（１）において、Ｒ^１は、水素原子、炭素数が１～８のアルキル基、又は炭素数４～２０のアルコキシカルボニルアルキル基を表し、Ｒ^２は、水素原子、又は炭素数が１～８のアルキル基を表す。Ｘはハロゲン原子又は水素原子である。Ｙ^１及びＹ^２はそれぞれ独立に水酸基又は水素原子であり、Ｙ^１及びＹ^２の少なくともいずれか１つが水酸基である。） Preferred specific examples of benzotriazole compounds include compounds represented by the following general formula (1).

(In formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxycarbonylalkyl group having 4 to 20 carbon atoms, and R ² represents a hydrogen atom or a represents an alkyl group of ∼8, X is a halogen atom or a hydrogen atom, Y ¹ and Y ² are each independently a hydroxyl group or a hydrogen atom, and at least one of Y ¹ and Y ² is a hydroxyl group.)

In Formula (1), the alkyl groups of R ¹ and R ² may have a linear structure or a branched structure. The alkoxycarbonylalkyl group may have a linear structure or a branched structure. Examples of R ¹ and R ² include hydrogen atom, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, pentyl group, hexyl group and octyl group. In addition to these, R ¹ includes a methoxycarbonylpropyl group, an octyloxycarbonylpropyl group, and the like. Among them, R ¹ is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom, a methyl group, a tert-butyl group, a pentyl group or an octyl group. R ¹ and R ² may be the same or different.
The halogen atom of X includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom.
Either one of Y ¹ and Y ² may be a hydroxyl group, or both of them may be a hydroxyl group. Moreover, it is preferable that ^Y2 is at least a hydroxyl group.
Further, specific examples of the compound represented by formula (1) include 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di- t-Butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, Octyl 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate , 3-(5-chloro-2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenylpropionate methyl, 2-(3,5-di-tert-amyl- 2-hydroxyphenyl)benzotriazole, 2-(2,4-dihydroxyphenyl)-2H-benzotriazole and the like.
One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.

The content of the ultraviolet absorber in the polymer film is preferably 0.01% by mass or more and 2% by mass or less based on the total amount of the polymer film. By making it 0.01% by mass or more, it is possible to appropriately absorb ultraviolet rays contained in sunlight and the like, appropriately prevent deterioration of the polymer film due to ultraviolet rays even when used outdoors, and improve durability. can be done. Moreover, by setting the content to 2% by mass or less, it is possible to prevent the polymer film from being tinted by the ultraviolet absorber, and it becomes easy to exhibit an effect commensurate with the content.
The content of the ultraviolet absorber is more preferably 0.03% by mass or more and 1.5% by mass or less, still more preferably 0.05% by mass or more and 1.2% by mass or less, and 0.1% by mass or more. 0.9% by mass or less is even more preferable.

(Plasticizer)
The polymeric film may further contain a plasticizer. A polymer film becomes flexible by containing a plasticizer. Therefore, when used for an interlayer film for laminated glass, for example, it improves the flexibility of the laminated glass and also improves the penetration resistance. Furthermore, it is also possible to improve the adhesiveness to other members such as laminated glass members. The plasticizer is particularly effective when a polyvinyl acetal resin is used as the resin.
Examples of plasticizers include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphorus plasticizers such as organic phosphate plasticizers and organic phosphite plasticizers. etc. Among them, organic ester plasticizers are preferred.

Organic ester plasticizers include, for example, triethylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol dicaprylate, triethylene glycol di-n-octanoate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate, ethylene glycol di-2-ethylbutyrate, 1,3-propylene glycol di-2-ethylbutyrate, 1,4-butylene glycol di-2-ethylbutyrate, 1,2-butylene glycol di-2-ethylbutyrate, diethylene glycol di-2-ethylbutyrate , diethylene glycol di-2-ethylhexanoate, dipropylene glycol di-2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicapriate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n-heptanoate, triethylene glycol di-2-ethylbutyrate, dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, diisononyl adipate, heptylnonyl adipate, dibutyl sebacate, oil-modified alkyd sebacate, mixture of phosphate and adipate, mixed adipate and the like. Mixed adipates include adipates prepared from two or more alcohols selected from alkyl alcohols having 4 to 9 carbon atoms and cyclic alcohols having 4 to 9 carbon atoms.
Among the above plasticizers, triethylene glycol-di-2-ethylhexanoate (3GO) is particularly preferably used.

The content of the plasticizer in the polymer film is not particularly limited, but is preferably 10 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin contained in the polymer film. When the content of the plasticizer is 10 parts by mass or more, the polymer film becomes moderately flexible and has good adhesiveness, etc., and when used as an interlayer film for laminated glass, the laminated glass has good penetration resistance. becomes. Also, when the content of the plasticizer is 100 parts by mass or less, separation of the plasticizer from the polymer film is prevented. The content of the plasticizer is more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, still more preferably 35 parts by mass or more, and more preferably 70 parts by mass or less, still more preferably is 63 parts by mass or less.

[Other additives]
The polymer film of the present invention may contain additives other than those described above, and may contain additives such as coloring agents, adhesive strength modifiers, heat shielding agents, fluorescent whitening agents, and crystal nucleating agents. good. 1 type of these additives may be used and 2 or more types may be used.

In addition to the resin, the polymer film of the present invention contains at least one of an antioxidant, a light stabilizer, a carbon material, an ultraviolet absorber, a plasticizer, and other additives, which are optionally blended as described above, in addition to the resin. It is preferably made of a resin composition containing
In addition, the polymer film is mainly composed of a resin, or a resin and a plasticizer, and the total amount of the resin and the plasticizer in the polymer film is usually 70% by mass or more, preferably 70% by mass or more, based on the total amount of the polymer film. is 80% by mass or more, more preferably 90% by mass or more and less than 100% by mass. By setting the total amount to less than 100% by mass, the polymer film can contain additives such as antioxidants, light stabilizers, carbon materials, and ultraviolet absorbers.

The polymer film of the present invention may constitute a monolayer film consisting of one layer, or may constitute a multilayer film having two or more layers. The multilayer film may have at least one layer of the above polymer film of the present invention. That is, the multilayer film is preferably a laminated film obtained by integrating the polymer film of the present invention and a film other than the polymer film of the present invention. Moreover, the multilayer film may be a laminated film having two or more layers of the polymer film of the present invention, and even in that case, the multilayer film may have films other than the polymer film of the present invention.

The film other than the polymer film of the present invention is not particularly limited as long as it is a film containing the above resin, and may be composed of the resin alone. It is preferably made of a resin composition containing at least one of an agent, a carbon material, an ultraviolet absorber, a plasticizer, and other additives.

The multilayer film may have a two-layer structure in which two or more films are laminated in the thickness direction, a three-layer structure in which three or more films are laminated, or four or more films. may be laminated. Among these, a multilayer film having a 2- to 5-layer structure is preferred, and a multilayer film having a 2- to 3-layer structure is more preferred.

The thickness of the polymer film is not particularly limited, and is, for example, 0.05 mm or more and 2.5 mm or less, preferably 0.1 mm or more and 2.0 mm or less, more preferably 0.2 mm or more and 1.0 mm or less.
The thickness of the multilayer film including the polymer film is not particularly limited, and is, for example, 0.1 mm or more and 3 mm or less, preferably 0.15 mm or more and 2.5 mm or less, more preferably 0.2 mm or more and 1.5 mm or less. .

[Optical Properties of Polymer Film]
In the polymer film of the present invention, the visible light transmittance (Tv) of the laminated glass produced by bonding two clear glass plates via the polymer film is 50% or more from the viewpoint of transparency. is preferred. In addition, the visible light transmittance (Tv) is more preferably 70% or more, further preferably 80% or more, further preferably 85% or more from the viewpoint of being easy to apply to automobile window glass when laminated glass is made. Even more preferable. In the present invention, as described above, a carbon material is preferably used, and high transparency can be ensured by suppressing the amount used.
From the viewpoint of transparency, the visible light transmittance (Tv) is preferably as high as possible, for example, 99% or less. The visible light transmittance (Tv) can be measured according to JIS R3212 (2015).

The polymer film of the present invention preferably has a yellowness index (YI) of 20 or less for laminated glass produced by bonding two clear glass plates via a polymer film. When the yellowness index (YI) is 20 or less, it is possible to suppress coloration and obtain a highly designed polymer film. Moreover, the yellowness index (YI) is more preferably 15 or less, still more preferably 10 or less, and even more preferably 5 or less. In the present invention, as described above, a carbon material is preferably used, but a low yellowness can be ensured by using fullerenes and suppressing the amount used. The yellowness index (YI) is preferably as low as possible, and should be 0 or more, but practically, for example, 0.5 or more is sufficient. The yellowness index (YI) can be measured using a spectrophotometer according to JIS K7105.

A multilayer film having the polymer film of the present invention may also have the above optical properties. That is, the preferred upper limit or lower limit of the visible light transmittance (Tv) and the yellowness index (YI) of laminated glass produced by bonding two clear glass plates via a multilayer film, and The lower limit or upper limit is the same as the values described for the visible light transmittance (Tv) and yellowness (YI) of the laminated glass produced by bonding via the polymer film.

The clear glass plate used in the above measurements of visible light transmittance (Tv) and yellowness index (YI) has a thickness of 2.5 mm and a visible light transmittance of 90 measured in accordance with JIS R 3106:1998. 0.5%. In addition, the clear glass plate is specified in JIS Z 8781-1 (2012), JIS Z 8781-2 (2012), and JIS Z 8781-4 (2013), CIE standard illuminant D65, 10 ° field of view, etc. a*=−0.6, b*=0.2, haze is less than 0.2%, obtained using the color function. The above clear glass plate is also referred to as reference clear glass.

(Method for producing polymer film)
The polymer film of the present invention can be obtained, for example, by mixing a resin and various additives that are optionally blended, and molding the resulting resin composition by extrusion molding, press molding, or the like.
Here, from the viewpoint of enhancing the dispersibility in the resin composition, the carbon material such as fullerenes, for example, when using a plasticizer, should be mixed with the plasticizer and sufficiently dispersed in the plasticizer. and may be mixed with the resin. At this time, a dispersant or the like may be appropriately added to the plasticizer. In addition, when using additives other than carbon materials, depending on the type of additive, additives other than carbon materials may be mixed with the resin after being blended with the plasticizer and sufficiently dispersed in the plasticizer. .

In the case of constructing a multilayer film, the polymer film may be obtained by molding each layer by extrusion molding, press molding, etc., and laminating them, as in the case of a single-layer structure. For example, a method of preparing two or more extruders and attaching a multi-layer feed block to the tips of the plurality of extruders for co-extrusion is preferred. Moreover, when a plurality of layers are provided and there are two or more layers having the same composition, two or more layers having the same composition may be extruded from one extruder.
In addition, the multilayer film is prepared by preparing a plurality of films, placing the plurality of films between a pair of laminated glass members, and performing thermocompression bonding (press molding) to produce a laminated glass and a plurality of films. A multilayer film formed by integrating films may also be produced together.

The polymer film of the present invention can be used in various applications without any particular limitation, but is preferably used in applications exposed to light including ultraviolet light such as sunlight. The polymer film of the present invention may be used, for example, in various vehicles such as automobiles, vehicles such as aircraft and ships, construction, solar cells, electronic devices, foods, and the like. Moreover, the polymer film of the present invention may be used as an adhesive film, a protective film, an optical film, a gas barrier film, etc., and is preferably used as an adhesive film. An adhesive film is generally placed between two members and may be used to adhere the two members together.
By using a thermoplastic resin as the resin, the polymer film of the present invention can be easily adhered to other members by thermocompression bonding, so that it can be suitably used as an adhesive film. Moreover, the polymer film of the present invention is preferably used as an interlayer for laminated glass that is placed between two glass members. In each application, the polymeric film may be used as a monolayer film or as a multilayer film.

<Laminated glass>
The present invention further provides laminated glass. In laminated glass, the polymer film of the present invention is preferably used as an interlayer film for laminated glass. The laminated glass comprises two laminated glass members (first and second laminated glass members) and a polymer film disposed between the laminated glass members. In the laminated glass, a single layer film made of a polymer film may be arranged between two laminated glass members, or a multilayer film containing a polymer film may be arranged.
Two laminated glass members are bonded via a polymer film or a multilayer film containing a polymer film. The polymeric film or multilayer film adheres on one side to one laminated glass member and on the other side to the other laminated glass member. The structures of the polymer film and multilayer film are as described above.
Laminated glass may be produced by disposing the polymer film or multilayer film described above between two laminated glass members and integrating them by thermocompression bonding or the like. Alternatively, a plurality of films including a polymer film are prepared, the plurality of films are stacked between a pair of laminated glass members, and the plurality of films and the laminated glass member are integrated by thermocompression bonding or the like. It may be manufactured by

(Laminated glass member)
A laminated glass member used in laminated glass includes a glass plate, and the glass plate may be either inorganic glass or organic glass, but inorganic glass is preferred. Examples of inorganic glass include, but are not limited to, clear glass, float plate glass, polished plate glass, figured glass, wired plate glass, lined plate glass, green glass, and the like.
Also, as the organic glass, what is generally called resin glass is used, and it is not particularly limited, but examples thereof include organic glass composed of resins such as polycarbonate, acrylic resin, acrylic copolymer resin, and polyester.
The two laminated glass members may be made of the same material, or may be made of different materials. For example, one may be inorganic glass and the other may be organic glass, but it is preferable that both of the two laminated glass members are inorganic glass or organic glass.
The thickness of each laminated glass member is not particularly limited, but is, for example, approximately 0.1 to 15 mm, preferably 0.5 to 5 mm. The thickness of each laminated glass member may be the same or different, but preferably the same.

[Optical properties of laminated glass]
From the same viewpoint as above, the laminated glass of the present invention preferably has optical properties similar to those described for the polymer film. That is, the visible light transmittance (Tv) of the laminated glass is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, even more preferably 85% or more, and is, for example, 99% or less. .
In addition, the yellowness index (YI) of the laminated glass is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, even more preferably 5 or less, and may be 0 or more, but practical may be, for example, 0.5 or more.

The laminated glass of the present invention can be used for various vehicles such as automobiles, vehicles such as aircraft and ships, and window glass for buildings, etc., but is preferably used as laminated glass for automobiles. Laminated glass for automobiles may be windshield glass (front glass), side glass, rear glass, or roof glass.

The present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

The measurement method and evaluation method in this example are as follows.

[Electron spin nuclear magnetic resonance (ESR) measurement]
About 10 mg was cut from the polymer film to prepare an ESR measurement sample, and ESR measurement was performed under the following conditions to obtain an ESR spectrum. Each sample was irradiated with ultraviolet light having a wavelength of 365 nm in the order of 20%, 60%, and 100% output, and an ESR spectrum was obtained at each output. The number of peaks (number of peak divisions) and the maximum peak height were detected in each of the obtained ESR spectra.
(ESR analysis conditions)
Measuring device: Electron spin resonance spectrometer (manufactured by Bruker, "Bruker E500")
Measurement mode: cw mode Microwave frequency: about 9.4 GHz
Microwave intensity: 2.0mW
Sweep magnetic field range: 20mT (200 Gauss)
Modulation magnetic field amplitude: 0.3 mT (3.0 Gauss)
Measurement temperature: room temperature (294K)
Standard sample: DPPH (1,1-diphenyl-2-picrylhydrazyl) solution Wavelength, light source: 365 nm (manufactured by Hamamatsu Photonics, “LIGHTNINGCURE spot light source LC8 L9566-01A”), output (irradiation intensity) set at 100% 100mW/ ^cm2

[Tv (transparency)]
Visible light transmittance (Tv) was measured using a spectrophotometer ("U-4100" manufactured by Hitachi High Technology) in accordance with JIS R3212 (2015). At the time of measurement, it was placed 13 cm away from the integrating sphere on the optical path between the light source and the integrating sphere and parallel to the normal to the optical axis so that only the parallel light transmitted through the laminated glass was received by the integrating sphere. A laminated glass was installed, and the spectral transmittance was measured. Visible light transmittance was calculated from the obtained spectral transmittance. The measurement conditions were a scan speed of 300 nm/min and a slit width of 8 nm, and other conditions were measured according to JIS R 3212 (2015).

[YI (color)]
The yellowness index (YI) of the laminated glass was measured according to JIS K7105 using a spectrophotometer ("U-4100" manufactured by Hitachi High-Technology Co., Ltd.).

[Durability evaluation]
A sample cut to 1 cm x 2.5 mm is attached to clear glass, and set in a light resistance tester ("SX-75" manufactured by Suga Test Instruments Co., Ltd.) so that the sample side is on the xenon irradiation side, and the black panel temperature is 83. C., a temperature inside the chamber of ^50.degree . The molecular weight (M1) of the polymer film before irradiation with xenon light and the molecular weight (M2) of the polymer film after irradiation with xenon light were measured. A molecular weight retention rate (%) was calculated from M2/M1×100.
(molecular weight measurement)
The molecular weight of the polymer film is the number average molecular weight, measured by gel permeation chromatography (GPC), and calculated by polystyrene conversion. GPC measurement used Shodex KF-806L (manufactured by Showa Denko KK) as a column. Tetrahydrofuran (THF) was used as the solvent and mobile phase. Furthermore, the GPC measurement conditions were a flow rate of 1.0 ml/min and a measurement temperature of 40°C. In this measurement, since the peak of additives other than the resin appears on the low molecular weight side, the molecular weight of the resin contained in the polymer film is obtained from the peak of the resin that appears on the high molecular weight side, excluding the additive peak. rice field.

Components used in Examples and Comparative Examples are as follows.
(1) Resin PVB: Polyvinyl butyral resin, degree of acetalization 69 mol%, amount of hydroxyl groups 30 mol%, degree of acetylation 1 mol%, average degree of polymerization of PVA used for synthesis 1700
(2) plasticizer 3GO: triethylene glycol di-2-ethylhexanoate (3) antioxidant BHT: 2,6-di-t-butyl-p-cresol Irganox 1010: pentaerythritol tetrakis [3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate], product name “Irganox 1010”, manufactured by BASF Corporation (4) UV absorber T326: represented by formula (1), and X is a chlorine atom, R ¹ is a methyl group, R ² is a tert-butyl group, Y ¹ is a hydrogen atom, and Y ² is a hydroxyl group. Trade name "Tinuvin 326", manufactured by BASF (5) light stabilizer (HALS)
HS765: hindered amine light stabilizer, manufactured by BASF, product name "Tinuvin765"
(6) Carbon material Fullerene: Fullerene _C60 , manufactured by Frontier Carbon, product name “nanom purple ST”
Hydrogenated fullerene: Hydrogenated fullerene _C60 , manufactured by Frontier Carbon, product name "nanom spectra A100"

[Examples 1 to 6]
(Preparation of polymer film)
A resin composition obtained by mixing and dispersing a carbon material in a plasticizer according to the formulation shown in Table 1, then charging it into an extruder together with polyvinyl butyral resin (PVB) and other additives, and kneading them. was extruded from an extruder to obtain a polymer film with a thickness of 760 μm. ESR measurement was performed on the resulting polymer film. Further, the extruded resin composition was further press-molded to obtain a polymer film having a thickness of 100 μm, and the durability was evaluated.

(Production of laminated glass)
Two sheets of clear glass each measuring 100 mm long×100 mm wide×2.5 mm thick were prepared. As the clear glass, the standard clear glass described in the specification was used. The polymer film having a thickness of 760 μm obtained above was sandwiched between two sheets of clear glass, and temporarily press-bonded by a vacuum bag method. The temporarily pressure-bonded laminate is held in an autoclave under conditions of a temperature of 140 ° C. and a pressure of 1.2 MPa for 20 minutes, and then the temperature is lowered to 20 ° C. and returned to atmospheric pressure to complete the main pressure bonding. A laminated glass was obtained in which two sheets of clear glass were adhered by a polymer film (intermediate film). The optical properties of the obtained laminated glass were measured. Table 1 shows the results.

[Comparative Examples 1 and 2]
According to the composition of Table 1, each component was put into an extruder, and each component was kneaded and extruded by the extruder to obtain a polymer film having a thickness of 760 μm and a thickness of 100 μm. ESR measurement and durability evaluation were performed in the same manner as in Example 1 for the obtained polymer film. After that, similarly to Example 1, a laminated glass was produced, and each optical characteristic of the obtained laminated glass was measured. Table 1 shows the results.

As shown in Table 1, in Examples 1 to 4, peaks in electron spin nuclear magnetic resonance (ESR) were detected, and as shown in FIG. The intensity ratios of the peaks when the intensity was 60% and 20% were both 0.6 or more and 1.4 or less. In Examples 5 and 6, electron spin nuclear magnetic resonance (ESR) peaks were detected, but four peaks were not detected as shown in FIG. Therefore, in Examples 1 to 6, the durability in an environment exposed to ultraviolet rays was improved, and the molecular weight retention rate was high even when accelerated deterioration was caused by irradiation with xenon light.
On the other hand, in Comparative Examples 1 and 2, peaks in electron spin nuclear magnetic resonance (ESR) were detected, and the number of the peaks was four. Any of the intensity ratios of the peaks was less than 0.6. Therefore, the durability under the ultraviolet exposure environment was not sufficiently improved, and the molecular weight retention rate was lowered when accelerated deterioration was caused by irradiation with xenon light.

Claims (11)

When irradiated with ultraviolet light having a wavelength of 365 nm, a peak in electron spin nuclear magnetic resonance (ESR) is detected, and 4 peaks are not detected, or even if 4 peaks are detected, the irradiation intensity is 100%. A polymer film having a peak intensity ratio of 0.6 or more and 1.4 or less when the intensity is 60% and 20%. The polymer film according to claim 1, comprising at least one resin selected from the group consisting of polyvinyl acetal resins, olefin resins, ionomer resins, ethylene-vinyl acetate copolymer resins, polyurethane resins, and acrylic resins. The polymer film according to claim 1 or 2, which contains a polyvinyl acetal resin. The polymer film according to any one of claims 1 to 3, which contains a carbon material. The polymer film according to claim 4, wherein the content of the carbon material is 0.005% by mass or more and 0.1% by mass or less. The polymer film according to claim 4 or 5, wherein the carbon material is a fullerene. The polymer film according to claim 6, wherein the fullerenes include hydrogenated fullerenes. The polymer film according to any one of claims 1 to 7, comprising at least one selected from the group consisting of antioxidants and light stabilizers. The polymer film according to claim 8, wherein the mass ratio of the light stabilizer and the antioxidant is 1:20 to 1:1. The polymer film according to any one of claims 1 to 9, comprising a carbon material and an antioxidant, and wherein the mass ratio of the carbon material and the antioxidant is 1:40 to 1:1. . A first laminated glass member, a second laminated glass member, and the polymer film according to any one of claims 1 to 10, wherein the first laminated glass member and the second laminated glass A laminated glass in which the polymer film is arranged between members.

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