Laminate containing thermoplastic resin film and glass plate
The thermoplastic resin film with a pigment and hindered amine light stabilizer addresses the issue of color unevenness in conventional films by enhancing light resistance and maintaining transparency.
Patent Information
- Application Number
- JP2022090967
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Priority Date
- 2017-03-31
- Filing Date
- 2022-06-03
- Publication Date
- 2025-08-14
- Estimated Expiration
- 2038-03-30
AI Technical Summary
Conventional thermoplastic resin films exhibit low light resistance, leading to color unevenness after light irradiation, which is not effectively addressed by existing technologies.
A thermoplastic resin film comprising a thermoplastic resin, a pigment, and a hindered amine light stabilizer, with specific layer configurations and compositions to enhance light resistance and prevent color unevenness.
The resin film effectively suppresses color unevenness and maintains high transparency even after prolonged exposure to light, ensuring consistent color tone and reduced discoloration.
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Abstract
Description
[Technical Field]
[0001] The present invention relates to a thermoplastic resin film that is suitably used by being laminated to another member such as a glass plate, etc. The present invention also relates to a glass plate-containing laminate using the thermoplastic resin film. [Background technology]
[0002] BACKGROUND ART Glass-plate-containing laminates in which a resin film is bonded to a glass plate are known. Among glass-plate-containing laminates, laminated glass is widely used.
[0003] Laminated glass is excellent in safety because it scatters only a small amount of glass fragments even when broken by an external impact. For this reason, the laminated glass is widely used in automobiles, railway vehicles, aircraft, ships, buildings, etc. The laminated glass is manufactured by sandwiching a thermoplastic resin film between a pair of glass plates. In addition to laminated glass, the thermoplastic resin film may also be bonded to a member other than glass plates.
[0004] The thermoplastic resin film used in the above laminated glass is disclosed, for example, in Patent Document 1 listed below.
[0005] Patent Document 1 listed below discloses an interlayer film that has a low tendency to yellow, high transmittance for UV-A rays and visible light, and low transmittance for UV-B rays. This interlayer film contains polyvinyl acetal, a plasticizer, and an oxanilide-type compound that is a UV absorber. Patent Document 1 also describes that the interlayer film may contain a HAS / HALS / NOR-HALS-type non-aromatic light stabilizer and may also contain a dye. [Prior art documents] [Patent documents]
[0006] [Patent Document 1] US2012 / 0052310A1 Summary of the Invention [Problem to be solved by the invention]
[0007] Conventional thermoplastic resin films such as those described in Patent Document 1 have low light resistance, and after being irradiated with light, the color tone changes between the edge and the inside of the edge, which can cause color unevenness.
[0008] An object of the present invention is to provide a thermoplastic resin film that can suppress the occurrence of color unevenness after light irradiation. Another object of the present invention is to provide a glass plate-containing laminate using the above thermoplastic resin film. [Means for solving the problem]
[0009] According to a broad aspect of the present invention, there is provided a thermoplastic resin film (sometimes abbreviated herein as "resin film") comprising a thermoplastic resin, a pigment, and a hindered amine light stabilizer.
[0010] In a specific aspect of the resin film according to the present invention, the thermoplastic resin is a polyvinyl acetal resin or an ionomer resin.
[0011] In a specific aspect of the resin film according to the present invention, the resin film contains a plasticizer.
[0012] The resin film according to the present invention contains, as the pigment, a phthalocyanine compound, a quinacrine compound, Lydon It is preferable that the pigment contains a phthalocyanine compound, an azo compound, a pentaphene compound, a dioxazine compound, a perylene compound, an indole compound, or carbon black. It is preferable that the maximum absorption wavelength of the phthalocyanine compound is 500 nm or more and 740 nm or less. The resin film according to the present invention may contain a phthalocyanine compound as the pigment, and Lydon The compound may include a compound, a perylene compound, or an indole compound, and may also include carbon black.
[0013] In a specific aspect of the resin film according to the present invention, when a glass plate-containing laminate is obtained by sandwiching a thermoplastic resin film between two sheets of green glass having a thickness of 2 mm in accordance with JIS R3208, the haze value of the obtained glass plate-containing laminate is 5% or less.
[0014] In a specific aspect of the resin film according to the present invention, the resin film includes a first surface layer and a second surface layer.
[0015] In a specific aspect of the resin film according to the present invention, the resin film includes an intermediate layer between the first surface layer and the second surface layer.
[0016] In a specific aspect of the resin film according to the present invention, the intermediate layer contains the pigment.
[0017] In a specific aspect of the resin film according to the present invention, when the intermediate layer contains the hindered amine light stabilizer, the first surface layer contains or does not contain the hindered amine light stabilizer, and the first surface layer contains the hindered amine light stabilizer, the content of the hindered amine light stabilizer in 100% by weight of the intermediate layer is greater than the content of the hindered amine light stabilizer in 100% by weight of the first surface layer; and when the second surface layer contains or does not contain the hindered amine light stabilizer, and the second surface layer contains the hindered amine light stabilizer, the content of the hindered amine light stabilizer in 100% by weight of the intermediate layer is greater than the content of the hindered amine light stabilizer in 100% by weight of the second surface layer.
[0018] In a specific aspect of the resin film according to the present invention, the hindered amine light stabilizer is a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to a nitrogen atom of a piperidine structure.
[0019] The resin film according to the present invention is preferably a thermoplastic resin film that is used by being stuck to a glass plate.
[0020] According to a broad aspect of the present invention, there is provided a glass-plate-containing laminate comprising a first glass plate and the above-described thermoplastic resin film, wherein the thermoplastic resin film is bonded to the first glass plate.
[0021] In a specific aspect of the glass-plate-containing laminate according to the present invention, the glass-plate-containing laminate includes the first glass plate as a first laminated glass member, the thermoplastic resin film, and a second laminated glass member, the thermoplastic resin film being bonded to the first glass plate, the thermoplastic resin film being bonded to the second laminated glass member, and the thermoplastic resin film being disposed between the first glass plate and the second laminated glass member.
[0022] The glass plate-containing laminate according to the present invention may be an automobile side glass, an automobile rear glass, or an automobile roof glass. [Effects of the Invention]
[0023] The thermoplastic resin film according to the present invention contains a thermoplastic resin, a pigment, and a hindered amine light stabilizer, and therefore can suppress the occurrence of color unevenness after the thermoplastic resin film according to the present invention is irradiated with light. [Brief explanation of the drawings]
[0024] [Figure 1] FIG. 1 is a cross-sectional view showing a glass plate-containing laminate using a thermoplastic resin film according to one embodiment of the present invention. [Figure 2] FIG. 2 is a cross-sectional view showing a modified example of a glass plate-containing laminate using a thermoplastic resin film according to one embodiment of the present invention. [Figure 3] FIG. 3 shows laminated glass on which color unevenness occurred in the evaluation of color unevenness after light irradiation. DETAILED DESCRIPTION OF THE INVENTION
[0025] The present invention will be described in detail below.
[0026] The thermoplastic resin film according to the present invention (sometimes abbreviated as "resin film" in this specification) is preferably used by being bonded to another member such as a glass plate. The other member is a member to be bonded.
[0027] The resin film according to the present invention contains a thermoplastic resin, a pigment, and a hindered amine light stabilizer.
[0028] Since the present invention has the above-mentioned configuration, it is possible to suppress the occurrence of color unevenness after light irradiation. The resin film of the present invention has high light resistance. After the resin film of the present invention is irradiated with light, the color tone is less likely to change between the edge and the inside of the edge, and color unevenness is less likely to occur.
[0029] The resin film according to the present invention is preferably used by being attached to a glass plate to obtain a glass-plate-containing laminate. In the present invention, the light resistance of the glass-plate-containing laminate can be improved and the occurrence of color unevenness can be suppressed.
[0030] Furthermore, since the present invention employs the above-described configuration, discoloration can also be suppressed. When the glass plate-containing laminate has high transparency, the high transparency can be maintained even when used for a long period of time or exposed to high temperatures, and a decrease in visible light transmittance can be prevented.
[0031] The resin film may have a one-layer structure, a two-layer or more structure, a three-layer or more structure, or a four-layer or more structure. The resin film may have a two-layer or more structure and include a first surface layer and a second surface layer. The resin film may have a three-layer or more structure and include an intermediate layer between the first surface layer and the second surface layer. The resin film may have two or more intermediate layers. The resin film may include a first intermediate layer and a second intermediate layer.
[0032] A glass plate-containing laminate is obtained by sandwiching a thermoplastic resin film between two 2 mm thick sheets of green glass according to JIS R3208. The total light transmittance of the obtained glass plate-containing laminate is preferably 1% or more, more preferably 4% or more, preferably 50% or less, more preferably 35% or less, even more preferably 20% or less, and particularly preferably 10% or less. The thermoplastic resin film preferably has a region that satisfies the lower or upper limit of the total light transmittance.
[0033] From the viewpoint of effectively suppressing color unevenness after light irradiation, the total light transmittance of the surface layer is preferably higher than that of the intermediate layer, and is preferably 10% or more, more preferably 50% or more higher than that of the intermediate layer.
[0034] The total light transmittance is the sum of the parallel light transmittance and the diffuse light transmittance. The total light transmittance is measured in accordance with JIS R3106:1998. Specifically, a spectrophotometer is used, and the object to be measured is placed parallel to and in close contact with the opening of the integrating sphere so that all transmitted light is received by the integrating sphere, and the spectral transmittance is measured. The total light transmittance refers to the visible light transmittance calculated from the spectral transmittance measured in this state. An example of the spectrophotometer is the "U-4100" manufactured by Hitachi High-Technologies Corporation.
[0035] Hereinafter, each material that can be used for the resin film according to the present invention will be described in detail.
[0036] (thermoplastic resin) The resin film contains a thermoplastic resin, such as a polyvinyl acetal resin, an ionomer resin, an ethylene-vinyl acetate copolymer resin, an ethylene-acrylic acid copolymer resin, a polyurethane resin, a polyvinyl alcohol resin, or a cycloolefin resin.
[0037] In the resin film according to the present invention, the thermoplastic resin contained in the resin film is preferably a polyvinyl acetal resin or an ionomer resin, more preferably a polyvinyl acetal resin. The surface layer and the intermediate layer preferably contain a polyvinyl acetal resin or an ionomer resin. The polyvinyl acetal resin and the ionomer resin may each be used alone or in combination of two or more.
[0038] The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol with an aldehyde. The polyvinyl acetal resin is preferably an acetalized product of polyvinyl alcohol. The polyvinyl alcohol can be produced, for example, by saponifying polyvinyl acetate. The degree of saponification of the polyvinyl alcohol is generally within the range of 70 to 99.9 mol%.
[0039] The average degree of polymerization of the polyvinyl alcohol is preferably 200 or more, more preferably 500 or more, and preferably 3500 or less, more preferably 3000 or less, and even more preferably 2500 or less. When the average degree of polymerization is equal to or greater than the lower limit, the penetration resistance of the glass plate-containing laminate is further improved. When the average degree of polymerization is equal to or less than the upper limit, the resin film is easily formed.
[0040] The average degree of polymerization of the polyvinyl alcohol is determined by a method in accordance with JIS K6726 "Testing method for polyvinyl alcohol."
[0041] The number of carbon atoms in the acetal group contained in the polyvinyl acetal resin is not particularly limited. The aldehyde used in producing the polyvinyl acetal resin is not particularly limited. The number of carbon atoms in the acetal group in the polyvinyl acetal resin is preferably 3 or 4. When the number of carbon atoms in the acetal group in the polyvinyl acetal resin is 3 or more, the glass transition temperature of the resin film becomes sufficiently low.
[0042] The aldehyde is not particularly limited. Generally, an aldehyde having 1 to 10 carbon atoms is preferably used. Examples of the aldehyde having 1 to 10 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, and benzaldehyde. Propionaldehyde, n-butylaldehyde, isobutyraldehyde, n-hexylaldehyde, or n-valeraldehyde is preferred, with propionaldehyde, n-butylaldehyde, or isobutyraldehyde being more preferred, and n-butylaldehyde being even more preferred. The aldehydes may be used alone or in combination of two or more.
[0043] The hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin is preferably 15 mol% or more, more preferably 18 mol% or more, and preferably 40 mol% or less, more preferably 35 mol% or less. When the hydroxyl group content is equal to or greater than the lower limit, the adhesive strength of the resin film is further increased. When the hydroxyl group content is equal to or less than the upper limit, the flexibility of the resin film is increased, making the resin film easier to handle.
[0044] The hydroxyl group content of the polyvinyl acetal resin is the molar fraction calculated by dividing the number of ethylene groups having hydroxyl groups by the total number of ethylene groups in the main chain, and is expressed as a percentage. The number of ethylene groups having hydroxyl groups can be measured, for example, in accordance with JIS K6728 "Testing Methods for Polyvinyl Butyral."
[0045] The acetylation degree (acetyl group amount) of the polyvinyl acetal resin is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, even more preferably 0.5 mol% or more, and preferably 30 mol% or less, more preferably 25 mol% or less, and even more preferably 20 mol% or less. When the acetylation degree is above the lower limit, the compatibility of the polyvinyl acetal resin with the plasticizer is increased. When the acetylation degree is below the upper limit, the moisture resistance of the resin film and the glass plate-containing laminate is increased.
[0046] The degree of acetylation is a molar fraction calculated by dividing the amount of ethylene groups having acetyl groups by the total amount of ethylene groups in the main chain, and is expressed as a percentage. The amount of ethylene groups having acetyl groups can be measured, for example, in accordance with JIS K6728 "Testing Methods for Polyvinyl Butyral."
[0047] The degree of acetalization of the polyvinyl acetal resin (the degree of butyralization in the case of a polyvinyl butyral resin) is preferably 60 mol% or more, more preferably 63 mol% or more, preferably 85 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less. When the degree of acetalization is equal to or greater than the lower limit, the compatibility of the polyvinyl acetal resin with the plasticizer is increased. When the degree of acetalization is equal to or less than the upper limit, the reaction time required to produce the polyvinyl acetal resin is shortened.
[0048] The degree of acetalization is determined as follows. First, the amount of ethylene groups to which hydroxyl groups are bonded and the amount of ethylene groups to which acetyl groups are bonded are subtracted from the total amount of ethylene groups in the main chain to determine the value. The obtained value is divided by the total amount of ethylene groups in the main chain to determine the molar fraction. The value expressed as a percentage of this molar fraction is the degree of acetalization.
[0049] The hydroxyl group content (hydroxyl group amount), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from the results of measurements made in accordance with JIS K6728 "Testing Methods for Polyvinyl Butyral." However, measurements made in accordance with ASTM D1396-92 may also be used. When the polyvinyl acetal resin is a polyvinyl butyral resin, the hydroxyl group content (hydroxyl group amount), acetalization degree (butyralization degree), and acetylation degree are preferably calculated from the results of measurements made in accordance with JIS K6728 "Testing Methods for Polyvinyl Butyral."
[0050] (plasticizer) From the viewpoint of appropriately increasing the adhesive strength of the resin film, the resin film preferably contains a plasticizer. The surface layer and the intermediate layer preferably contain a plasticizer. The combined use of a polyvinyl acetal resin and a plasticizer further increases the adhesive strength of the resin film according to the present invention to glass plates, laminated glass members, other resin films, etc. The plasticizer may be used alone or in combination of two or more.
[0051] The plasticizer is not particularly limited. Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and organic phosphoric acid plasticizers such as organic phosphoric acid plasticizers and organic phosphorous acid plasticizers. Organic ester plasticizers are preferred. The plasticizer is preferably a liquid plasticizer.
[0052] The monobasic organic acid ester is not particularly limited, and examples thereof include glycol esters obtained by reacting glycol with a monobasic organic acid. Examples of the glycol include triethylene glycol, tetraethylene glycol, and tripropylene glycol. Examples of the monobasic organic acid include butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptyl acid, n-octylic acid, 2-ethylhexyl acid, n-nonyl acid, and decylic acid.
[0053] The polybasic organic acid ester is not particularly limited, and examples thereof include ester compounds of a polybasic organic acid with an alcohol having a linear or branched structure and having 4 to 8 carbon atoms. Examples of the polybasic organic acid include adipic acid, sebacic acid, and azelaic acid.
[0054] Examples of the organic ester plasticizer include triethylene glycol di-2-ethylpropanoate, 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, 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, diethylene glycol di-n-octanoate, tetraethylene glycol di-n-heptanoate, diethylene glycol di-n-octanoate, di ... Examples of suitable organic ester plasticizers include ethylene 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 dicaprylate, dihexyl adipate, dioctyl adipate, hexylcyclohexyl adipate, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, diisodecyl adipate, heptylnonyl adipate, dibutyl sebacate, oil-modified alkyd sebacate, and a mixture of a phosphate ester and an adipate. Other organic ester plasticizers may also be used. Adipic acid esters other than those listed above may also be used.
[0055] The organic phosphoric acid plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, and triisopropyl phosphate.
[0056] The plasticizer is preferably a diester plasticizer represented by the following formula (1):
[0057] [ka]
[0058] In the above formula (1), R1 and R2 each represent an organic group having 5 to 10 carbon atoms, R3 represents an ethylene group, an isopropylene group, or an n-propylene group, and p represents an integer of 3 to 10. In the above formula (1), R1 and R2 each preferably represent an organic group having 6 to 10 carbon atoms.
[0059] The plasticizer preferably comprises triethylene glycol di-2-ethylhexanoate (3GO) or triethylene glycol di-2-ethylbutyrate, and more preferably comprises triethylene glycol di-2-ethylhexanoate.
[0060] The content of the plasticizer is not particularly limited. In the resin film, the content of the plasticizer is preferably 25 parts by weight or more, more preferably 30 parts by weight or more, preferably 60 parts by weight or less, more preferably 50 parts by weight or less, even more preferably 45 parts by weight or less, and even more preferably 40 parts by weight or less, relative to 100 parts by weight of the thermoplastic resin. When the content of the plasticizer is above the lower limit, the penetration resistance of the glass plate-containing laminate is further increased. When the content of the plasticizer is below the upper limit, the transparency of the resin film is further increased.
[0061] (pigment) From the viewpoint of suppressing color unevenness after light irradiation, the resin film contains the pigment together with the hindered amine light stabilizer. From the viewpoint of effectively suppressing color unevenness after light irradiation, it is preferable that the intermediate layer contains the pigment. The surface layer may or may not contain the pigment. When the resin film has multiple layers, it is preferable that the pigment and the hindered amine light stabilizer are contained in the same layer.
[0062] Whether a colorant is a dye or a pigment can be determined from the classification according to the color index.
[0063] In this specification, the terms "pigment" and "dye" may be defined as follows for colorants not listed in the Color Index. A polyvinyl butyral resin (polyvinyl alcohol polymerization degree 1700, hydroxyl group content 30 mol%, acetylation degree 1 mol%, butyralization degree 69 mol%) is prepared. 100 parts by weight of this polyvinyl butyral resin, 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO), and a colorant in an amount of 0.015 wt% based on the total weight of the polyvinyl butyral resin, 3GO, and colorant are kneaded and extruded to obtain a resin film (single layer) with a thickness of 760 μm. When a laminated glass is produced using this resin film and two clear glass sheets (2.5 mm thick) with a visible light transmittance of 90% measured in accordance with JIS R3106:1998, the colorant that gives the resulting laminated glass a haze value of 0.35% or greater is defined as a pigment. A colorant with a haze value of less than 0.35% is a dye.
[0064] The pigment may be an organic pigment or an inorganic pigment. The organic pigment may be an organic pigment having a metal atom or an organic pigment not having a metal atom. Only one type of the pigment may be used, or two or more types may be used in combination.
[0065] The organic pigments include phthalocyanine compounds, quinacrine compounds, Lydon compounds, azo compounds, pentaphene compounds, perylene compounds, indole compounds, and dioxazine compounds.
[0066] The color tone of the organic pigment is preferably yellow, orange, red, violet, blue, or green.
[0067] Examples of the inorganic pigment include carbon black, iron oxide, zinc oxide, and titanium oxide.
[0068] The resin film according to the present invention contains, as the pigment, a phthalocyanine compound, a quinacrine compound, Lydon It is preferable that the pigment contains a phthalocyanine compound, an azo compound, a pentaphene compound, a dioxazine compound, a perylene compound, an indole compound, or carbon black. It is preferable that the maximum absorption wavelength of the phthalocyanine compound is 500 nm or more and 740 nm or less. The resin film according to the present invention may contain a phthalocyanine compound as the pigment, and Lydon The compound may include a compound, a perylene compound, or an indole compound, and may also include carbon black.
[0069] The phthalocyanine compound includes phthalocyanine and phthalocyanine derivatives. The phthalocyanine compound has a phthalocyanine skeleton.
[0070] The phthalocyanine compound preferably contains a vanadium atom or a copper atom, more preferably a copper atom. The phthalocyanine compound may contain a vanadium atom. The phthalocyanine compound is more preferably a phthalocyanine containing a vanadium atom or a copper atom, or a derivative of a phthalocyanine containing a vanadium atom or a copper atom, and more preferably a phthalocyanine containing a copper atom or a derivative of a phthalocyanine containing a copper atom. From the viewpoint of further improving the heat-shielding properties of the resin film and the glass-plate-containing laminate, the phthalocyanine compound preferably has a structural unit in which an oxygen atom is bonded to a copper atom.
[0071] From the viewpoint of further suppressing color unevenness after light irradiation, the maximum absorption wavelength of the phthalocyanine compound is preferably 500 nm or more and 740 nm or less.
[0072] The above Kinaku Lydon The compound is quinacrine Lydon and Kinak Lydon Derivatives of the above quinacrine are also included. Lydon Is Kinaku Lydon It has a skeleton.
[0073] The perylene compound includes perylene and perylene derivatives. The perylene has a perylene skeleton.
[0074] The azo compound has an azo skeleton.
[0075] The pentaphene compound includes pentaphene and pentaphene derivatives. The pentaphene has a pentaphene skeleton.
[0076] The indole compound includes indole and indole derivatives. The indole has an indole skeleton.
[0077] The dioxazine compound includes dioxazine and dioxazine derivatives. The dioxazine has a dioxazine skeleton.
[0078] From the viewpoint of reducing the haze value and effectively suppressing color unevenness after light irradiation, the content of the pigment is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, even more preferably 0.03% by weight or more, preferably 0.4% by weight or less, more preferably 0.2% by weight or less, and even more preferably 0.1% by weight or less, based on 100% by weight of the resin film.
[0079] Furthermore, when the resin film is multilayered, from the viewpoints of reducing the haze value and effectively suppressing color unevenness after light irradiation, the content of the pigment in 100% by weight of the layers containing the pigment is preferably 0.001% by weight or more, more preferably 0.01% by weight or more, and even more preferably 0.03% by weight or more. When the resin film is multilayered, from the viewpoints of reducing the haze value and effectively suppressing color unevenness after light irradiation, the content of the pigment in 100% by weight of the layers containing the pigment is preferably 0.4% by weight or less, more preferably 0.2% by weight or less, and even more preferably 0.1% by weight or less.
[0080] (hindered amine light stabilizer) From the viewpoint of suppressing color unevenness and discoloration after light irradiation, the resin film contains the hindered amine light stabilizer together with the pigment. Furthermore, by using the hindered amine light stabilizer, discoloration is further suppressed even when the resin film is used for a long period of time or exposed to sunlight, and the visible light transmittance is further prevented from decreasing. From the viewpoint of effectively suppressing color unevenness after light irradiation, it is preferable that the intermediate layer contains the hindered amine light stabilizer. The surface layer contains or does not contain the hindered amine light stabilizer. The surface layer may contain the hindered amine light stabilizer, or may not contain the hindered amine light stabilizer. Only one type of hindered amine light stabilizer may be used, or two or more types may be used in combination.
[0081] Examples of the hindered amine light stabilizer include a hindered amine light stabilizer in which an alkyl group, an alkoxy group, or a hydrogen atom is bonded to a nitrogen atom of a piperidine structure. From the viewpoint of further suppressing discoloration, a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to a nitrogen atom of a piperidine structure is preferred. The hindered amine light stabilizer is preferably a hindered amine light stabilizer in which an alkyl group is bonded to a nitrogen atom of a piperidine structure, and is also preferably a hindered amine light stabilizer in which an alkoxy group is bonded to a nitrogen atom of a piperidine structure.
[0082] Examples of the hindered amine light stabilizer in which an alkyl group is 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.
[0083] Examples of the hindered amine light stabilizer in which an alkoxy group is bonded to the nitrogen atom of the piperidine structure include "TinuvinXT-850FF" and "TinuvinXT-855FF" manufactured by BASF, and "ADEKA STAB LA-81" manufactured by ADEKA.
[0084] 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.
[0085] From the viewpoint of further suppressing discoloration, the molecular weight of the light stabilizer is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 700 or less.
[0086] From the viewpoint of further suppressing discoloration, the molecular weight of the hindered amine light stabilizer is preferably 2,000 or less, more preferably 1,000 or less, and even more preferably 700 or less.
[0087] From the viewpoint of further suppressing color unevenness and discoloration after light irradiation, the content of the hindered amine light stabilizer in 100% by weight of the resin film is preferably 0.0025% by weight or more, more preferably 0.025% by weight or more, and preferably 0.5% by weight or less, more preferably 0.3% by weight or less.
[0088] Furthermore, when the resin film has multiple layers, from the viewpoint of further suppressing color unevenness and discoloration after light irradiation, the content of the hindered amine light stabilizer in 100% by weight of the layer containing the hindered amine light stabilizer is preferably 0.0025% by weight or more, more preferably 0.025% by weight or more, and preferably 0.5% by weight or less, more preferably 0.3% by weight or less.
[0089] From the viewpoint of further suppressing color unevenness and discoloration after light irradiation, when the surface layers (first surface layer and second surface layer) contain the hindered amine light stabilizer, the content of the hindered amine light stabilizer in 100% by weight of the intermediate layer is preferably higher than the content of the hindered amine light stabilizer in 100% by weight of the surface layer. From the viewpoint of further suppressing color unevenness and discoloration after light irradiation, the absolute value of the difference between the content of the hindered amine light stabilizer in 100% by weight of the intermediate layer and the content of the hindered amine light stabilizer in 100% by weight of the surface layer is preferably 0.001% by weight or more, more preferably 0.0025% by weight or more, and even more preferably 0.025% by weight or more.
[0090] (metal salts) The resin film and the surface layer preferably contain a magnesium salt, an alkali metal salt, or an alkaline earth metal salt (hereinafter, these may be collectively referred to as metal salt M). The intermediate layer may contain the metal salt M. Use of the metal salt M makes it easier to control the adhesive strength of the resin film according to the present invention to glass plates, laminated glass members, other resin films, etc. The metal salt M may be used alone or in combination of two or more.
[0091] The metal salt M preferably contains Li, Na, K, Rb, Cs, Mg, Ca, Sr, or Ba as a metal. The metal salt contained in the resin film is preferably K or Mg. In this case, both K and Mg may be contained.
[0092] Furthermore, the metal salt M is more preferably an alkali metal salt of an organic acid having 2 to 16 carbon atoms or an alkaline earth metal salt of an organic acid having 2 to 16 carbon atoms, and even more preferably a magnesium salt of a carboxylic acid having 2 to 16 carbon atoms or a potassium salt of a carboxylic acid having 2 to 16 carbon atoms.
[0093] Examples of the magnesium salts of carboxylic acids having 2 to 16 carbon atoms and the potassium salts of carboxylic acids having 2 to 16 carbon atoms include magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutyrate, potassium 2-ethylbutanoate, magnesium 2-ethylhexanoate, and potassium 2-ethylhexanoate.
[0094] The total content of Mg and K in the resin film and the total content of Mg and K in the layer (surface layer, etc.) containing Mg or K is preferably 5 ppm or more, more preferably 10 ppm or more, even more preferably 20 ppm or more, and preferably 300 ppm or less, more preferably 250 ppm or less, and even more preferably 200 ppm or less. When the total content of Mg and K is equal to or more than the above lower limit and equal to or less than the above upper limit, the adhesive strength of the resin film to a glass plate, a laminated glass member, another resin film, etc. can be more effectively controlled.
[0095] (UV screening agent) The resin film, the surface layer, and the intermediate layer preferably contain an ultraviolet ray blocking agent. By using the ultraviolet ray blocking agent, discoloration of the resin film is further suppressed even when the resin film is used for a long period of time or at high temperatures, and the visible light transmittance is further prevented from decreasing. The ultraviolet ray blocking agent may be used alone or in combination of two or more kinds.
[0096] The ultraviolet screening agent includes an ultraviolet absorbing agent, and the ultraviolet screening agent is preferably an ultraviolet absorbing agent.
[0097] Examples of the ultraviolet screening agent include metal-based ultraviolet screening agents (ultraviolet screening agents containing a metal), metal oxide-based ultraviolet screening agents (ultraviolet screening agents containing a metal oxide), benzotriazole-based ultraviolet screening agents (ultraviolet screening agents having a benzotriazole structure), benzophenone-based ultraviolet screening agents (ultraviolet screening agents having a benzophenone structure), triazine-based ultraviolet screening agents (ultraviolet screening agents having a triazine structure), malonic acid ester-based ultraviolet screening agents (ultraviolet screening agents having a malonic acid ester structure), oxalic acid anilide-based ultraviolet screening agents (ultraviolet screening agents having an oxalic acid anilide structure), and benzoate-based ultraviolet screening agents (ultraviolet screening agents having a benzoate structure).
[0098] Examples of the metal-based ultraviolet shielding agent include platinum particles, platinum particles whose surfaces are coated with silica, palladium particles, and palladium particles whose surfaces are coated with silica. The ultraviolet shielding agent is preferably not a heat-shielding particle.
[0099] The above-mentioned ultraviolet screening agent is preferably a benzotriazole-based ultraviolet screening agent, a benzophenone-based ultraviolet screening agent, a triazine-based ultraviolet screening agent, or a benzoate-based ultraviolet screening agent, more preferably a benzotriazole-based ultraviolet screening agent or a benzophenone-based ultraviolet screening agent, and even more preferably a benzotriazole-based ultraviolet screening agent.
[0100] Examples of the metal oxide ultraviolet screening agent include zinc oxide, titanium oxide, and cerium oxide. Furthermore, the surface of the metal oxide ultraviolet screening agent may be coated. Examples of the coating material for the surface of the metal oxide ultraviolet screening agent include insulating metal oxides, hydrolyzable organosilicon compounds, and silicone compounds.
[0101] Examples of the insulating metal oxide include silica, alumina, zirconia, etc. The insulating metal oxide has a band gap energy of, for example, 5.0 eV or more.
[0102] Examples of the benzotriazole-based UV screening agent include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole ("Tinuvin P" manufactured by BASF), 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole ("Tinuvin 320" manufactured by BASF), 2-(2'-hydroxy-3'-t-butyl-5-methylphenyl)-5-chlorobenzotriazole ("Tinuvin 326" manufactured by BASF), and 2-(2'-hydroxy-3',5'-di-amylphenyl)benzotriazole ("Tinuvin 328" manufactured by BASF). Because of their excellent UV absorption performance, the UV screening agent is preferably a benzotriazole-based UV screening agent containing a halogen atom, and more preferably a benzotriazole-based UV screening agent containing a chlorine atom.
[0103] Examples of the benzophenone-based ultraviolet screening agent include octabenzone ("Chimassorb 81" manufactured by BASF).
[0104] Examples of the triazine-based ultraviolet screening agent include "LA-F70" manufactured by ADEKA Corporation and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol ("Tinuvin 1577FF" manufactured by BASF).
[0105] Examples of the malonic acid ester-based ultraviolet screening agent include dimethyl 2-(p-methoxybenzylidene)malonate, tetraethyl-2,2-(1,4-phenylenedimethylidene)bismalonate, and 2-(p-methoxybenzylidene)-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)malonate.
[0106] Commercially available malonic acid ester-based ultraviolet screening agents include Hostavin B-CAP, Hostavin PR-25, and Hostavin PR-31 (all manufactured by Clariant).
[0107] Examples of the oxalic acid anilide-based ultraviolet screening agent include oxalic acid diamides having an aryl group substituted on the nitrogen atom, such as N-(2-ethylphenyl)-N'-(2-ethoxy-5-t-butylphenyl)oxalic acid diamide, N-(2-ethylphenyl)-N'-(2-ethoxy-phenyl)oxalic acid diamide, and 2-ethyl-2'-ethoxy-oxyanilide ("SanduvorVSU" manufactured by Clariant).
[0108] Examples of the benzoate-based ultraviolet screening agents include 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate ("Tinuvin 120" manufactured by BASF).
[0109] From the viewpoint of further suppressing discoloration and further suppressing a decrease in visible light transmittance, the content of the ultraviolet ray blocking agent in 100% by weight of the resin film and 100% by weight of the layer containing the ultraviolet ray blocking agent is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, even more preferably 0.3% by weight or more, and particularly preferably 0.5% by weight or more. From the viewpoint of further suppressing discoloration and further suppressing a decrease in visible light transmittance, the content of the ultraviolet ray blocking agent in 100% by weight of the resin film and 100% by weight of the layer containing the ultraviolet ray blocking agent is preferably 2.5% by weight or less, more preferably 2% by weight or less, even more preferably 1% by weight or less, and particularly preferably 0.8% by weight or less.
[0110] (antioxidant) The resin film, the surface layer, and the intermediate layer preferably contain an antioxidant. By using the antioxidant, discoloration of the resin film is further suppressed even when the resin film is used for a long period of time or at high temperatures, and the visible light transmittance is further prevented from decreasing. The antioxidant may be used alone or in combination of two or more.
[0111] Examples of the antioxidant include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. The phenol-based antioxidants are antioxidants having a phenol skeleton. The sulfur-based antioxidants are antioxidants containing sulfur atoms. The phosphorus-based antioxidants are antioxidants containing phosphorus atoms.
[0112] The antioxidant is preferably a phenol-based antioxidant or a phosphorus-based antioxidant.
[0113] Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol (BHT), butylhydroxyanisole (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, bis(3,3'-t-butylphenol)butyric acid glycol ester, and bis(3-t-butyl-4-hydroxy-5-methylbenzenepropanoate)ethylenebis(oxyethylene). One or more of these antioxidants are preferably used.
[0114] Examples of the phosphorus-based antioxidant include tridecyl phosphite, tris(tridecyl)phosphite, triphenyl phosphite, trinonylphenyl phosphite, bis(tridecyl)pentaerythritol diphosphite, bis(decyl)pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl)phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl ester phosphorous acid, and 2,2'-methylenebis(4,6-di-t-butyl-1-phenyloxy)(2-ethylhexyloxy)phosphorus, etc. One or more of these antioxidants are preferably used.
[0115] Commercially available antioxidants include, for example, "IRGANOX 245" manufactured by BASF, "IRGAFOS 168" manufactured by BASF, "IRGAFOS 38" manufactured by BASF, "Sumilizer BHT" manufactured by Sumitomo Chemical Co., Ltd., "H-BHT" manufactured by Sakai Chemical Industry Co., Ltd., "IRGANOX 1010" manufactured by BASF, and "ADEKA STAB AO-40" manufactured by ADEKA Corporation.
[0116] From the viewpoint of further suppressing discoloration and further suppressing a decrease in visible light transmittance, the content of the antioxidant is preferably 0.1 wt% or more based on 100 wt% of the resin film and 100 wt% of the layer containing the antioxidant. Furthermore, since the effect of adding the antioxidant becomes saturated, the content of the antioxidant is preferably 2 wt% or less based on 100 wt% of the resin film.
[0117] (Other ingredients) The resin film may contain, as necessary, additives such as a flame retardant, an antistatic agent, a moisture-resistant agent, a fluorescent brightener, an infrared absorber, etc. These additives may be used alone or in combination of two or more.
[0118] (Other details of the resin film) From the viewpoint of effectively improving sound insulation, it is preferable that the intermediate layer includes a layer having a glass transition temperature of 10°C or lower. The glass transition temperature of the intermediate layer is measured according to the following procedure. The resin composition for forming the intermediate layer or the intermediate layer itself is kneaded as a material and press-molded using a press molding machine to obtain a test piece with an average thickness of 0.35 mm. The obtained test piece is left for 12 hours under conditions of 25°C and a relative humidity of 30%. After leaving for 12 hours, the viscoelasticity is measured using an ARES-G2 manufactured by TA INSTRUMENTS. Parallel plates with a diameter of 8 mm are used as a jig. The measurement is performed under conditions of decreasing the temperature from 100°C to -10°C at a rate of 3°C / min, a frequency of 1 Hz, and a strain of 1%, and the peak temperature of the loss tangent in the obtained measurement result is taken as the glass transition temperature Tg (°C).
[0119] The thickness of the resin film is not particularly limited. From the viewpoint of practical use and of sufficiently enhancing the heat-shielding property, the thickness of the resin film is preferably 0.1 mm or more, more preferably 0.25 mm or more, preferably 3 mm or less, more preferably 1.5 mm or less. When the thickness of the resin film is above the lower limit, the penetration resistance of the glass plate-containing laminate is further improved. When the thickness of the resin film is below the upper limit, the transparency of the resin film is further improved.
[0120] The method for producing the resin film is not particularly limited. Conventionally known methods can be used as the method for producing the resin film. For example, a production method of kneading the compounded components and molding the resin film can be mentioned. A production method of extrusion molding is preferred because it is suitable for continuous production.
[0121] The kneading method is not particularly limited. Examples of the kneading method include a method using an extruder, a plastograph, a kneader, a Banbury mixer, a calendar roll, etc. The method using an extruder is preferred because it is suitable for continuous production, and the method using a twin-screw extruder is more preferred.
[0122] (Glass plate-containing laminate) FIG. 1 is a cross-sectional view showing an example of a glass plate-containing laminate using a thermoplastic resin film according to one embodiment of the present invention.
[0123] The glass-plate-containing laminate 1 shown in FIG. 1 includes a resin film 2, a first laminated glass member 21 (first glass plate), and a second laminated glass member 22 (which may be a second glass plate). The resin film 2 is a single-layer resin film. The resin film 2 is used to obtain a glass-plate-containing laminate. The resin film 2 is a resin film that is used by being bonded to a glass plate. The glass-plate-containing laminate 1 is laminated glass.
[0124] The resin film 2 is disposed and sandwiched between a first laminated glass member 21 and a second laminated glass member 22. The first laminated glass member 21 is laminated on a first surface 2a (one surface) of the resin film 2. The second laminated glass member 22 is laminated on a second surface 2b (the other surface) of the resin film 2 opposite the first surface 2a.
[0125] FIG. 2 is a cross-sectional view showing a modified example of a glass plate-containing laminate using a thermoplastic resin film according to one embodiment of the present invention.
[0126] The glass-plate-containing laminate 11 shown in FIG. 2 includes a resin film 12, a first laminated glass member 21 (first glass plate), and a second laminated glass member 22. The resin film 12 is a multilayer resin film. The resin film 12 is used to obtain a glass-plate-containing laminate. The resin film 12 is a resin film that is used by being bonded to a glass plate. The glass-plate-containing laminate 11 is laminated glass.
[0127] The resin film 12 has a structure in which a first layer 13 (first surface layer), a second layer 14 (intermediate layer), and a third layer 15 (second surface layer) are laminated in this order. In this embodiment, the second layer 14 is a sound-insulating layer. The first and third layers 13 and 15 are protective layers.
[0128] The resin film 12 is disposed and sandwiched between a first laminated glass member 21 and a second laminated glass member 22. The first laminated glass member 21 is laminated on the outer surface 13a of the first layer 13. The second laminated glass member 22 is laminated on the outer surface 15a of the second layer 15.
[0129] As described above, the glass plate-containing laminate of the present invention only needs to include a first glass plate and the resin film of the present invention. The resin film is preferably disposed between the first laminated glass member (first glass plate) and the second laminated glass member.
[0130] When the thermoplastic resin film according to the present invention is used as at least one layer of a multilayer film having two or more layers, the multilayer film is preferably a sound-insulating film having a sound-insulating layer in order to improve the sound insulation of the laminated glass. The multilayer film is a film containing the resin film according to the present invention. The multilayer film may have a sound-insulating layer and a protective layer. Examples of the multilayer film include a two-layer structure consisting of a sound-insulating layer and a protective layer, a three-layer structure consisting of a protective layer, a sound-insulating layer, and a protective layer, and a four-layer or more structure consisting of at least one sound-insulating layer and at least one protective layer. Figure 2 shows a multilayer film having a first layer 13, a second layer 14, and a third layer 15. In this case, the resin film according to the present invention can be used for the first layer 13, and the resin film according to the present invention can also be used for the third layer 15. For example, in Figure 2, the multilayer film may have only the first layer 13 and the second layer 14. In this case, the resin film according to the present invention can be used for the first layer 13, and the resin film according to the present invention can also be used for the second layer 14.
[0131] In the case of a multilayer film having a two-layer structure of a sound-insulating layer and a protective layer, the sound-insulating layer may be a resin film according to the present invention, the protective layer may be a resin film according to the present invention, and it is preferable that the protective layer be a resin film according to the present invention. In the case of a multilayer film having a three-layer structure of a protective layer, a sound-insulating layer, and another protective layer, the protective layer may include a resin film according to the present invention, and the sound-insulating layer may be a resin film according to the present invention. It is preferable that the protective layer be a resin film according to the present invention. In the case of a multilayer film having a four-layer or more layer structure including at least one sound-insulating layer and at least one protective layer, the sound-insulating layer may be a resin film according to the present invention, and the protective layer may be a resin film according to the present invention. It is preferable that the protective layer be a resin film according to the present invention.
[0132] In the multilayer film, the sound-insulating layer has a role of imparting sound insulation properties. The sound-insulating layer preferably contains a polyvinyl acetal resin (X) and a plasticizer.
[0133] The polyvinyl acetal resin (X) can be produced, for example, by acetalizing polyvinyl alcohol (PVA) with an aldehyde. The polyvinyl acetal resin (X) is preferably an acetalized product of polyvinyl alcohol. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate. The degree of saponification of the polyvinyl alcohol is generally within the range of 70 to 99.9 mol%.
[0134] The average degree of polymerization of the polyvinyl alcohol (PVA) used in producing the polyvinyl acetal resin (X) is preferably 200 or more, preferably 5000 or less, and more preferably 4000 or less. When the average degree of polymerization is equal to or greater than the lower limit, the penetration resistance is further improved. When the average degree of polymerization is equal to or less than the upper limit, the sound insulating layer is easily formed.
[0135] In producing the polyvinyl acetal resin (X), the number of carbon atoms in the aldehyde used to acetalize the polyvinyl alcohol is preferably 4 or more, and preferably 6 or less. When the number of carbon atoms in the aldehyde is equal to or greater than the lower limit, a sufficient amount of plasticizer can be stably incorporated, thereby achieving excellent sound insulation. In addition, bleeding out of the plasticizer can be prevented. When the number of carbon atoms in the aldehyde is equal to or less than the upper limit, the polyvinyl acetal resin (X) can be easily synthesized, ensuring productivity.
[0136] The aldehyde having 4 to 6 carbon atoms may be a linear aldehyde or a branched aldehyde. Examples of the aldehyde having 4 to 6 carbon atoms include n-butylaldehyde and n-valeraldehyde.
[0137] The hydroxyl group content of the polyvinyl acetal resin (X) is preferably 30 mol% or less, more preferably 28 mol% or less, even more preferably 26 mol% or less, and particularly preferably 24 mol% or less. When the hydroxyl group content of the polyvinyl acetal resin (X) is equal to or less than the above upper limit, it is possible to contain a plasticizer in an amount necessary to exhibit sound insulation properties and prevent the plasticizer from bleeding out. The hydroxyl group content of the polyvinyl acetal resin (X) is preferably 10 mol% or more, more preferably 15 mol% or more, and even more preferably 20 mol% or more.
[0138] The degree of acetalization of the polyvinyl acetal resin (X) is preferably 60 mol% or more, more preferably 65 mol% or more, even more preferably 68 mol% or more, and preferably 85 mol% or less. When the degree of acetalization of the polyvinyl acetal resin (X) is equal to or greater than the lower limit, the hydrophobicity of the sound-insulating layer can be increased, allowing the sound-insulating layer to contain an amount of plasticizer necessary for achieving sound-insulating properties, and preventing bleed-out and whitening of the plasticizer. When the degree of acetalization of the polyvinyl acetal resin (X) is equal to or less than the upper limit, the polyvinyl acetal resin (X) can be easily synthesized, ensuring productivity.
[0139] The degree of acetylation of the polyvinyl acetal resin (X) is preferably 0.1 mol% or more, more preferably 1 mol% or more, even more preferably 5 mol% or more, particularly preferably 8 mol% or more, preferably 30 mol% or less, more preferably 25 mol% or less, and even more preferably 20 mol% or less. When the degree of acetylation of the polyvinyl acetal resin (X) is at least the above-mentioned lower limit, it is possible to contain a plasticizer in an amount necessary to exhibit sound insulation properties, and bleed-out can be prevented. On the other hand, when the degree of acetylation of the polyvinyl acetal resin (X) is at most the above-mentioned upper limit, it is possible to increase the hydrophobicity of the sound insulation layer and prevent whitening.
[0140] In particular, since the sound-insulating layer can easily contain a plasticizer in an amount necessary for exhibiting sound-insulating properties, the polyvinyl acetal resin (X) is preferably a polyvinyl acetal resin having an acetylation degree of 8 mol% or more, or a polyvinyl acetal resin having an acetylation degree of less than 8 mol% and an acetalization degree of 65 mol% or more.More preferably, the polyvinyl acetal resin (X) is a polyvinyl acetal resin having an acetylation degree of 8 mol% or more, or a polyvinyl acetal resin having an acetylation degree of less than 8 mol% and an acetalization degree of 68 mol% or more.
[0141] The content of the plasticizer in the sound-insulating layer relative to 100 parts by weight of the polyvinyl acetal resin (X) in the sound-insulating layer is preferably at least 45 parts by weight, more preferably at least 50 parts by weight, even more preferably at least 55 parts by weight, and preferably at most 80 parts by weight, more preferably at most 75 parts by weight, and even more preferably at most 70 parts by weight. When the content of the plasticizer is at least the above-mentioned lower limit, high sound-insulating properties can be exhibited, and when it is at most the above-mentioned upper limit, bleeding out of the plasticizer is unlikely to occur, and a decrease in the transparency and adhesiveness of the multilayer film can be prevented.
[0142] The thickness of the sound-insulating layer is preferably 50 μm or more, more preferably 80 μm or more, and preferably 300 μm or less. When the thickness of the sound-insulating layer is equal to or greater than the above lower limit, sufficient sound insulation can be achieved. The thickness of the sound-insulating layer indicates an average thickness. The cross-sectional shape of the sound-insulating layer in the thickness direction may be rectangular, and the sound-insulating layer may have a wedge-shaped portion.
[0143] The sound-insulating layer may have one end and another end opposite the one end, and may have a shape in which the thickness of the other end is greater than the thickness of the one end. The sound-insulating layer preferably has a portion whose cross-sectional shape in the thickness direction is wedge-shaped. In this case, the minimum thickness of the sound-insulating layer is preferably 50 μm or more, more preferably 80 μm or more, and even more preferably 100 μm or more. When the minimum thickness of the sound-insulating layer is equal to or greater than the above-mentioned lower limit, sufficient sound insulation can be achieved. There is no particular upper limit on the maximum thickness of the sound-insulating layer. In consideration of the thickness as a multilayer film, the maximum thickness of the sound-insulating layer is preferably 300 μm or less, more preferably 200 μm or less.
[0144] The protective layer serves to prevent a decrease in the adhesion between the multilayer film and the glass plate or laminated glass member due to bleeding out of a large amount of plasticizer contained in the sound-insulating layer, and also serves to impart penetration resistance to the multilayer film. The protective layer preferably contains a polyvinyl acetal resin (Y) and a plasticizer.
[0145] The polyvinyl acetal resin (Y) can be produced, for example, by acetalizing polyvinyl alcohol (PVA) with an aldehyde. The polyvinyl acetal resin (Y) is preferably an acetalized product of polyvinyl alcohol. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate. The degree of saponification of the polyvinyl alcohol is generally within the range of 70 to 99.9 mol%.
[0146] The average degree of polymerization of the polyvinyl alcohol (PVA) used in producing the polyvinyl acetal resin (Y) is preferably 200 or more, preferably 5000 or less, more preferably 4000 or less. When the average degree of polymerization is equal to or greater than the lower limit, the penetration resistance of the glass plate-containing laminate is further improved. When the average degree of polymerization is equal to or less than the upper limit, the protective layer is easily formed.
[0147] In producing the polyvinyl acetal resin (Y), the carbon number of the aldehyde used to acetalize the polyvinyl alcohol is preferably 3 or more, and preferably 4 or less. When the carbon number of the aldehyde is equal to or more than the lower limit, the penetration resistance of the multilayer film is improved. When the carbon number of the aldehyde is equal to or less than the upper limit, the productivity of the polyvinyl acetal resin (Y) is improved.
[0148] The aldehyde having 3 to 4 carbon atoms may be a linear aldehyde or a branched aldehyde. Examples of the aldehyde having 3 to 4 carbon atoms include n-butyl aldehyde.
[0149] The hydroxyl group content of the polyvinyl acetal resin (Y) is preferably 33 mol% or less, and preferably 28 mol% or more. When the hydroxyl group content of the polyvinyl acetal resin (Y) is the upper limit or less, whitening of the multilayer film can be prevented. When the hydroxyl group content of the polyvinyl acetal resin (Y) is the lower limit or more, the penetration resistance of the multilayer film is increased.
[0150] The degree of acetalization of the polyvinyl acetal resin (Y) is preferably 60 mol% or more, more preferably 65 mol% or more, and preferably 80 mol% or less, more preferably 69 mol% or less. When the degree of acetalization of the polyvinyl acetal resin (Y) is equal to or greater than the lower limit, a plasticizer can be contained in an amount necessary to exhibit sufficient penetration resistance. When the degree of acetalization of the polyvinyl acetal resin (Y) is equal to or less than the upper limit, the adhesive strength between the protective layer and the glass plate or laminated glass member can be ensured.
[0151] The degree of acetylation of the polyvinyl acetal resin (Y) is preferably 0.1 mol% or more, more preferably 2 mol% or more, and preferably 7 mol% or less. When the degree of acetylation of the polyvinyl acetal resin (Y) is equal to or less than the upper limit, the hydrophobicity of the protective layer can be increased, and whitening can be prevented.
[0152] The content of the plasticizer in the protective layer is preferably 20 parts by weight or more, more preferably 30 parts by weight or more, even more preferably 35 parts by weight or more, and preferably 45 parts by weight or less, more preferably 43 parts by weight or less, relative to 100 parts by weight of the polyvinyl acetal resin (Y) in the protective layer. When the content of the plasticizer is equal to or more than the lower limit, penetration resistance can be ensured, and when it is equal to or less than the upper limit, bleeding out of the plasticizer can be prevented, thereby preventing a decrease in the transparency and adhesiveness of the multilayer film.
[0153] Since the sound insulation of the glass plate-containing laminate is further improved, the hydroxyl group content of the polyvinyl acetal resin (Y) is preferably larger than the hydroxyl group content of the polyvinyl acetal resin (X), more preferably by 1 mol % or more, even more preferably by 5 mol % or more, and particularly preferably by 8 mol % or more. By adjusting the hydroxyl group contents of the polyvinyl acetal resin (X) and the polyvinyl acetal resin (Y), the content of plasticizer in the sound insulation layer and the protective layer can be controlled, and the glass transition temperature of the sound insulation layer can be lowered. As a result, the sound insulation of the glass plate-containing laminate is further improved.
[0154] The content of the plasticizer in the sound-insulating layer relative to 100 parts by weight of the polyvinyl acetal resin (X) in the sound-insulating layer is defined as the content (X). The content of the plasticizer in the protective layer relative to 100 parts by weight of the polyvinyl acetal resin (Y) in the protective layer is defined as the content (Y). Since the sound-insulating properties of the glass-plate-containing laminate are further improved, the content (X) is preferably larger than the content (Y), more preferably 5 parts by weight or more, even more preferably 15 parts by weight or more, and particularly preferably 20 parts by weight or more. By adjusting the content (X) and the content (Y), the glass transition temperature of the sound-insulating layer is lowered. As a result, the sound-insulating properties of the glass-plate-containing laminate are further improved.
[0155] The thickness of the protective layer is not particularly limited as long as it can fulfill its role as a protective layer. However, if the protective layer has irregularities, it is preferable to make the protective layer as thick as possible so as to prevent the irregularities from being transferred to the interface with the sound-insulating layer that directly contacts it. Specifically, the thickness of the protective layer is preferably 100 μm or more, more preferably 300 μm or more, even more preferably 400 μm or more, and particularly preferably 450 μm or more. The thickness of the protective layer is not particularly limited, but in order to ensure that the sound-insulating layer is thick enough to achieve sufficient sound insulation, it is substantially about 500 μm or less. The thickness of the protective layer indicates the average thickness. The cross-sectional shape of the protective layer in the thickness direction may be rectangular, and the protective layer may have a wedge-shaped portion.
[0156] The protective layer may have one end and another end opposite the one end, and the thickness of the other end may be greater than the thickness of the one end. The protective layer preferably has a portion having a wedge-shaped cross section in the thickness direction. The minimum thickness of the protective layer is not particularly limited, as long as it is adjusted within a range that allows the protective layer to fulfill its role. However, if the protective layer has irregularities, it is preferable that the minimum thickness of the protective layer be as thick as possible to prevent the irregularities from being transferred to the interface with the sound-insulating layer that directly contacts it. Specifically, the minimum thickness of the protective layer is preferably 100 μm or more, more preferably 300 μm or more, even more preferably 400 μm or more, and particularly preferably 450 μm or more. The upper limit of the maximum thickness of the protective layer is not particularly limited. To ensure a protective layer thick enough to achieve sufficient sound insulation, the maximum thickness of the protective layer is preferably 1000 μm or less, more preferably 800 μm or less.
[0157] The thermoplastic resin film of the present invention may have one end and another end opposite the one end. The one end and the other end are opposite ends of the resin film. When the thermoplastic resin film of the present invention is used as an interlayer film for laminated glass, the resulting laminated glass can be suitably used as a head-up display. Therefore, in the thermoplastic resin film of the present invention, the thickness of the other end is preferably greater than the thickness of the one end. The thermoplastic resin film of the present invention may have a wedge-shaped cross-section. A film including the thermoplastic resin film of the present invention may have a wedge-shaped cross-section. If the thermoplastic resin film has a wedge-shaped cross-section, when used as an interlayer film for laminated glass, adjusting the wedge angle θ of the wedge shape according to the installation angle of the laminated glass enables image display in a head-up display without causing double images. From the viewpoint of further suppressing double images, the wedge angle θ is preferably 0.1 mrad or more, more preferably 0.2 mrad or more, even more preferably 0.3 mrad or more, and preferably 1 mrad or less, more preferably 0.9 mrad or less. For example, when a thermoplastic resin film having a wedge-shaped cross section is produced by extrusion molding a resin composition using an extruder, the shape of the resin film or multilayer film may have a minimum thickness in a region slightly inward from one end of the thin side and a maximum thickness in a region slightly inward from one end of the thick side. In this specification, such a shape is also included in the wedge shape. Specifically, the region slightly inward from one end of the thin side is, for example, a region extending from one end of the thin side to a distance of 0X to 0.2X inward from the end of the thin side, where X is the distance between the end and the other end. Specifically, the region slightly inward from one end of the thick side is, for example, a region extending from one end of the thick side to a distance of 0X to 0.2X inward from the end of the thick side, where X is the distance between the end and the other end.
[0158] When the thermoplastic resin film of the present invention has a wedge-shaped cross section, the thermoplastic resin film can be used to form a multilayer film including a sound-insulating layer and a protective layer. By setting the thickness of the sound-insulating layer within a certain range and laminating the protective layer, the cross-sectional shape of the entire multilayer film can be adjusted to a wedge shape with a certain wedge angle.
[0159] Examples of the laminated glass member include glass plates and PET (polyethylene terephthalate) films. Laminated glass includes not only laminated glass in which a resin film is sandwiched between two glass plates, but also laminated glass in which a resin film is sandwiched between a glass plate and a PET film or the like. Laminated glass is a laminate including glass plates, and preferably contains at least one glass plate. The second laminated glass member is preferably a glass plate or a PET film.
[0160] The glass plate includes inorganic glass and organic glass. The inorganic glass includes float glass, heat-absorbing glass, heat-reflecting glass, polished glass, patterned glass, and lined glass. The organic glass is a synthetic resin glass that replaces inorganic glass. The organic glass includes polycarbonate plates and poly(meth)acrylic resin plates. The poly(meth)acrylic resin plates include polymethyl(meth)acrylate plates.
[0161] The thickness of the laminated glass member is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. The thickness of the glass plate is preferably 1 mm or more, preferably 5 mm or less, more preferably 3 mm or less. When the laminated glass member is a PET film, the thickness of the PET film is preferably 0.03 mm or more, preferably 0.5 mm or less.
[0162] The method for producing the glass-plate-containing laminate is not particularly limited. The glass-plate-containing laminate can be obtained by laminating the resin film to the first glass plate. Furthermore, for example, the resin film is sandwiched between the first laminated glass member and the second laminated glass member, and the members are passed through a pressure roll, or placed in a rubber bag and subjected to reduced pressure suction to remove any air remaining between the first laminated glass member and the resin film and between the second laminated glass member and the resin film. This is followed by pre-bonding at approximately 70 to 110°C to obtain a laminate. The laminate is then placed in an autoclave or pressed at approximately 120 to 150°C and a pressure of 1 to 1.5 MPa to bond the laminate. In this way, a laminated glass, which is a glass-plate-containing laminate, can be obtained.
[0163] The resin film and the glass-plate-containing laminate can be used for automobiles, railway vehicles, aircraft, ships, buildings, etc. The resin film and the glass-plate-containing laminate can also be used for applications other than these. The resin film and the glass-plate-containing laminate are preferably resin films and glass-plate-containing laminates for vehicles or buildings, more preferably resin films and glass-plate-containing laminates for vehicles. The resin film and the glass-plate-containing laminate can be used for automobile windshields, side windows, rear windows, roof windows, etc. The glass-plate-containing laminate according to the present invention may be automobile side windows, automobile rear windows, or automobile roof windows.
[0164] From the viewpoint of enhancing the transparency of the glass plate-containing laminate, when a glass plate-containing laminate is obtained by sandwiching a thermoplastic resin film between two sheets of green glass having a thickness of 2 mm in accordance with JIS R3208, the haze value of the obtained glass plate-containing laminate is preferably 5% or less, more preferably 3% or less, and even more preferably 1.2% or less.
[0165] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
[0166] Example , reference exampleIn the comparative examples, the following materials were used.
[0167] (Polyvinyl cetal resin) Polyvinyl butyral resin (PVB (1)) (degree of polymerization of polyvinyl alcohol: 1700, hydroxyl group content: 30 mol%, acetylation degree: 1 mol%, acetalization degree (butyralization degree): 69 mol%) Polyvinyl butyral resin (PVB (2)) (degree of polymerization of polyvinyl alcohol: 3000, hydroxyl group content: 23 mol%, acetylation degree: 12 mol%, acetalization degree (butyralization degree): 65 mol%)
[0168] For polyvinyl butyral (PVB) resin, the butyralization degree (acetalization degree), acetylation degree, and hydroxyl group content were measured according to JIS K6728 "Testing methods for polyvinyl butyral." Note that when measured according to ASTM D1396-92, the values were similar to those obtained by the method according to JIS K6728 "Testing methods for polyvinyl butyral."
[0169] (plasticizer) Triethylene glycol di-2-ethylhexanoate (3GO)
[0170] (pigment) Carbon black pigment (CAS No. 1333-86-4) Copper phthalocyanine pigment (1) (CAS No. 147-14-8) (maximum absorption wavelength 600 nm) Copper phthalocyanine pigment (2) (CAS No. 1328-53-6) (maximum absorption wavelength 640 nm) Kinaku Lydon Pigment (CAS No. 3089-17-6) Perylene pigment (CAS No. 4948-15-6) Indole pigment (CAS No. 5590-18-1)
[0171] Maximum absorption wavelength measurement method: A chloroform solution was obtained by mixing 0.002 parts by weight of pigment with 100 parts by weight of chloroform. The obtained chloroform solution was placed in a quartz cell for a spectrophotometer with an optical path length of 1.0 mm. The transmittance from 300 to 2500 nm was measured using a recording spectrophotometer (Hitachi, Ltd., "U4100") to determine the maximum absorption wavelength. The maximum absorption wavelength refers to the wavelength at which the transmittance shows a minimum value and the wavelength at which this minimum value is the smallest, i.e., the maximum absorption wavelength.
[0172] (dye) Anthraquinone dye (1) (CAS No. 81-42-5) (hindered amine light stabilizer) Tinuvin 765 (BASF, NC (alkyl group) type) Tinuvin 770 (BASF, NH (hydrogen group) type) Tinuvin 123 (BASF, NOR (alkoxy group) type)
[0173] (metal salts) Mixture (1) (Mixture of magnesium acetate and magnesium 2-ethylbutyrate)
[0174] (UV screening agent) Tinuvin 326 (BASF)
[0175] (antioxidant) BHT (2,6-di-t-butyl-p-cresol) IRGANOX 1010 (BASF, antioxidant containing a phenolic skeleton) ADK STAB AO-40 (manufactured by ADEKA Corporation, antioxidant containing a phenolic structure) ("AO-40" in the table)
[0176] ( reference Example 1) Preparation of composition X for forming the first and third resin layers: To 100 parts by weight of PVB (1), 40 parts by weight of 3GO was added, and further, Tinuvin 765, Tinuvin 326, BHT, and mixture (1) were added so that the contents in the entire resin film (all layers) obtained were as shown in Table 1 below, and the mixture was thoroughly kneaded with a mixing roll to obtain composition X.
[0177] Preparation of composition Y for forming intermediate layer: 3GO and carbon black pigment were added to PVB (1) in the amounts shown in Table 1 below, and the mixture was thoroughly kneaded with a mixing roll to obtain composition Y.
[0178] Preparation of resin film: Composition X for forming the first and third resin layers and composition Y for forming the intermediate layer were co-extruded using a co-extruder to produce a resin film (760 μm thick, 100 cm wide) having a laminated structure of first resin layer / intermediate layer / third resin layer. The cross-sectional shape of the resin film was wedge-shaped, the thickness decreasing from one end to the other, and the intermediate layer, 20 cm long in the width direction, was embedded between the first and third resin layers, and the maximum thickness of the intermediate layer was 380 μm.
[0179] Laminated glass production: The resulting resin film was cut into a 15 cm x 15 cm piece. The cutout was performed so that the thickest part of the interlayer was located at the edge of the resulting laminated glass, and the thickness of the interlayer decreased from the edge to the opposite edge. The resin film was then sandwiched between two 2 mm thick green glass sheets (15 cm x 15 cm x 2 mm, visible light transmittance 85%) conforming to JIS R3208, held at 90°C for 30 minutes in a vacuum laminator, and vacuum pressed to obtain a laminated glass.
[0180] ( reference Example 2 9. Examples 10- 13 and Comparative Example 1) The types and amounts of the ingredients in the composition were set as shown in Tables 1 and 2 below. reference In the same manner as in Example 1, a resin film and a laminated glass were obtained.
[0181] ( reference Example 14) Preparation of composition X for forming the first, third, and fifth resin layers: To 100 parts by weight of PVB (1), 40 parts by weight of 3GO was added, and further, Tinuvin 765, Tinuvin 326, BHT, and mixture (1) were added so that the contents in the entire resin film (all layers) obtained were as shown in Table 3 below, and the mixture was thoroughly kneaded with a mixing roll to obtain composition X.
[0182] Preparation of composition Y for forming intermediate layer: 3GO and carbon black pigment were added to PVB (1) in the amounts shown in Table 3 below, and the mixture was thoroughly kneaded with a mixing roll to obtain composition Y.
[0183] Preparation of composition Z for forming a sound insulation layer: 3GO was added to PVB (2) in the amount shown in Table 3 below, and the mixture was thoroughly kneaded with a mixing roll to obtain composition Z.
[0184] Preparation of resin film: Composition X for forming the first, third, and fifth resin layers, composition Y for forming the intermediate layer, and composition Z for forming the sound-insulating layer were co-extruded using a co-extruder to produce a resin film (760 μm thick, 100 cm wide) having a laminated structure of first resin layer / intermediate layer / third resin layer / sound-insulating layer / fifth resin layer. The cross-sectional shape of the resin film was wedge-shaped, the thickness decreasing from one end to the other, and the intermediate layer, 20 cm long in the width direction, was embedded between the first and third resin layers and had a maximum thickness of 160 μm. Furthermore, the cross-sectional shape of the sound-insulating layer was rectangular and had a thickness of 100 μm, and the cross-sectional shape of the fifth resin layer was rectangular and had a thickness of 160 μm.
[0185] Laminated glass production: referenceA laminated glass was produced in the same manner as in Example 1.
[0186] ( reference Example 15 22. Examples 23- 26 and Comparative Example 2) The types and amounts of the ingredients in the composition were set as shown in Tables 3 and 4 below. reference In the same manner as in Example 1, a resin film and a laminated glass were obtained.
[0187] ( reference Example 27) Preparation of composition X for forming the first and third resin layers: To 100 parts by weight of PVB (1), 40 parts by weight of 3GO was added, and further, Tinuvin 765, Tinuvin 326, BHT, and mixture (1) were added so that the contents in the entire resin film (all layers) were as shown in Table 5. Furthermore, carbon black pigment was added to the first and third resin layers so that the contents were as shown in Table 5, and the mixture was thoroughly kneaded with a mixing roll to obtain composition X.
[0188] Preparation of composition Y for forming a sound insulation layer: 3GO was added to PVB (2) in the amount shown in Table 5 below, and the mixture was thoroughly kneaded with a mixing roll to obtain composition Y.
[0189] Preparation of resin film: Composition X for forming the first and third resin layers and composition Y for forming the sound-insulating layer (intermediate layer) were co-extruded using a co-extruder to produce a resin film (thickness 800 μm, width 100 cm) having a laminated structure of first resin layer / sound-insulating layer / third resin layer. The first resin layer, sound-insulating layer, and third resin layer all had rectangular cross-sectional shapes. The thicknesses of the first resin layer and third resin layer were 350 μm, and the sound-insulating layer was 100 μm.
[0190] Laminated glass production: The resulting resin film was cut into a size of 15 cm long x 15 cm wide. Next, the resin film was sandwiched between two 2 mm thick green glass sheets conforming to JIS R3208 (15 cm long x 15 cm wide x 2 mm thick, visible light transmittance 85%), held at 90°C for 30 minutes in a vacuum laminator, and vacuum pressed to obtain laminated glass.
[0191] (Reference example 28 ~4 0 and Comparative Example 3) Resin films and laminated glasses were obtained in the same manner as in Reference Example 27, except that the types and amounts of the components of the compositions were set as shown in Tables 5 and 6 below.
[0192] (evaluation) (1) Haze measurement The haze value of the obtained laminated glass was measured using a haze meter ("TC-HIIIDPK" manufactured by Tokyo Denshoku Co., Ltd.) in accordance with JIS K6714. reference Example 1 9, Examples 10 to 13, Reference Examples 14 to 22, Examples 23 to For the laminated glasses obtained in No. 26 and Comparative Examples 1 and 2, the haze value was measured at the thickest part of the interlayer of the obtained laminated glass.
[0193] (2) Total light transmittance The total luminous transmittance (TvD) of the thickest part of the interlayer of the obtained laminated glass was measured in accordance with JIS R3106:1998. Using a spectrophotometer (Hitachi High-Tech Corporation's "U-4100"), the obtained laminated glass was placed parallel to and in close contact with the opening of an integrating sphere so that all transmitted light was received by the integrating sphere, and the spectral transmittance was measured. The visible light transmittance calculated from the obtained spectral transmittance was taken as the total luminous transmittance. reference Example 1 9, Examples 10 to 13, Reference Examples 14 to 22, Examples 23 to For the laminated glasses obtained in No. 26 and Comparative Examples 1 and 2, the total light transmittance was measured at the thickest part of the interlayer of the obtained laminated glass.
[0194] (3) Evaluation of color unevenness after light exposure Reference example 27 ~4For the laminated glass obtained in Comparative Example 0 and Comparative Example 3, measuring 15 cm in length and 15 cm in width, one side of the laminated glass was set to face the light source, and the laminated glass was set at a distance of 230 mm from the light source. Furthermore, the laminated glass was set so that two of the four sides were exposed to light, and the remaining two sides were hidden from light by a fixing frame. Using "H75" manufactured by Suga Testing Instruments, the black panel temperature was 50°C, and the irradiation intensity was 70 W / m 2 The light was set to a wavelength of 300 to 400 nm, and the black panel temperature was 50°C. The light was irradiated for 1000 hours. Color unevenness was evaluated by visual observation according to the following criteria. Figure 3 shows laminated glass that exhibited color unevenness.
[0195] In addition, reference Example 1 9, Examples 10 to 13, Reference Examples 14 to 22, Examples 23 to For the laminated glass obtained in No. 26 and Comparative Examples 1 and 2, the color tone differs between the side with the thick intermediate layer and the side with the thin intermediate layer due to differences in the thickness of the thermoplastic resin film intermediate layer. Therefore, the side with the thick intermediate layer was not compared with the side with the thin intermediate layer, but rather one of the other two sides was placed so that it was exposed to light and the other side was hidden from light by a fixed frame, and the change in color tone and color unevenness were compared.
[0196] [Criteria for determining color unevenness after exposure to light] ○: The color tone is the same on the two edges exposed to light and in the area 5 mm to 25 mm from the inner edge of the edges, and no color unevenness occurs. ×: The color tone differs between the two edges exposed to light and the area 5 mm to 25 mm from the inner edge of the edges, resulting in color unevenness.
[0197] (4) Discoloration after exposure to light Furthermore, the change in color tone of the laminated glass before and after light irradiation was measured in terms of color difference ΔE before and after storage in accordance with JIS K 8781-4:2013 using a spectrophotometer (Hitachi High-Tech Corporation's "U-4100"). The measurement was performed at the center of the laminated glass. Discoloration was evaluated based on the color difference ΔE according to the following criteria.
[0198] [Criteria for determining color unevenness after exposure to light] ○: ΔE is 3 or less △: ΔE is greater than 3 and less than 10 ×: ΔE exceeds 10
[0199] Details and results are shown in Tables 1 to 6 below. In Tables 1 to 6 below, the content of plasticizer in each layer indicates the content relative to 100 parts by weight of the polyvinyl acetal resin in each layer. In Tables 1 to 6 below, the contents of pigment, dye, hindered amine light stabilizer, UV screening agent, and antioxidant indicate the content in 100% by weight of each layer. In Tables 1 to 6 below, the total content (ppm) of Mg and K indicates the concentration in each layer.
[0200] (5) Identification of pigments After subjecting thermoplastic resin films to supercritical extraction using carbon dioxide or Soxhlet extraction using organic solvents, the extracted thermoplastic resin films were analyzed using pyrolysis GC, MALDI-TOF-MS, TOF-SIMS, LC-MS, GC-MS, TEM-EDS, and NMR. In addition, the thermoplastic resin films after Soxhlet extraction were dissolved in solvent and the thermoplastic resin was extracted using methods such as reprecipitation. The solvent used for precipitation was then evaporated, and the resulting colored components were identified using XRD, NMR, MALDI-TOF-MS, TOF-SIMS, LC-MS, GC-MS, IR, and UV-Vis spectroscopy. When multiple pigments were present, they were separated using HPLC or GPC. After identification, quantitative analysis was performed using calibration curves created using HPLC peak areas or UV-Vis spectroscopy.
[0201] [Table 1]
[0202] [Table 2]
[0203] [Table 3]
[0204] [Table 4]
[0205] [Table 5]
[0206] [Table 6] [Explanation of symbols]
[0207] 1...Glass plate-containing laminate (laminated glass) 2...Resin film 2a...First surface 2b...Second surface 11...Glass plate-containing laminate (laminated glass) 12...Resin film 13...First layer (first surface layer) 14...Second layer (middle layer) 15...Third layer (second surface layer) 13a...Outer surface 15a...outer surface 21...First laminated glass member (first glass plate) 22...Second laminated glass member
Claims
1. a first surface layer; and a second surface layer; and a thermoplastic resin film including an intermediate layer disposed between the first surface layer and the second surface layer; the thermoplastic resin film contains a thermoplastic resin, a pigment, and a hindered amine light stabilizer; the thermoplastic resin film contains a quinacridone compound, a perylene compound, or an indole compound as the pigment, the intermediate layer contains the pigment, the first surface layer and the second surface layer do not contain a pigment, a thermoplastic resin film, wherein the first surface layer and the second surface layer contain the hindered amine light stabilizer;
2. The thermoplastic resin film according to claim 1 , wherein the thermoplastic resin is a polyvinyl acetal resin or an ionomer resin.
3. The thermoplastic resin film according to claim 1 or 2, which contains a plasticizer.
4. The thermoplastic resin film according to any one of claims 1 to 3, wherein the pigment comprises a phthalocyanine compound.
5. The thermoplastic resin film according to claim 4, wherein the phthalocyanine compound has a maximum absorption wavelength of 500 nm or more and 740 nm or less.
6. The thermoplastic resin film according to any one of claims 1 to 5, wherein when a glass plate-containing laminate is obtained by sandwiching the thermoplastic resin film between two sheets of green glass having a thickness of 2 mm in accordance with JIS R3208, the haze value of the obtained glass plate-containing laminate is 5% or less.
7. The thermoplastic resin film according to any one of claims 1 to 6, wherein the hindered amine light stabilizer is a hindered amine light stabilizer in which an alkyl group or an alkoxy group is bonded to a nitrogen atom of a piperidine structure.
8. The thermoplastic resin film according to any one of claims 1 to 7, which is a thermoplastic resin film that is used by being stuck to a glass plate.
9. a first glass plate; The thermoplastic resin film according to any one of claims 1 to 8, A glass plate-containing laminate, in which the thermoplastic resin film is bonded to the first glass plate.
10. the first glass plate as a first laminated glass member; the thermoplastic resin film; a second laminated glass member; the thermoplastic resin film is bonded to the first glass plate, the thermoplastic resin film is bonded to the second laminated glass member; The glass-plate-containing laminate according to claim 9 , wherein the thermoplastic resin film is disposed between the first glass plate and the second laminated glass member.
11. The glass-plate-containing laminate according to claim 9 or 10, which is a side glass for an automobile.
12. The glass-plate-containing laminate according to claim 9 or 10, which is a rear glass for an automobile.
13. The glass-plate-containing laminate according to claim 9 or 10, which is an automobile roof glass.
Citation Information
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