JP2011042552A - Interlayer film for laminated glass and laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an interlayer film for laminated glass which obtains laminated glass having excellent heat sealdability, and also maintains the excellent heat insulating property of the laminated glass over a long period. <P>SOLUTION: The interlayer film 1 for laminated glass is provided with: a first layer 2; and a second layer 3 laminated on either side 2a of the first layer 2. The second layer 3 includes a polyvinyl acetate resin and a plasticizer. The first layer 2 includes a thermoplastic resin and at least one selected from an immonium compound and an aluminum compound. In the thermoplastic resin comprised in the first layer 2, the content of a hydroxy group is ≤25 mol%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an interlayer film for laminated glass having excellent heat shielding properties, and more specifically, an interlayer film for laminated glass capable of obtaining a laminated glass satisfying performance requirements of cool car regulations in the United States, and the interlayer for laminated glass The present invention relates to a laminated glass using a film.

  Laminated glass is excellent in safety because it has less scattering of glass fragments even if it is damaged by external impact. For this reason, the said laminated glass is widely used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc. The laminated glass is manufactured by sandwiching an interlayer film for laminated glass between a pair of glass plates.

  Infrared rays having a wavelength longer than that of visible light having a wavelength of 780 nm or more have a smaller energy amount than ultraviolet rays. However, infrared rays have a large thermal effect, and once infrared rays are absorbed by a substance, they are released as heat. For this reason, infrared rays are generally called heat rays.

  In order to effectively block the infrared rays (heat rays), Patent Document 1 listed below includes a heat-shielding particle such as tin-doped indium oxide particles (ITO particles) or antimony-doped tin oxide particles (ATO particles). An interlayer film for glass is disclosed.

  However, even with the laminated glass using the interlayer film for laminated glass described in Patent Document 1, the heat shielding property may not be sufficiently high.

WO01 / 25162

  In recent years, in the United States, the California Air Resources Board (CARB) has proposed reducing the amount of carbon dioxide emitted from automobiles in order to reduce greenhouse gases. In order to reduce the amount of carbon dioxide emitted from automobiles, the CARB regulates the heat energy that passes through the laminated glass and flows into the automobile, reducing the fuel consumed by the air conditioner and reducing the fuel consumption of the automobile. We are considering improvement. Specifically, the CARB plans to introduce Cool Car Regulations (Cool Cars Standards).

  Specifically, in the above-mentioned cool car regulation, in 2012, Tts (Total Solar Transmission) of laminated glass used in automobiles is required to be 50% or less. In 2016, the Tts of the laminated glass is required to be 40% or less.

  Further, the laminated glass is required not only to have the Tts of 50% or less, but also to have a visible light transmittance of 70% or more. That is, it is required to reduce the Tts while keeping the visible light transmittance high.

  When an interlayer film for laminated glass containing thermal barrier particles as described in Patent Document 1 is used, it is extremely difficult to obtain laminated glass satisfying both Tts of 50% or less and visible light transmittance of 70% or more. is there.

  An object of the present invention is to use a laminated glass interlayer film capable of obtaining a laminated glass excellent in heat shielding properties and capable of maintaining the superior heat shielding properties of the laminated glass over a long period of time, and the laminated glass interlayer film. It is to provide laminated glass.

  A limited object of the present invention is to provide an interlayer film for laminated glass capable of obtaining a laminated glass having a low Tts and a high visible light transmittance, which is a required performance in the cool car regulations in the United States, and the interlayer film for laminated glass It is providing the laminated glass using this.

  According to the present invention, a first layer and a second layer laminated on one surface of the first layer are provided, and the second layer contains a polyvinyl acetal resin and a plasticizer. The first layer contains a thermoplastic resin and at least one of an immonium compound and an aminium compound, and the thermoplastic resin contained in the first layer has a hydroxyl group content rate. An interlayer film for laminated glass is provided in which is a thermoplastic resin of 25 mol% or less.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the thermoplastic resin having a hydroxyl group content of 25 mol% or less contained in the first layer is a polyvinyl acetal resin or (meth) acrylic. Resin, ethylene-vinyl acetate copolymer resin or ionomer resin.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the thermoplastic resin having a hydroxyl group content of 25 mol% or less contained in the first layer is a polyvinyl acetal resin.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the thermoplastic resin having a hydroxyl group content of 25 mol% or less contained in the first layer is a (meth) acrylic resin. .

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the (meth) acrylic resin has a carboxyl group.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, at least one of the first layer and the second layer further contains metal oxide particles.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the metal oxide particles are tin-doped indium oxide particles.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, a third layer laminated on the other surface of the first layer is further provided, and the third layer is a polyvinyl acetal. Contains a resin and a plasticizer.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, at least one of the first layer, the second layer, and the third layer further includes an ultraviolet absorber. contains.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, at least one of the first layer, the second layer, and the third layer further contains an antioxidant. To do.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, at least one of the first layer, the second layer, and the third layer further includes a light stabilizer. contains.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the first layer further contains a chelating agent.

  The laminated glass according to the present invention comprises first and second laminated glass constituent members and an intermediate film sandwiched between the first and second laminated glass constituent members, and the intermediate film comprises: 1 is an interlayer film for laminated glass constructed according to the present invention.

  The interlayer film for laminated glass according to the present invention has a multilayer structure in which the first and second layers are laminated, and the first layer includes at least one of a thermoplastic resin, an immonium compound, and an aminium compound. Since the thermoplastic resin contained in the first layer is a thermoplastic resin having a hydroxyl group content of 25 mol% or less, it is possible to obtain a laminated glass excellent in heat shielding properties. it can. Furthermore, the excellent heat shielding property of the obtained laminated glass can be maintained over a long period of time.

FIG. 1 is a partially cutaway cross-sectional view schematically showing an interlayer film for laminated glass according to an embodiment of the present invention. FIG. 2 is a partially cutaway sectional view showing an example of laminated glass using the interlayer film for laminated glass shown in FIG.

  Details of the present invention will be described below.

(Interlayer film for laminated glass)
In FIG. 1, the intermediate film for laminated glasses which concerns on one Embodiment of this invention is typically shown with partial notch sectional drawing.

  The intermediate film 1 shown in FIG. 1 is laminated on the first layer 2, the second layer 3 laminated on one surface 2 a of the first layer 2, and the other surface 2 b of the first layer 2. And a third layer 4. The intermediate film 1 is used to obtain a laminated glass. The intermediate film 1 is an intermediate film for laminated glass.

  The second layer 3 and the third layer 4 include a polyvinyl acetal resin and a plasticizer. Since the second layer 3 includes a polyvinyl acetal resin and a plasticizer, the adhesive force of the outer surface 3a of the second layer 3 is high. Since the third layer 4 includes a polyvinyl acetal resin and a plasticizer, the adhesion force of the outer surface 4a of the third layer 4 is high.

  The first layer 2 contains a thermoplastic resin, metal oxide particles 5, and at least one of an immonium compound and an aminium compound. The thermoplastic resin contained in the first layer 2 is a thermoplastic resin having a hydroxyl group content of 25 mol% or less.

  The main feature of this embodiment is that the first layer 2 contains a thermoplastic resin and at least one of an immonium compound and an aminium compound, and further uses the specific thermoplastic resin. It is in.

  Furthermore, since the metal oxide particles 5 and at least one of the immonium compound and the aminium compound are used in combination by using the metal oxide particles 5, the heat shielding property of the interlayer film for laminated glass or the laminated glass is further enhanced. be able to. In addition, a laminated glass having a sufficiently low Tts (Total Solar Transmission) and a sufficiently high visible light transmittance (Visible Transmittance) can be obtained.

  The use of the interlayer film for laminated glass according to the present invention, for example, to meet the required performance of cool car regulations (Cool Cars Standards) scheduled to be introduced by the California Air Resources Board (CARB (California Air Resources Board)) Glass can be obtained. Specifically, the Tts of the laminated glass can be 50% or less. Furthermore, the visible light transmittance of the laminated glass can be 70% or more.

  Conventionally, when an interlayer film for laminated glass containing heat shielding particles such as ITO particles is used, it is possible to obtain a laminated glass satisfying both the Tts of 50% or less and the visible light transmittance of 70% or more. It was extremely difficult. However, by using the interlayer film for laminated glass according to the present invention, it is possible to obtain a laminated glass satisfying both the Tts of 50% or less and the visible light transmittance of 70% or more. Therefore, it can meet the cool car regulations in the United States.

  In the present specification, the Tts and the visible light transmittance are required by the cool car regulation. The Tts is measured by, for example, a measurement method determined by cool car regulations. The visible light transmittance is measured in accordance with, for example, JIS R3211 (1998).

  Furthermore, the polyvinyl acetal resin generally has many hydroxyl groups in one molecule. When a polyvinyl acetal resin having a high hydroxyl group content and at least one of an immonium compound and an aminium compound are used in combination, the immonium compound and the aminium compound are deteriorated by the hydroxyl group. For this reason, the heat-shielding property of the interlayer film for laminated glass or laminated glass is lowered.

  However, in the present embodiment, since a thermoplastic resin having a hydroxyl group content of 25 mol% or less is used, the immonium compound and the aminium compound are unlikely to deteriorate. For this reason, the excellent heat-shielding property of the interlayer film for laminated glass or the laminated glass can be maintained for a long time.

  The intermediate film 1 has a three-layer structure in which a second layer 3, a first layer 2, and a third layer 4 are stacked in this order. Thus, it is preferable that the first layer 2 is sandwiched between the second and third layers 3 and 4. In this case, the glass constituent member can be firmly bonded to both surfaces of the intermediate film 1. However, the third layer 4 is not necessarily used. That is, the second layer 3 may be laminated only on one surface 2 a of the first layer 2. In this case, the outer surface 3a of the second layer 3 is a layer on which laminated glass constituent members are laminated. The intermediate film may have a laminated structure of four or more layers.

  The thickness of the intermediate film is not particularly limited. The thickness of the intermediate film indicates the total thickness of each layer constituting the intermediate film. Therefore, in the case of the intermediate film 1, the thickness of the intermediate film 1 indicates the total thickness of the first to third layers 2 to 4. From the viewpoint of practical use and from the viewpoint of sufficiently increasing the heat shielding property and adhesiveness, the preferred lower limit of the thickness of the interlayer film is 0.1 mm, the more preferred lower limit is 0.25 mm, the preferred upper limit is 3 mm, and the more preferred upper limit is 1. .5 mm. When the thickness of the intermediate film is too thin, the penetration resistance of the laminated glass tends to decrease.

  From the viewpoint of practical use and the viewpoint of sufficiently increasing the adhesiveness, the preferred lower limit of each thickness of the second and third layers 3 and 4 is 0.01 mm, the more preferred lower limit is 0.1 mm, and the preferred upper limit is 0.00. 76 mm, and a more preferable upper limit is 0.4 mm.

  From the viewpoint of practical use and from the viewpoint of sufficiently increasing the heat shielding property, the preferred lower limit of the thickness of the first layer 2 is 0.001 mm, the more preferred lower limit is 0.01 mm, the still more preferred lower limit is 0.05 mm, and the preferred upper limit is 0.76 mm, a more preferable upper limit is 0.4 mm, and a more preferable upper limit is 0.2 mm.

  Hereinafter, details of materials constituting the first to third layers 2 to 4 will be described.

(Thermoplastic resin)
Each of the first to third layers 2 to 4 includes a thermoplastic resin. As for the said thermoplastic resin, only 1 type may be used and 2 or more types may be used together.

  Examples of the thermoplastic resin include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, polyvinyl alcohol resin, (meth) acrylic resin, and ionomer resin.

  The second and third layers 3 and 4 contain a polyvinyl acetal resin as a thermoplastic resin.

  The first layer 2 contains a thermoplastic resin having a hydroxyl group content of 25 mol% or less as a thermoplastic resin.

  From the viewpoint of improving the initial heat shielding property and the heat shielding property after the lapse of time, the thermoplastic resin having a hydroxyl group content of 25 mol% or less contained in the first layer 2 is a polyvinyl acetal resin or a (meth) acrylic resin. An ethylene-vinyl acetate copolymer resin or an ionomer resin is preferable, and a polyvinyl acetal resin or a (meth) acrylic resin is more preferable.

  The thermoplastic resin contained in the first layer 2 is preferably a polyvinyl acetal resin having a hydroxyl group content of 25 mol% or less. In this case, since all of the first to third layers 2 to 4 contain the polyvinyl acetal resin, the affinity is enhanced, and the first layer 2 and the second and third layers 3 and 4 Can be further improved. The content of the hydroxyl group in the thermoplastic resin contained in the first layer 2 is preferably 20 mol% or less, more preferably 15 mol% or less, and preferably 10 mol% or less. More preferably, it is particularly preferably 5 mol% or less.

  It is preferable that the 1st layer 2 contains the below-mentioned plasticizer. A plasticizer is preferably used when the thermoplastic resin of the first layer 2 is a polyvinyl acetal resin having a hydroxyl group content of 25 mol% or less. By the combined use of a polyvinyl acetal resin having a hydroxyl group content of 25 mol% or less and a plasticizer, the adhesion between the first layer 2 and the second and third layers 3 and 4 can be further enhanced.

  The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol. The polyvinyl alcohol can be obtained, for example, by saponifying polyvinyl acetate. The saponification degree of the polyvinyl alcohol resin is generally in the range of 80 to 99.8 mol%.

  The preferable lower limit of the polymerization degree of the polyvinyl alcohol is 200, the more preferable lower limit is 500, the preferable upper limit is 3,000, and the more preferable upper limit is 2,500. When the said polymerization degree is too low, there exists a tendency for the penetration resistance of a laminated glass to fall. When the said polymerization degree is too high, shaping | molding of the intermediate film for laminated glasses may become difficult.

  The aldehyde is not particularly limited. In general, an aldehyde having 1 to 10 carbon atoms is preferably used as the aldehyde. Examples of the aldehyde having 1 to 10 carbon atoms include n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutyraldehyde, n-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, and n-decyl. Examples include aldehyde, formaldehyde, acetaldehyde, and benzaldehyde. Among these, n-butyraldehyde, n-hexylaldehyde or n-valeraldehyde is preferable, and n-butyraldehyde is more preferable. As for the said aldehyde, only 1 type may be used and 2 or more types may be used together.

  From the viewpoint of further enhancing the adhesive strength of the outer surfaces 3a and 4a of the second and third layers 3 and 4, the hydroxyl content of the polyvinyl acetal resin of the second and third layers 3 and 4 (the amount of hydroxyl groups) ) Is preferably higher than the hydroxyl group content of the thermoplastic resin of the first layer 2, for example, preferably exceeding 25 mol%. The more preferable lower limit of the hydroxyl group content of the polyvinyl acetal resin contained in the second and third layers 3 and 4 is 30 mol%, the preferable upper limit is 40 mol%, and the more preferable upper limit is 35 mol%. If the hydroxyl group content is too low, the adhesion of the second and third layers 3 and 4 may be lowered. On the other hand, if the hydroxyl group content is too high, the flexibility of the intermediate film 1 is lowered, and problems with handling of the intermediate film 1 are likely to occur.

  When the 1st layer 2 contains polyvinyl acetal resin, the content rate of the hydroxyl group of the polyvinyl acetal resin of the 1st layer 2 is 25 mol% or less. Thereby, deterioration of the immonium compound and aminium compound by a hydroxyl group can be suppressed. Therefore, the excellent heat shielding property of the laminated glass can be maintained for a long time. The upper limit with preferable hydroxyl group content of the polyvinyl acetal resin of a 1st layer is 20 mol%, and a preferable minimum is 0.1 mol%.

  The hydroxyl group content of the polyvinyl acetal resin is a molar fraction obtained by dividing the amount of ethylene groups to which hydroxyl groups are bonded by the total amount of ethylene groups in the main chain. The amount of ethylene group to which the hydroxyl group is bonded can be determined, for example, by measuring the amount of ethylene group to which the hydroxyl group of polyvinyl alcohol as a raw material is bonded in accordance with JIS K6726 “Testing method for polyvinyl alcohol”. it can.

  The preferable lower limit of the degree of acetylation (acetyl group amount) of the polyvinyl acetal resins of the second and third layers 3 and 4 is 0.1 mol%, the more preferable lower limit is 0.3 mol%, and the more preferable lower limit is 0.5. Mole%, a preferred upper limit is 30 mole%, a more preferred upper limit is 25 mole%, and a more preferred upper limit is 20 mole%.

  The upper limit with the preferable acetylation degree of the polyvinyl acetal resin of the 1st layer 2 is 25 mol%, and a more preferable upper limit is 20 mol%.

  If the degree of acetylation is too low, the compatibility between the polyvinyl acetal resin and the plasticizer may be reduced. If the degree of acetylation is too high, the moisture resistance of the interlayer film may be lowered.

  The degree of acetylation is obtained by subtracting the amount of ethylene groups to which acetal groups are bonded and the amount of ethylene groups to which hydroxyl groups are bonded from the total amount of ethylene groups of the main chain, The mole fraction obtained by dividing by. The amount of ethylene group to which the acetal group is bonded can be measured, for example, according to JIS K6728 “Testing method for polyvinyl butyral”.

  The preferable lower limit of the degree of acetalization of the polyvinyl acetal resin of the second and third layers 3 and 4 is 60 mol%, the more preferable lower limit is 63 mol%, the preferable upper limit is 85 mol%, the more preferable upper limit is 80 mol%, A preferable upper limit is 75 mol%.

  The preferable lower limit of the degree of acetalization of the polyvinyl acetal resin of the first layer 2 is 60 mol%, the more preferable lower limit is 63 mol%, the preferable upper limit is 85 mol%, and the more preferable upper limit is 80 mol%.

  When the degree of acetalization is too low, the compatibility between the polyvinyl acetal resin and the plasticizer may be low, and the glass transition temperature of the interlayer film for laminated glass may not be sufficiently lowered. When the said acetalization degree is too high, reaction time required in order to manufacture polyvinyl acetal resin may become long.

  The degree of acetalization is a mole fraction obtained by dividing the amount of ethylene groups to which acetal groups are bonded by the total amount of ethylene groups in the main chain.

  The degree of acetalization is obtained by measuring the amount of acetyl group and the amount of vinyl alcohol by a method based on JIS K6728 “Testing method for polyvinyl butyral” or by a method using nuclear magnetic resonance (NMR). The molar fraction can be calculated from the result, and then calculated by subtracting the amount of acetyl group and the amount of vinyl alcohol from 100 mol%.

  When the polyvinyl acetal resin is a polyvinyl butyral resin, the degree of acetalization (degree of butyralization) and the amount of acetyl group are determined in accordance with JIS K6728 “Testing methods for polyvinyl butyral” and infrared absorption spectrum (IR) or It can be calculated from the results measured by a method using nuclear magnetic resonance (NMR).

  The thermoplastic resin contained in the first layer 2 is preferably a (meth) acrylic resin having a hydroxyl group content of 25 mol% or less. By using the (meth) acrylic resin, the initial heat shielding property and the heat shielding property after aging can be further enhanced. Furthermore, the thermoplastic resin contained in the first layer 2 is preferably a (meth) acrylic resin having a hydroxyl group content of 25 mol% or less and having a carboxyl group. When the (meth) acrylic resin has a carboxyl group, the initial heat shielding property and the heat shielding property after aging can be further enhanced.

  The (meth) acrylic resin is obtained by polymerizing a single (meth) acrylate monomer or two or more (meth) acrylate monomers. Examples of the (meth) acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Moreover, in order to obtain the (meth) acrylic resin which has a carboxyl group, it is preferable to use (meth) acrylic acid as a polymerization component.

  The hydroxyl group content of the thermoplastic resin, for example, the (meth) acrylic resin indicates the amount of the monomer having a hydroxyl group out of a total of 100 mol% of all monomers constituting the (meth) acrylic resin. The content rate of the said hydroxyl group shows the quantity of the unit which has a hydroxyl group in 100 mol% of all units.

(Plasticizer)
The second and third layers 3 and 4 contain a plasticizer.

  From the viewpoint of increasing the adhesive force on the surface of the first layer 2, the first layer 2 preferably contains a plasticizer. When the thermoplastic resin of the first layer 2 is a polyvinyl acetal resin having a hydroxyl group content of 25 mol% or less, the first layer 2 particularly preferably contains a plasticizer.

  The plasticizer is not particularly limited. A conventionally known plasticizer can be used as the plasticizer. As for the said plasticizer, only 1 type may be used and 2 or more types may be used together.

  Examples of the plasticizer include organic ester plasticizers such as monobasic organic acid esters and polybasic organic acid esters, and phosphate plasticizers such as organic phosphate plasticizers and organic phosphite plasticizers. It is done. Of these, organic ester plasticizers are preferred. The plasticizer is preferably a liquid plasticizer.

  The monobasic organic acid ester is not particularly limited. For example, glycol ester obtained by reaction of glycol with monobasic organic acid, and ester of triethylene glycol or tripropylene glycol with monobasic organic acid. Etc. 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, heptylic acid, n-octylic acid, 2-ethylhexylic acid, n-nonyl acid, and decyl acid.

  The polybasic organic acid ester is not particularly limited, and examples thereof include an ester compound of a polybasic organic acid and an alcohol having a linear or branched structure having 4 to 8 carbon atoms. Examples of the polybasic organic acid include adipic acid, sebacic acid, and azelaic acid.

  The organic ester plasticizer is not particularly limited, and 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-ethyl butyrate, 1,4-butylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl butyrate, diethylene glycol di-2-ethyl hexanoate, dipropylene glycol 2-ethylbutyrate, triethylene glycol di-2-ethylpentanoate, tetraethylene glycol di-2-ethylbutyrate, diethylene glycol dicapryate, triethylene glycol di-n-heptanoate, tetraethylene glycol di-n -Heptanoate, triethylene glycol di-2-ethylbutyrate, triethylene glycol bis-2-ethylbutyrate, triethylene glycol di-2-ethylhexanoate, triethylene glycol diheptanoate, tetraethylene glycol dihepta Noate, dihexyl adipate, dioctyl adipate, hexyl cyclohexyl adipate, a mixture of heptyl adipate and nonyl adipate, diisononyl adipate, heptylnonyl adipate, Bhasin dibutyl oil-modified sebacic alkyds, and mixtures of phosphoric acid esters and adipic acid esters. Other adipic acid esters other than the above-mentioned adipic acid esters may be used.

  The organophosphate plasticizer is not particularly limited, and examples thereof include tributoxyethyl phosphate, isodecylphenyl phosphate, and triisopropyl phosphate.

  The plasticizer is preferably at least one of triethylene glycol di-2-ethylhexanoate (3GO) and triethylene glycol di-2-ethylbutyrate (3GH).

  Content of the said plasticizer in the 1st-3rd layers 2-4 is not specifically limited. A preferable lower limit of the plasticizer content is 25 parts by weight, a more preferable lower limit is 30 parts by weight, a preferable upper limit is 60 parts by weight, and a more preferable upper limit is 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When content of the said plasticizer satisfy | fills the said preferable minimum, the penetration resistance of a laminated glass can be improved further. When content of the said plasticizer satisfy | fills the said preferable upper limit, transparency of an intermediate film can be improved further. The content of the plasticizer in the first layer 2 is preferably larger than the content of the plasticizer in the second and third layers 3 and 4, more preferably 10 parts by weight or more, and 15 weights. More preferably, there are more parts. By increasing the content of the plasticizer, the sound insulating properties of the interlayer film for laminated glass are improved.

(Metal oxide particles)
The first layer 2 may contain metal oxide particles. The second and third layers 3 and 4 may or may not contain metal oxide particles. From the viewpoint of further improving the heat shielding property of the laminated glass, the second and third layers 3 and 4 preferably each contain metal oxide particles. At least one of the first layer 2 and the second layer 3 preferably contains metal oxide particles.

  The metal oxide particles are not particularly limited as long as they are particles formed of a metal oxide. Only 1 type may be used for a metal oxide particle, and 2 or more types may be used together.

  Infrared rays having a wavelength longer than that of visible light having a wavelength of 780 nm or more have a smaller energy amount than ultraviolet rays. However, infrared rays have a large thermal effect, and once infrared rays are absorbed by a substance, they are released as heat. For this reason, infrared rays are generally called heat rays. By using the metal oxide particles, infrared rays (heat rays) can be effectively blocked.

  Specific examples of the metal oxide particles include aluminum-doped tin oxide particles, indium-doped tin oxide particles, antimony-doped tin oxide particles (ATO particles), gallium-doped zinc oxide particles (GZO particles), and indium-doped zinc oxide particles (IZO particles). ), Aluminum doped zinc oxide particles (AZO particles), niobium doped titanium oxide particles, sodium doped tungsten oxide particles, cesium doped tungsten oxide particles, thallium doped tungsten oxide particles, rubidium doped tungsten oxide particles, tin doped indium oxide particles (ITO particles) And tin-doped zinc oxide particles and silicon-doped zinc oxide particles. Especially, since the shielding function of a heat ray is high, ATO particle | grains, GZO particle | grains, ITO particle | grains or cesium dope tungsten oxide particle | grains are preferable, and ITO particle | grains are more preferable.

  A preferable lower limit of the average particle diameter of the metal oxide particles is 0.01 μm, a more preferable lower limit is 0.02 μm, a preferable upper limit is 0.1 μm, and a more preferable upper limit is 0.05 μm. When the average particle diameter satisfies the above preferable lower limit, the heat ray shielding property can be sufficiently enhanced. When the average particle diameter satisfies the preferable upper limit, the dispersibility of the metal oxide particles can be improved.

  The “average particle diameter” indicates a volume average particle diameter. The average particle diameter can be measured using a particle size distribution measuring apparatus (“UPA-EX150” manufactured by Nikkiso Co., Ltd.) or the like.

  Content of the said metal oxide particle in the 1st-3rd layers 2-4 is not specifically limited. The preferred lower limit of the content of the metal oxide particles is 0.01 parts by weight, the more preferred lower limit is 0.1 parts by weight, the preferred upper limit is 3 parts by weight, and the more preferred upper limit is 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. 1 part by weight. When the content of the metal oxide particles in the first to third layers 2 to 4 is within the preferable range, the heat shielding property can be sufficiently increased, the Tts can be sufficiently decreased, and the above The visible light transmittance can be sufficiently increased. For example, the Tts can be 50% or less, and the visible light transmittance can be 70% or more.

(Immonium compounds and aminium compounds)
The first layer 2 contains at least one of the immonium compound and the aminium compound (hereinafter also referred to as component X). The first layer 2 may contain only an immonium compound, may contain only an aminium compound, or may contain both an immonium compound and an aminium compound.

  In the intermediate film 1, the metal oxide particles may be used, and the combined use of the metal oxide particles and the component X can sufficiently block infrared rays (heat rays).

  The content of component X in the first layer 2 is not particularly limited. The preferable lower limit of the content of component X is 0.001 part by weight, the more preferable lower limit is 0.01 part by weight, the preferable upper limit is 3 parts by weight, and the more preferable upper limit is 1 part by weight with respect to 100 parts by weight of the thermoplastic resin. The upper limit is more preferably 0.5 parts by weight. When the content of the component X in the first layer 2 is within the above preferable range, the heat shielding property can be sufficiently increased, the Tts can be sufficiently lowered, and the visible light transmittance is sufficiently increased. Can be high. For example, the Tts can be 50% or less, and the visible light transmittance can be 70% or more.

(Other ingredients)
Each of the first to third layers 2 to 4 is an ultraviolet absorber, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture resistant agent, and a fluorescence, as necessary. You may contain additives, such as a whitening agent and an infrared absorber.

  At least one of the first layer 2, the second layer 3, and the third layer preferably contains an ultraviolet absorber. Moreover, it is preferable that at least one of the first layer 2, the second layer 3, and the third layer contains an antioxidant. Furthermore, it is preferable that at least one of the first layer 2, the second layer 3, and the third layer contains a light stabilizer.

  The first layer 2 preferably contains a chelating agent. In this case, the ultraviolet shielding performance of the first layer 2 is improved.

(Interlayer film for laminated glass)
The interlayer film for laminated glass according to the present invention is used for obtaining laminated glass.

  FIG. 2 shows an example of a laminated glass using the intermediate film 1 shown in FIG.

  A laminated glass 11 shown in FIG. 2 includes an intermediate film 1 and first and second laminated glass constituting members 12 and 13. The intermediate film 1 is an intermediate film for laminated glass. The intermediate film 1 is sandwiched between the first and second laminated glass constituent members 12 and 13. Therefore, the laminated glass 11 is configured by laminating the first laminated glass constituting member 12, the intermediate film 1, and the second laminated glass constituting member 13 in this order. The first laminated glass constituting member 12 is laminated on the outer surface 3 a of the second layer 3. The second laminated glass component 13 is laminated on the outer surface 4 a of the third layer 4.

  Examples of the first and second laminated glass constituent members 12 and 13 include glass plates, polycarbonate films, and PET (polyethylene terephthalate) films. The laminated glass 11 includes not only a laminated glass in which an interlayer film for laminated glass is sandwiched between two glass plates, but also a laminated glass in which an interlayer film for laminated glass is sandwiched between a glass plate and a PET film or the like. included. The laminated glass 11 is a glass plate-containing laminate, and it is sufficient that at least one glass plate is used. The another laminated glass constituent member may be a glass plate.

  Examples of the glass plate include inorganic glass and organic glass. Examples of the inorganic glass include float plate glass, heat ray absorbing plate glass, polished plate glass, mold plate glass, mesh plate glass, and wire plate glass. The organic glass is a synthetic resin glass used as a substitute for inorganic glass. Examples of the organic glass include polycarbonate plates and poly (meth) acrylic resin plates. A polymethyl (meth) acrylate board etc. are mentioned as said poly (meth) acrylic resin board.

  Although the thickness of the laminated glass component members 12 and 13 is not specifically limited, It is preferable to exist in the range of 1-3 mm. Moreover, when the laminated glass structural members 12 and 13 are glass plates, it is preferable that the thickness of this glass plate exists in the range of 1-3 mm. When the laminated glass constituent members 12 and 13 are PET films, the thickness of the PET film is preferably in the range of 0.03 to 0.5 mm.

  The manufacturing method of the laminated glass 11 is not specifically limited. For example, the intermediate film 1 is sandwiched between the first and second laminated glass constituent members 12 and 13 and passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure, so that the first and second The air remaining between the laminated glass constituent members 12 and 13 and the intermediate film 1 is deaerated. Then, it pre-adheres at about 70-110 degreeC, and a laminated body is obtained. Next, the laminated body is put in an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. In this way, the laminated glass 11 can be obtained. Further, as described above, the intermediate film 1 may be formed simultaneously with the production of the laminated glass 11.

  The laminated glass 1 can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. The laminated glass 1 can be used for a windshield, side glass, rear glass, roof glass, or the like of an automobile. Since the Tts is low and the visible light transmittance is high, the laminated glass 1 is suitably used for an automobile.

  From the viewpoint of satisfying the required performance of the cool car regulations, the Tts of the laminated glass 1 is preferably 50% or less, and preferably 40% or less. Furthermore, from the viewpoint of satisfying the required performance of the cool car regulations, the visible light transmittance of the laminated glass 1 is preferably 70% or more.

  The present invention will be described in more detail with reference to the following examples. The present invention is not limited to these examples.

Example 1
Preparation of composition A:
Using a horizontal microbead mill, 30 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, 40 parts by weight of ITO particles (volume average particle diameter 20 nm), and immonium (Japan) 26 parts by weight of a mixture (50% by weight: 50% by weight) of “CIR-RL” manufactured by Carlit and “KAYASORB IRG-022” manufactured by Nippon Kayaku Co., Ltd. and 4 parts by weight of a polyphosphate ester as a dispersant Mixing was performed to obtain a dispersion.

  100 parts by weight of a polyvinyl butyral resin (a) (average polymerization degree 2300, butyralization degree 65.1 mol%, acetylation degree 14.4 mol%, hydroxyl group content 20.5 mol%), and the resulting dispersion 3GO was thoroughly mixed to obtain a composition A. In addition, it adjusted so that ITO particle | grains might become 2.4 weight part and 3GO 60 weight part with respect to 100 weight part of polyvinyl butyral resin (a).

Preparation of composition B:
Polyvinyl butyral resin (b) (average polymerization degree 1700, butyralization degree 68.5 mol%, acetylation degree 0.9 mol%, hydroxyl group content 30.6 mol%) 100 parts by weight and 3GO 40 parts by weight are mixed And composition B was obtained.

Laminated glass production:
The obtained composition A was used as a first layer forming composition. Further, the obtained composition B was used as the second and third layer forming compositions. Composition A and composition B were coextruded to produce an interlayer film for laminated glass in which the second layer, the first layer, and the third layer were laminated in this order. The thickness of the first layer was 0.1 mm, and the thickness of the second and third layers was 0.35 mm.

  The obtained interlayer film for laminated glass was cut into a size of 300 mm long × 300 mm wide.

  The obtained interlayer film for laminated glass was sandwiched between two transparent float glasses (length 300 mm × width 300 mm × thickness 2.5 mm) to obtain a laminate. Next, the obtained laminate was put in a rubber bag and deaerated for 20 minutes at a vacuum degree of 2.6 kPa. While being deaerated, the laminate was stored in an oven at 90 ° C. for 30 minutes to obtain a laminated glass provided with an interlayer film for laminated glass.

(Example 2)
Preparation of composition C:
In preparing the composition A of Example 1, the polyvinyl butyral resin (a) was replaced with the polyvinyl butyral resin (c) (average polymerization degree 2500, butyralization degree 75 mol%, acetylation degree 17 mol%, hydroxyl group content 8). The composition C was obtained in the same manner except that it was changed to (mol%).

Laminated glass production:
A first layer was produced in the same manner as in Example 1 except that the composition C was used as the first layer forming composition instead of the composition A. A laminated glass provided with an interlayer film for laminated glass was obtained in the same manner as in Example 1 except that the obtained first layer was used.

(Example 3)
Preparation of composition D:
In ethyl acetate, 80 parts by weight of n-butyl acrylate and 20 parts by weight of acrylic acid were copolymerized and crosslinked using an isocyanate crosslinking agent to prepare an acrylic pressure-sensitive adhesive. Furthermore, 1.4 parts by weight of aminium (“CIR-963” manufactured by Nippon Carlit Co., Ltd.) was mixed with 100 parts by weight of the solid content of the acrylic pressure-sensitive adhesive to obtain a composition D.

Laminated glass production:
The obtained composition D was used as a first layer forming composition. Composition D was applied, and ethyl acetate was volatilized to produce a first layer having a thickness of 0.1 mm.

  The composition B obtained in Example 1 was used as the second and third layer forming compositions. The composition B was sufficiently melt-kneaded with a mixing roll, and then press-molded at 150 ° C. for 30 minutes using a press molding machine to produce second and third layers each having a thickness of 0.35 mm.

  The second layer, the first layer, and the third layer were laminated in this order to produce an interlayer film for laminated glass having a thickness of 0.8 mm. Moreover, it carried out similarly to Example 1, and obtained the laminated glass provided with the intermediate film for laminated glasses.

Example 4
Preparation of composition E:
In ethyl acetate, 80 parts by weight of n-butyl acrylate and 20 parts by weight of acrylic acid were copolymerized and crosslinked using an isocyanate crosslinking agent to prepare an acrylic pressure-sensitive adhesive. Furthermore, with respect to 100 parts by weight of the solid content of the acrylic pressure-sensitive adhesive, 2.1 parts by weight of ITO particles (volume average particle diameter 20 nm), immonium (“CIR-RL” manufactured by Nippon Carlit Co., Ltd. and “Nippon Kayaku Co., Ltd.” A composition E was obtained by mixing 1.4 parts by weight of a mixture with KAYASORB IRG-022 (50% by weight: 50% by weight) and 0.4 parts by weight of a polyphosphate ester as a dispersant.

Laminated glass production:
A first layer was produced in the same manner as in Example 3 except that the composition E was used as the first layer forming composition instead of the composition D. A laminated glass provided with an interlayer film for laminated glass was obtained in the same manner as in Example 3 except that the obtained first layer was used.

(Example 5)
Preparation of composition F:
A composition F was obtained in the same manner except that the content of aminium (“CIR-963” manufactured by Nippon Carlit Co., Ltd.) was changed to 0.8 parts by weight when preparing the composition D of Example 3. .

Laminated glass production:
An interlayer film for laminated glass was obtained in the same manner as in Example 3 except that the composition F was used as the first layer forming composition instead of the composition D. Furthermore, a laminated glass provided with an interlayer film for laminated glass was obtained in the same manner as in Example 3 except that the float glass was changed to green glass.

(Example 6)
Preparation of composition G:
1.4 parts by weight of aminium (“CIR-963” manufactured by Nippon Carlit Co., Ltd.) is mixed with 100 parts by weight of ethylene-vinyl acetate copolymer resin (vinyl acetate content: 33% by mass) to obtain composition G. It was.

Laminated glass production:
An interlayer film for laminated glass was obtained in the same manner as in Example 3 except that the composition G was used as the first layer forming composition instead of the composition D. A laminated glass provided with the interlayer film for laminated glass was obtained in the same manner as in Example 3 except that the obtained interlayer film for laminated glass was used.

(Example 7)
Preparation of composition H:
In preparing the composition B of Example 1, the same except that 1.6 parts by weight of an ultraviolet absorber (“Tinubin 328” manufactured by Ciba) was mixed with 100 parts by weight of the polyvinyl butyral resin (b). Thus, a composition H was obtained.

Laminated glass production:
An interlayer film for laminated glass was obtained in the same manner as in Example 1 except that the composition H was used as the second and third layer forming compositions instead of the composition B. Furthermore, it carried out similarly to Example 1, and obtained the laminated glass provided with the intermediate film for laminated glasses.

(Comparative Example 1)
Preparation of composition I:
Using a horizontal microbead mill, 56 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) as a plasticizer, 40 parts by weight of ITO particles (volume average particle diameter 20 nm), and as a dispersant 4 parts by weight of polyphosphate ester was mixed to obtain a dispersion.

  100 parts by weight of a polyvinyl butyral resin (b) (average polymerization degree 1700, butyralization degree 68.5 mol%, acetylation degree 0.9 mol%, hydroxyl group content 30.6 mol%), and the resulting dispersion 3GO was thoroughly mixed to obtain a composition. In addition, it adjusted so that an ITO particle might be 1 weight part and 3GO might be 40 weight part with respect to 100 weight part of polyvinyl butyral resin (b), and the composition I was obtained.

Laminated glass production:
Using the obtained composition I, an interlayer film for laminated glass having a thickness of 0.8 mm was obtained. Furthermore, the laminated glass provided with the intermediate film for laminated glasses was obtained like Example 1 except having changed the float glass into the green glass.

(Comparative Example 2)
Preparation of composition J:
100 parts by weight of polyvinyl butyral resin (b) (average polymerization degree 1700, butyralization degree 68.5 mol%, acetylation degree 0.9 mol%, hydroxyl group content 30.6 mol%) and triethylene as a plasticizer A mixture of 50 parts by weight of glycol di-2-ethylhexanoate (3GO) and immonium (“CIR-RL” manufactured by Nippon Carlit Co., Ltd. and “KAYASORB IRG-022” manufactured by Nippon Kayaku Co., Ltd. (50 wt%: 50 % By weight))) and 0.23 part by weight were mixed to obtain a composition J.

Laminated glass production:
Using the obtained composition J, an interlayer film for laminated glass having a thickness of 0.8 mm was obtained. Furthermore, it carried out similarly to Example 1, and obtained the laminated glass provided with the intermediate film for laminated glasses.

(Evaluation)
(1) Measurement of Tts at the beginning and after lapse of time According to the measurement method defined by the cool car regulations, the Tts of the obtained laminated glass was measured. Specifically, the Tts was measured by measuring in accordance with JIS R3106 (1998) using a spectrophotometer (“U-4100” manufactured by Hitachi High-Tech). The Tts of the laminated glass immediately after the production and the Tts of the laminated glass after the ultraviolet irradiation test was performed on the laminated glass in accordance with JIS R3212 (1998) were measured.

(2) Measurement of visible light transmittance at initial stage and after lapse of time Using a spectrophotometer ("U-4100" manufactured by Hitachi High-Tech), in accordance with JIS R3211 (1998), the wavelength of laminated glass at 380 to 780 nm. The visible light transmittance was measured. The visible light transmittance of the laminated glass immediately after the production and the visible light transmittance of the laminated glass after performing an ultraviolet irradiation test on the laminated glass in accordance with JIS R3212 (1998) were measured.

(3) Evaluation of penetration resistance The obtained laminated glass (length 300 mm x width 300 mm) was adjusted so that the surface temperature was 25 ° C. Next, in accordance with JIS R3212 (1998), from a height of 4 m, a hard sphere having a mass of 2260 g and a diameter of 82 mm was dropped onto the center portion of the laminated glass for each of the six laminated glasses. For all six laminated glasses, the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. If the number of laminated glasses in which the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was 3 or less, it was rejected. In the case of four sheets, the penetration resistance of six new laminated glasses was evaluated. In the case of 5 sheets, one additional laminated glass was additionally tested, and the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. In the same way, from a height of 5 m and 6 m, a hard sphere having a mass of 2260 g and a diameter of 82 mm is dropped on the center of the laminated glass for each of the 6 laminated glasses, thereby improving the penetration resistance of the initial laminated glass. evaluated.

  Table 1 below shows the measurement results of the Tts and the visible light transmittance, and the evaluation results of penetration resistance.

DESCRIPTION OF SYMBOLS 1 ... Intermediate film for laminated glasses 2 ... 1st layer 2a ... One side 2b ... The other side 3 ... 2nd layer 3a ... Outer surface 4 ... 3rd layer 4a ... Outer surface 5 ... Metal oxide Particle 11 ... Laminated glass 12 ... First laminated glass component 13 ... Second laminated glass component

Claims (13)

A first layer and a second layer stacked on one side of the first layer;
The second layer contains a polyvinyl acetal resin and a plasticizer,
The first layer contains a thermoplastic resin and at least one of an immonium compound and an aminium compound;
The interlayer film for laminated glass, wherein the thermoplastic resin contained in the first layer is a thermoplastic resin having a hydroxyl group content of 25 mol% or less.   The thermoplastic resin having a hydroxyl group content of 25 mol% or less contained in the first layer is a polyvinyl acetal resin, a (meth) acrylic resin, an ethylene-vinyl acetate copolymer resin, or an ionomer resin. The interlayer film for laminated glass according to claim 1.   The interlayer film for laminated glass according to claim 2, wherein the thermoplastic resin having a hydroxyl group content of 25 mol% or less contained in the first layer is a polyvinyl acetal resin.   The interlayer film for laminated glass according to claim 2, wherein the thermoplastic resin having a hydroxyl group content of 25 mol% or less contained in the first layer is a (meth) acrylic resin.   The interlayer film for laminated glass according to claim 4, wherein the (meth) acrylic resin has a carboxyl group.   The interlayer film for laminated glass according to claim 1 or 2, wherein at least one of the first layer and the second layer further contains metal oxide particles.   The interlayer film for laminated glass according to claim 6, wherein the metal oxide particles are tin-doped indium oxide particles. A third layer stacked on the other surface of the first layer;
The interlayer film for laminated glass according to claim 1 or 2, wherein the third layer contains a polyvinyl acetal resin and a plasticizer.   The interlayer film for laminated glass according to claim 8, wherein at least one of the first layer, the second layer, and the third layer further contains an ultraviolet absorber.   The interlayer film for laminated glass according to claim 8, wherein at least one of the first layer, the second layer, and the third layer further contains an antioxidant.   The interlayer film for laminated glass according to claim 8, wherein at least one of the first layer, the second layer, and the third layer further contains a light stabilizer.   The interlayer film for laminated glass according to claim 1 or 2, wherein the first layer further contains a chelating agent. First and second laminated glass components;
An intermediate film sandwiched between the first and second laminated glass constituent members,
Laminated glass, wherein the interlayer film is the interlayer film for laminated glass according to any one of claims 1 to 12.

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