JP2013001610A - Method for producing laminated glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing laminated glass capable of heating an intermediate film constituting a laminated glass material in excellent energy efficiency.SOLUTION: In this method for producing laminated glass, which is a method for producing laminated glass from a laminated glass material (X) formed by sandwiching an intermediate film made of a polymer between two glass sheets, the intermediate film made of the polymer contains a near-infrared absorbent, and the laminated glass material (X) is irradiated with a near-infrared ray to heat the intermediate film made of the polymer, and the glass sheets are press-bonded onto the intermediate film made of the polymer, to thereby obtain the laminated glass formed by bonding the glass sheets onto the intermediate film made of the polymer.

Description

  The present invention relates to a method for producing laminated glass.

At present, laminated glass is widely used for automobile applications, architectural applications, and the like. The laminated glass is obtained by joining two plate glasses through a polymer intermediate film.
Even when the laminated glass is subjected to an impact from the outside and the plate glass portion is damaged, the glass fragments are bonded to the polymer intermediate film, and thus the glass fragments can be prevented from scattering. For this reason, it is possible to prevent the human body from being damaged by glass fragments in the event of an accident by using laminated glass for automotive applications (for example, windshields of automobiles) and architectural applications, which is useful in terms of safety. It is high and it is difficult for a person to enter the inside of a car or a house from the outside, so that it is highly useful in terms of crime prevention.

  The polymer intermediate film is required to have strength, flexibility, and transparency, and to be capable of being firmly bonded to a plate glass. For this reason, the kind of polymer constituting the intermediate film is limited. As the polymer, ethylene-vinyl acetate copolymer (hereinafter also referred to as EVA) and polyvinyl butyral (hereinafter also referred to as PVB) are generally used.

  As a conventional method for producing a laminated glass, a polymer intermediate film is first sandwiched between two sheet glasses to obtain a laminated glass material. Next, the laminated glass material is heated using a heat source such as a heater and an oven, the polymer intermediate film is melted, and the plate glass and the polymer intermediate film are pressure-bonded to obtain a laminated glass. In the laminated glass material, the plate glass and the polymer intermediate film are not bonded but are merely in contact with each other.

  However, when an object is heated using a heat source, the object is heated from the surface near the heat source. That is, when the laminated glass material is heated using a heat source, the laminated glass material is heated from the surface of the plate glass portion constituting the laminated glass material, and then heat is transmitted to heat the polymer intermediate film. The original purpose of heating is to raise the temperature of the polymer intermediate film constituting the laminated glass material to a temperature suitable for bonding. When heating using a heat source, the energy used to heat the plate glass, etc. Could be wasted.

  In patent document 1, when manufacturing a laminated glass, as a method of fuse | melting the intermediate film of a laminated glass raw material, irradiating a near-infrared ray to a laminated glass raw material is proposed. In this method, since the plate glass portion hardly absorbs near-infrared rays, it is disclosed that near-infrared rays are mainly absorbed by the intermediate film and converted into heat, and the intermediate film can be heated and melted.

JP 2005-320206 A

  An object of this invention is to provide the manufacturing method of a laminated glass which can heat the intermediate film which comprises a laminated glass raw material efficiently.

  As a result of intensive studies to solve the above problems, the inventors of the present invention are characterized in that the laminated glass material described in Patent Document 1 irradiates the laminated glass material with near infrared rays. It was found that a normal intermediate film cannot absorb near infrared rays sufficiently.

The present inventors have found that an intermediate film can be heated with high energy efficiency by incorporating a near-infrared absorber in the polymer intermediate film, and have completed the present invention.
That is, the method for producing a laminated glass of the present invention is a method for producing a laminated glass from a laminated glass material (X) in which a polymer intermediate film is sandwiched between two plate glasses, wherein the polymer intermediate A near-infrared absorber is contained in the film, and the laminated glass material (X) is irradiated with near-infrared rays to heat the polymer intermediate film, and by pressing the plate glass to the polymer intermediate film A laminated glass in which a plate glass and a polymer intermediate film are bonded is obtained.

It is preferable that the near-infrared absorbent is a fine particle having a near-infrared absorption characteristic and an average particle diameter of 200 nm or less.
The near-infrared absorber preferably contains at least one selected from copper ions, metal oxides, borides, and tungstic acid derivatives. A phosphonic acid compound represented by the following formula (1), a copper salt, It is more preferable to contain the copper compound obtained by making this react.

〔式中Ｒ¹は、‐ＣＨ₂ＣＨ₂‐Ｒ¹¹で表わされる１価の基であり、Ｒ¹¹は水素原子、炭素数１〜２０のアルキル基、または炭素数１〜２０のフッ素化アルキル基を示す。〕
前記近赤外線の照射が、ハロゲンヒータ、ハロゲンランプ、赤外線乾燥用ランプ、近赤外線領域の光を発する発光ダイオード、近赤外線領域の光を発するレーザーから選択される少なくとも１種の光源によって行われることが好ましい。

[Wherein R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl having 1 to 20 carbon atoms. Indicates a group. ]
The near infrared irradiation may be performed by at least one light source selected from a halogen heater, a halogen lamp, an infrared drying lamp, a light emitting diode that emits light in the near infrared region, and a laser that emits light in the near infrared region. preferable.

The heating of the polymer intermediate film is preferably performed by heating means other than near infrared irradiation in addition to heating by near infrared irradiation.
The solar radiation transmittance (JIS R 3106) of at least one of the plate glasses may be 70% or more.

  The solar radiation transmittance (JIS R 3106) of at least one of the plate glasses may be less than 70%.

  In the method for producing a laminated glass of the present invention, since the polymer intermediate film contains a near-infrared absorber, when the glass material is irradiated with near infrared rays, the polymer intermediate film is heated more efficiently than before. be able to.

  Moreover, the laminated glass obtained with the manufacturing method of this invention is excellent in near-infrared absorptivity.

It is a spectral distribution figure of infrared rays bulb IR100V125WRHE made by Toshiba Corporation. It is a figure which shows the temperature change of the laminated glass raw material in Example 1. FIG. It is a figure which shows the temperature change of the laminated glass raw material in Example 2. FIG.

Next, the present invention will be specifically described.
The method for producing a laminated glass of the present invention is a method for producing a laminated glass from a laminated glass material (X) in which a polymer intermediate film is sandwiched between two plate glasses, wherein the polymer intermediate film A glass sheet containing a near-infrared absorber, heating the polymer interlayer by irradiating the laminated glass material (X) with near-infrared radiation, and pressing the sheet glass onto the polymer interlayer; It is characterized in that a laminated glass in which a glass interlayer and a polymer intermediate film are bonded is obtained.

In the present invention, near infrared means light having a wavelength of 780 to 2500 nm.
[Laminated glass material (X)]
In the method for producing laminated glass of the present invention, laminated glass is produced from the laminated glass material (X). The laminated glass material (X) has a layer structure in which a polymer intermediate film is sandwiched between two plate glasses. That is, the layer structure of the laminated glass material (X) is plate glass / polymer intermediate film / plate glass.

In the laminated glass material (X), the plate glass and the polymer intermediate film are not joined, but are merely in contact with each other.
The laminated glass material (X) can be obtained by sandwiching a polymer intermediate film between two plate glasses.

(Plate glass)
There is no limitation in particular as plate glass used for this invention, The normal glass conventionally used for the laminated glass can be used. As the plate glass, one having a high visible light transmittance is usually used, although it varies depending on the use of the laminated glass. Note that ordinary glass hardly absorbs near infrared rays, and when the laminated glass material is irradiated with near infrared rays, most of the near infrared rays reach the polymer intermediate film.

In addition, the shape of plate glass is determined according to the use of a laminated glass, and what was cut out to the predetermined shape is used normally.
The thickness of the plate glass is determined according to the use of the laminated glass and is not particularly limited. However, when the laminated glass is used for a windshield of an automobile, a plate glass having a thickness of about 2 mm is used.

As two plate glass used for this invention, the same kind of plate glass may be used and two types of plate glass may be used.
As the plate glass, it is preferable that the solar radiation transmittance (JIS R 3106) of at least one of the plate glass is 70% or more. When the solar radiation transmittance is 70% or more, near infrared rays are mainly absorbed by the polymer intermediate film and heated.

  As plate glass, the solar radiation transmittance (JIS R 3106) of at least one of the plate glass may be less than 70%. When a plate glass having a solar transmittance of less than 70% is used, not only the polymer intermediate film but also the plate glass itself absorbs near infrared rays and generates heat. When plate glass with low solar transmittance is used on the surface of laminated glass that is not irradiated with near-infrared rays, near-infrared rays that the polymer interlayer could not absorb are absorbed by the plate glass with low solar transmittance. Therefore, the heating efficiency is improved. In addition, green glass etc. are mentioned as glass with low solar radiation transmittance.

(Polymer intermediate film)
The polymer intermediate film used in the present invention contains a near infrared absorber.
The polymer intermediate film used in the present invention is composed of a polymer and a near infrared absorber, and may further contain other components. Since the polymer intermediate film contains a near-infrared absorber, it is possible to effectively absorb near infrared rays, and the polymer intermediate film is efficiently heated by being irradiated with near infrared rays.

  The polymer intermediate film may be a single layer structure film or a multilayer structure film. When the polymer intermediate film is a film having a multilayer structure, it is sufficient that at least one layer contains a near-infrared absorber.

  The polymer intermediate film used in the present invention is composed of a polymer and a near-infrared absorber, and may further contain other components. Examples of other components include a plasticizer, an ultraviolet absorber, a light stabilizer, and an antioxidant.

  Examples of the plasticizer include triethylene glycol-di-2-ethylhexanoate, triethylene glycol-di-2-ethylbutyrate, tetraethylene glycol-di-2-ethylhexanoate, and tetraethylene glycol dihepta. Noate, dihexyl adipate, tributoxyethyl phosphate, isodecylphenyl phosphate and the like. Examples of the UV absorber include salicylate UV absorbers such as p-tert-butylphenyl salicylate, benzophenone UV absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, and 2- (2 ′ Benzotriazole ultraviolet absorbers such as hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-octylphenyl) benzotriazole, ethyl-2 -Cyanoacrylate type ultraviolet absorbers such as cyano-3,3-diphenylacrylate. Examples of the light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, di (1, 2,2,6,6-pentamethyl-4-piperidyl) -butyl (3 ′, 5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- (2- (3- (3,5-di-) tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl) -4- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) -2,2,6,6-tetramethyl Piperidine, poly {(6-{(1,1,3,3-tetramethylbutyl) amino} -1,3,5-triazine-2,4-diyl) (1,6- {2,2,6, 6-tetramethyl-4- Peridinyl} aminohexamethylene)}, poly {{6- (morpholino) -S-triazine-2,4-diyl} {1,6- (2,2,6,6-tetramethyl-4-piperidyl) amino} Hexamethylene}, 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinetanol, dimethyl succinate polymer and the like. Examples of the antioxidant include hindered phenol antioxidants, trialkylphosphine antioxidants, and sulfur antioxidants.

  The polymer intermediate film used in the present invention preferably contains 0.1 to 10 parts by weight of a near-infrared absorber, and 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the polymer. It is more preferable. Further, when other components are contained, there is no particular limitation as long as the effects of the present invention are not impaired, but usually 0.01 to 50 parts by weight with respect to 100 parts by weight of the polymer. It is preferable.

In addition, as thickness of a polymer intermediate film, it is 0.1-2.0 mm normally, and it is preferable that it is 0.2-1.5 mm.
The polymer constituting the polymer intermediate film may be a polymer that can be strongly bonded to a plate glass. Specifically, the polymer may be polyvinyl acetal or ethylene-vinyl acetate. Examples thereof include at least one polymer selected from a polymer (EVA), poly (meth) acrylic acid ester, polyester, and polyurethane.

As the polymer, it is preferable to use a polymer having a softening point of 70 to 150 ° C.
The polymer is more preferably at least one polymer selected from polyvinyl acetal and EVA, and at least one polymer selected from polyvinyl butyral resin (PVB) and EVA. Is particularly preferred, and PVB or EVA is most preferred.

When the polymer intermediate film is a multilayer film, a polymer other than a polymer that can be strongly bonded to the plate glass may be used for the layer that does not contact the plate glass.
A commercially available product may be used as the polymer used in the present invention.

  The near infrared absorber contained in the polymer intermediate film is not particularly limited as long as it can absorb near infrared rays. Since laminated glass is often used for applications where transparency is required, normally near infrared absorbers have excellent visible light permeability when dispersed in a polymer interlayer. An infrared absorber is used.

  The near-infrared absorber is preferably fine particles having a near-infrared absorption property and an average particle size of 200 nm or less, and the average particle size is more preferably 10 to 100 nm from the viewpoint of transparency and dispersion stability.

As a near-infrared absorber, it is preferable to contain at least 1 sort (s) selected from a copper ion, a metal oxide, a boride, and a tungstic acid derivative.
As a near-infrared absorber containing a copper ion, a near-infrared absorber containing a copper compound obtained by reacting a phosphonic acid compound represented by the following formula (1) and a copper salt, an alkyl phosphate compound and Examples thereof include copper compounds and copper sulfides obtained by reacting with copper salts.

〔式中Ｒ¹は、‐ＣＨ₂ＣＨ₂‐Ｒ¹¹で表わされる１価の基であり、Ｒ¹¹は水素原子、炭素数１〜２０のアルキル基、または炭素数１〜２０のフッ素化アルキル基を示す。〕
金属酸化物を含有する近赤外線吸収剤としては、スズドープ酸化インジウム、アンチモンドープ酸化スズ等が挙げられる。

[Wherein R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl having 1 to 20 carbon atoms. Indicates a group. ]
Examples of the near infrared absorber containing a metal oxide include tin-doped indium oxide and antimony-doped tin oxide.

Examples of the near-infrared absorber containing a boride include lanthanum hexaboride, cerium hexaboride, neodymium hexaboride, praseodymium hexaboride and the like.
As a near-infrared absorber containing a tungstic acid derivative, a compound represented by the general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe) Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S , Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, one or more elements, W is tungsten, O is oxygen, 0. 001 ≦ x / y ≦ 1.1, 2.2 ≦ z / y ≦ 3.0).

As a near-infrared absorber, the near-infrared absorber containing the copper compound obtained by making the phosphonic acid compound represented by the said Formula (1) and copper salt react is more preferable.
A commercial item may be used as a near-infrared absorber used for the present invention.

  As a near-infrared absorber containing a copper salt compound obtained by reacting a phosphonic acid compound represented by the formula (1) with a copper salt, a phosphonic acid compound represented by the general formula (1) and Obtained from at least one phosphate ester compound selected from a phosphate ester compound represented by the following general formula (2a) and a phosphate ester compound represented by the following general formula (2b), and a copper salt: It is preferable that it is a near-infrared absorber.

［Ｒ²¹、Ｒ²²およびＲ²³は、−（ＣＨ₂ＣＨ₂Ｏ）_nＲ⁵で表される１価の基であり、ｎは４〜３５の整数であり、Ｒ⁵は、炭素数６〜２５のアルキル基又は炭素数６〜２５のアルキルフェニル基を示す。ただし、Ｒ²¹、Ｒ²²およびＲ²³は、それぞれ同一でも異なっていてもよい。］

[R ²¹ , R ²² and R ²³ are monovalent groups represented by — (CH ₂ CH ₂ O) _n R ⁵ , n is an integer of 4 to 35, and R ⁵ has 6 carbon atoms. -25 alkyl group or a C6-C25 alkylphenyl group is shown. However, R ²¹ , R ²² and R ²³ may be the same or different. ]

  In the present invention, the “phosphonic acid compound represented by the general formula (1)” is also referred to as “specific phosphonic acid compound”, and the phosphoric acid ester compound represented by the general formula (2a) and the general formula ( "At least one phosphate ester compound selected from the phosphate ester compounds represented by 2b)" is also referred to as "specific phosphate ester compound", and "phosphonate compound represented by the general formula (1)" And at least one phosphate ester compound selected from a phosphate ester compound represented by the following general formula (2a) and a phosphate ester compound represented by the following general formula (2b), and a copper salt “Near-infrared absorber” is also referred to as “near-infrared absorber (A)”.

  Although there is no limitation in particular as a manufacturing method of a near-infrared absorber (A), For example, the following method is mentioned. As a method for producing the near-infrared absorber (A), first, a specific phosphonic acid compound, a specific phosphate compound, and a copper salt are mixed in a solvent, and the near-infrared absorber (A) is included. A step of obtaining a reaction mixture is performed. Subsequently, a near-infrared absorber (A) can be obtained by refine | purifying the reaction mixture obtained at this process.

  The near-infrared absorber (A) in the reaction mixture obtained in this step is considered to have near-infrared absorption characteristics mainly due to the copper ions of the phosphonic acid copper salt obtained by reacting the specific phosphonic acid compound with the copper salt. . The phosphonic acid copper salt is considered to be maintained in a very fine state by the specific phosphate ester compound acting as a dispersant. The copper phosphonate is represented by the following general formula (3).

  In addition, in the near-infrared absorber (A) in the reaction mixture obtained in the step, the specific phosphonic acid compound is mainly coordinated with copper ions, and the specific phosphate ester compound is present therearound. I think that. Moreover, it is thought that the said specific phosphate ester compound coordinates to some copper ions. For this reason, the copper ion in a near-infrared absorber (A) is excellent in stability with respect to heat or the like. When the polymer intermediate film used in the present invention contains a near-infrared absorber (A), the polymer constituting the intermediate film is not affected by copper ions, is less colored, and is excellent in transparency.

［式中、Ｒ¹は、−ＣＨ₂ＣＨ₂−Ｒ¹¹で表される１価の基であり、Ｒ¹¹は水素原子、炭素数１〜２０のアルキル基、または炭素数１〜２０のフッ素化アルキル基を示す。］

[In the formula, R ¹ is a monovalent group represented by ^{_{-CH 2 CH 2 -R 11, R}} 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or a fluorine having 1 to 20 carbon atoms, Represents an alkyl group. ]

R ¹¹ in the general formulas (1) and (3) is hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl. Group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, perfluoroethyl group, perfluoropropyl group, perfluoro-n-butyl group, perfluorohexyl group, perfluorooctyl Group, perfluorodecyl group and the like.

Further, when the reaction mixture containing the near-infrared absorber (A) is produced by the above step, the R ¹¹ in the general formulas (1) and (3) is a group having a large carbon number or a group having a long molecular chain. If there, because the dispersibility tends to decrease, as the R ^11, preferably a hydrogen atom or a carbon number of 1 to 10 alkyl group, more has a carbon number of alkyl group having 2 to 8 preferable. It is preferable that R ¹¹ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms because the dispersibility of the near-infrared absorber (A) tends to be particularly excellent. Further, it is preferable that R ¹¹ is an alkyl group having 2 to 8 carbon atoms because it tends to be easy to purify the reaction mixture by sedimentation of the solid content and obtain the near-infrared absorber (A).

In at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (2a) and the phosphate ester compound represented by the general formula (2b), R ²¹ , R ²² and R ²³ is a monovalent group (polyoxyalkyl group) represented by — (CH ₂ CH ₂ O) _n R ⁵ . n is an integer of 4 to 35, and more preferably an integer of 6 to 25. When n is less than 4, the transparency of the polymer intermediate film may be insufficient. On the other hand, when n exceeds 35, the amount of the phosphoric ester compound necessary for obtaining a polymer intermediate film having sufficient transparency increases, resulting in high costs.

R ⁵ is an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms, and is an alkyl group having 12 to 20 carbon atoms. Is more preferable. If R ⁵ is a group having less than 6 carbon atoms, the transparency of the polymer intermediate film may be insufficient. Further, if R ⁵ is a group having more than 25 carbon atoms, the amount of the phosphoric acid ester compound necessary for obtaining a polymer intermediate film having sufficient transparency increases, which causes high costs.

  In obtaining the near-infrared absorber (A) in the step, at least one of the phosphoric acid ester compound represented by the general formula (2a) and the phosphoric acid ester compound represented by the general formula (2b) is used. However, it is preferable to use both the phosphoric acid ester compound represented by the general formula (2a) and the phosphoric acid ester compound represented by the general formula (2b). When the phosphate ester compound represented by the general formula (2a) and the phosphate ester compound represented by the general formula (2b) are used, the polymer intermediate film tends to be excellent in transparency and heat resistance, which is preferable. . When both the phosphate compound represented by the general formula (2a) and the phosphate compound represented by the general formula (2b) are used, the phosphate compound represented by the general formula (2a) The ratio of the phosphoric acid ester compound represented by the general formula (2b) is not particularly limited, but is usually 10:90 to 90:10 in molar ratio ((2a) :( 2b)).

  Moreover, as a phosphate ester compound represented by the said General formula (2a), it may be used individually by 1 type, or 2 or more types may be used, As a phosphate ester compound represented by the said General formula (2b) May be used alone or in combination of two or more.

  In addition, at least a part of at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (2a) and the phosphate ester compound represented by the general formula (2b) Phosphoric acid in the acid ester compound, that is, a compound obtained by neutralizing a hydroxyl group with a base may be used. Examples of the base used for neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, and calcium hydroxide. At least a part of at least one phosphate ester compound selected from the phosphate ester compound represented by the general formula (2a) and the phosphate ester compound represented by the general formula (2b) Even if the phosphoric acid in the compound, that is, the hydroxyl group is replaced with a compound neutralized with a base, the near-infrared absorber (A) can be obtained by the same method.

Moreover, when obtaining a near-infrared absorber (A) in the said process, you may further use another phosphorus compound, for example, phosphoric acid triester.
As the specific phosphate compound, a commercially available phosphate compound can also be used.

  As the copper salt, a copper salt capable of supplying divalent copper ions is usually used. As said copper salt, what is necessary is just copper salts other than the phosphonic acid copper salt represented by the said General formula (3). Examples of the copper salt include copper of organic acids such as anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous ethyl acetoacetate copper, anhydrous pyrophosphate, anhydrous naphthenic acid copper, and anhydrous copper citrate. Salt, hydrate or hydrate of copper salt of organic acid; copper salt of inorganic acid such as copper oxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, hydrate of copper salt of inorganic acid Or a hydrate; copper hydroxide is mentioned. In addition, as a copper salt, you may use individually by 1 type, or may use 2 or more types.

As the copper salt, anhydrous copper acetate and copper acetate monohydrate are preferably used from the viewpoint of solubility and removal of by-products.
The near-infrared absorber (A) obtained by the said process is obtained from a specific phosphonic acid compound, a specific phosphoric acid ester compound, and a copper salt. As the near-infrared absorber (A) obtained in the step, there is a phosphonic acid copper salt obtained by reacting the specific phosphonic acid compound with a copper salt, and the specific phosphoric acid ester compound is present therearound. Conceivable. Further, it is considered that there is also a phosphonic acid copper salt in which a part of the specific phosphonic acid compound constituting the phosphonic acid copper salt is replaced with the specific phosphoric acid ester compound.

Moreover, the average particle diameter of the near-infrared absorber (A) obtained at the said process becomes like this. Preferably it is 10-150 nm, More preferably, it is 20-100 nm.
Moreover, the quantity of each said component used at the said process is as follows. The specific phosphonic acid compound is preferably used in an amount of 5 mol or more, more preferably 8 to 100 mol, and particularly preferably 10 to 80 mol, per 1 mol of the specific phosphate compound. If it is less than 5 mol, the near-infrared absorption characteristics of the polymer intermediate film may deteriorate, or the heat resistance may decrease.

  The specific phosphonic acid compound is preferably 0.4 mol or more, more preferably 0.5 to 1.5 mol, and more preferably 0.7 to 1 per 1 mol of copper in the copper salt. Particularly preferred is 2 moles. Within the above range, the transparency and heat resistance of the polymer intermediate film are particularly excellent, which is preferable.

  In the step, as described above, the specific phosphonic acid compound, the specific phosphate ester compound, and a copper salt are mixed in a solvent to obtain a reaction mixture containing a near infrared absorber (A). Specifically, it can be carried out by the following method.

  In the step, the specific phosphonic acid compound reacts with the copper salt mainly in the presence of the specific phosphoric ester compound, and the reaction causes the particulate copper phosphonic acid salt not dissolved in the solvent. Produces. Since the phosphoric ester compound can act as a good dispersant during the reaction, the phosphonic acid copper salt can be kept highly dispersible and can suppress aggregation.

  In the step, not only the reaction between the specific phosphonic acid compound and the copper salt, but also the specific phosphate compound and the copper salt may react, for example. In addition, the specific phosphonic acid compound, the specific phosphate ester compound, and a part of the copper salt may remain without reacting.

  Examples of the solvent used in the above step include alcohols such as methanol and ethanol, tetrahydrofuran (THF), dimethylformamide (DMF), water, and the like, and ethanol, THF, or DMF is preferable from the viewpoint of satisfactory reaction. The reaction step is preferably performed at room temperature to 60 ° C, more preferably 20 to 40 ° C, preferably 0.5 to 5 hours, more preferably 1 to 3 hours.

  By this reaction, a reaction mixture containing the near-infrared absorber (A) is obtained. In addition to the near-infrared absorber (A), the reaction mixture contains by-products and the like depending on the solvent and the raw material used.

  A near-infrared absorber (A) can be obtained by refine | purifying the said reaction mixture. The purification method is not particularly limited. For example, the reaction mixture is dried under reduced pressure to obtain a near-infrared absorber (A), the reaction mixture is filtered, the solid content is dried, and the near-infrared absorber ( A method of obtaining A), a method of precipitating the solid content in the reaction mixture, removing the supernatant liquid to obtain a solid content, and then drying the obtained solid content to obtain a near-infrared absorber (A). . In addition, for the purpose of more precise purification between the removal of the supernatant and the drying of the solid, the obtained solid is dispersed again in the dispersion medium, the solid is settled, and the supernatant is You may perform operation which removes and obtains solid content.

  Examples of the sedimentation method include a method in which the solid content is settled by allowing the reaction mixture to stand, and a method in which the solid content is sedimented by centrifuging the reaction mixture. The method for removing the supernatant varies depending on the scale for producing the near-infrared absorber (A). For example, a method for removing the supernatant using a Pasteur pipette, a dropper, or the like, or removing the supernatant by decantation. The method of removing etc. are mentioned.

By the sedimentation or removal of the supernatant, it is possible to remove the solvent and the by-product soluble in the solvent in the reaction mixture.
As the dispersion medium, it is sufficient that the near-infrared absorber (A) can be dispersed and the raw material (the copper salt, the specific phosphonic acid compound, the specific phosphoric acid ester compound) can be dissolved, For example, methanol, ethanol, 2-propanol, etc. are mentioned.

  When the near-infrared absorbing agent (A) that can be obtained by the above method is contained in the polymer intermediate film, the polymer constituting the intermediate film is not affected by copper ions and is transparent without coloration. It is preferable because of its excellent properties. Moreover, since a near-infrared absorber (A) is excellent in the dispersibility with respect to the said polymer, it is preferable.

  The method for producing the polymer intermediate film used in the present invention is not particularly limited. For example, 1; a near-infrared absorbent dispersion is prepared from a near-infrared absorbent and a dispersion medium, and the dispersion and the monomer are mixed. After removing the dispersion medium, a near-infrared absorber-containing monomer is prepared, the monomer is polymerized, and if necessary, it is molded by a molding method such as extrusion molding, cast molding, injection molding, or press molding. A method for producing a polymer intermediate film, 2; a near-infrared absorber dispersion liquid is prepared from a near-infrared absorber and a dispersion medium, and the dispersion liquid is mixed with a polymer dissolved in a solvent to contain a near-infrared absorber A polymer solution is prepared, a polymer containing a near infrared absorber is prepared by a solvent casting method or the like, and the polymer containing the near infrared absorber is extruded, cast, injection molded, or pressed as necessary. Molding A method for producing a polymer intermediate film by molding according to the molding method, 3; a near-infrared absorbent dispersion is prepared from a near-infrared absorbent and a dispersion medium, and a powdery polymer is dispersed in the dispersion Then, by removing the dispersion medium, a master batch composed of a near-infrared absorber and a polymer is obtained, and using the master batch and the polymer, molding methods such as extrusion molding, cast molding, injection molding, press molding, etc. A method for producing a polymer intermediate film by molding with 4; obtaining a masterbatch comprising a near-infrared absorber and a polymer by kneading a near-infrared absorber and a powdered polymer; And a method of producing a polymer intermediate film by molding using a molding method such as extrusion molding, cast molding, injection molding, or press molding using a polymer.

(Laminated glass manufacturing method)
The method for producing a laminated glass of the present invention comprises heating the polymer intermediate film by irradiating the laminated glass material (X) with near-infrared rays, and pressing the plate glass to the polymer intermediate film, thereby increasing the thickness of the sheet glass. A laminated glass having a molecular intermediate film bonded thereto is obtained.

  In the method for producing a laminated glass of the present invention, the laminated glass material (X) is irradiated with near infrared rays. The light source for irradiating near infrared rays is not particularly limited, and is selected from a halogen heater, a halogen lamp, an infrared drying lamp, a light emitting diode that emits light in the near infrared region, and a laser that emits light in the near infrared region. It is preferably performed by at least one light source.

Examples of lasers that emit light in the near infrared region include semiconductor lasers, Nd-YAG lasers, dye lasers, and Ti-doped sapphire lasers.
From the viewpoint of ease of use and cost, the light source is preferably a halogen lamp, an infrared drying lamp, a light emitting diode that emits light in the near infrared region, or a semiconductor laser.

The light source only needs to include light in the near infrared region, and may include light having a wavelength other than the near infrared region.
The heating of the polymer intermediate film may be performed only by irradiation with near infrared rays, or may be performed by heating means other than irradiation with near infrared rays in addition to heating by irradiation with near infrared rays. Note that heating means other than near-infrared irradiation are also referred to as other heating means.

  Examples of other heating means include heating with warm air using an oven or the like, heating using an infrared heater, and the like. In addition, when the polymer intermediate film is heated by other heating means, the other heating is performed simultaneously with the near infrared irradiation, before the near infrared irradiation, or after the near infrared irradiation. Good.

  The polymer intermediate film is heated until the polymer intermediate film reaches a temperature at which it can be joined to the plate glass. The temperature at which the sheet glass can be joined varies depending on the type of polymer, but when the polymer is PVB, it is usually heated to 80 to 160 ° C, preferably 100 to 150 ° C.

  In the method for producing a laminated glass of the present invention, after heating the temperature of the polymer intermediate film constituting the laminated glass material (X) to a temperature suitable for bonding, the sheet glass is pressure-bonded to the polymer intermediate film, The plate glass and the polymer intermediate film are joined.

Although there is no limitation in particular as the method of performing the said crimping | compression-bonding, after heating the polymer intermediate film which comprises a laminated glass raw material (X), let this laminated glass raw material (X) pass a pair of pressure rollers. And a method of pressure-bonding plate glass to a polymer intermediate film. As another method, a laminated glass material (X) is put into a bag body, and before or after heating the polymer intermediate film constituting the laminated glass material (X), a vacuum pump or the like Is used to lower the pressure by discharging the gas inside the bag body, bring the bag body and the plate glass constituting the glass material (X) into close contact, and press the plate glass to the polymer intermediate film. . In addition, a bag body is normally formed from a polyethylene film or a polypropylene film. Note that a plurality of these methods may be performed to perform pressure bonding.
In addition, the specific example of the manufacturing method of the laminated glass of this invention is illustrated below.

  As a specific example of the method for producing the laminated glass of the present invention, first, the laminated glass material (X) is put into a bag body, and the pressure is lowered by discharging the gas inside the bag body with a vacuum pump. The plate glass constituting the material (X) is brought into close contact. By discharging the gas, the inside of the bag body is crushed by the atmospheric pressure in this state, and the plate glass and the polymer intermediate film are in close contact with each other under pressure. Next, near infrared irradiation is performed from the outside of the bag body toward the inside of the bag body, and the polymer intermediate film constituting the laminated glass material (X) inside the bag body is heated. In order to suitably absorb near infrared rays in the polymer intermediate film, it is preferable to use a light source capable of irradiating near infrared rays having a wavelength that is difficult to be absorbed by the bag. When the near-infrared irradiation raises the temperature of the polymer intermediate film and reaches a temperature at which bonding is possible, the glass plate that has been in close contact with the pressure applied and the polymer intermediate film are pressure-bonded and bonded together. A laminated glass is obtained. Next, near-infrared irradiation is stopped, the bag and the laminated glass are cooled, and the laminated glass is taken out from the bag.

  As another specific example of the method for producing the laminated glass of the present invention, first, the laminated glass material (X) is irradiated with near infrared rays, and the polymer intermediate film constituting the laminated glass material (X) is heated. Next, by passing the laminated glass material (X) through a pair of pressure rollers, the plate glass and the polymer intermediate film are pressure-bonded and joined to obtain a laminated glass. In addition, as a pair of pressure roller, the space | interval of a roller is smaller than the thickness of a laminated glass raw material (X), Therefore, when a laminated glass raw material (X) passes through a pressurized roller, both plate glass When air is present between the plate glass and the polymer intermediate film, it is pushed out of the system, and the plate glass and the polymer intermediate film are pressure-bonded and bonded to obtain a laminated glass.

  In addition, in the laminated glass obtained in the above specific examples and the like, if the bonding between the plate glass constituting the laminated glass and the polymer intermediate film is insufficient, the laminated glass is inserted into the autoclave, for example, as a finishing process. Then, heating and pressurization may be performed.

  The manufacturing method of the laminated glass of this invention can be performed by the above-mentioned method. In the method for producing a laminated glass of the present invention, since the polymer intermediate film contains a near infrared absorber, the polymer intermediate film can be efficiently heated by irradiation with near infrared rays.

  In the laminated glass obtained by the production method of the present invention, since the polymer intermediate film contains a near-infrared absorber, for example, when used for automobiles or for architectural purposes, the interior of the vehicle or building in the summer is used. An increase in temperature can be suppressed.

  EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.

[Example 1]
(Preparation of near infrared absorber)
A solution (a1) obtained by dissolving 1.16 g (5.83 × 10 ⁻³ mol) of copper acetate monohydrate in 60 g of ethanol, and equimolar ethylphosphonic acid 0 with respect to copper acetate monohydrate A solution (b1) prepared by dissolving .64 g and 0.5 g of the following phosphoric ester compound (A) in 5 g of ethanol was prepared.

The phosphate ester compound (A) includes a phosphate ester compound (monoester) represented by the general formula (2a) and a phosphate ester compound (diester) represented by the general formula (2b). And a triester in which the hydrogen atom of the hydroxyl group in the general formula (2b) is further substituted with the same group, wherein n is 10, and R ²¹ , R ²² , R ²³ are It is an alkyl group having 13 to 15 carbon atoms. In addition, the abundance ratio (molar ratio) of the monoester, diester, and triester in the phosphoric ester compound (A) is approximately 1: 1: 1.

Next, the solution (a1) and the solution (b1) obtained by the above method were mixed and reacted by stirring at room temperature for 2 hours.
After the reaction, the reaction solution was dried under reduced pressure at 50 ° C. until there was no odor of acetic acid to obtain 1.50 g of a solid (near infrared absorber).

  Toluene (near-infrared absorbent dispersion liquid) in which the obtained solid substance and 20 g of toluene were added to a glass container, and the near-infrared absorbent was dispersed by placing the whole glass container in an ultrasonic cleaner for 2 hours and carrying out a dispersion treatment. ) The average particle diameter of the near-infrared absorber (copper complex) in this dispersion was 55 nm. In addition, the average particle diameter was calculated | required using Otsuka Electronics Co., Ltd. ELSZ-2.

(Creation of polymer interlayer and laminated glass material)
Next, 2.75 g of this near-infrared absorber dispersion and 2.09 g of triethylene glycol bis-2-ethylhexanoate were dissolved in 150 ml of a toluene / ethanol (2/1) mixed solution, and polyvinyl butyral 5. 50 g was added and dissolved. A polyvinyl butyral resin containing a near infrared absorber was obtained from the polyvinyl butyral resin solution containing the near infrared absorber by a solvent casting method.

A polyvinyl butyral resin containing a near-infrared absorber obtained by a solvent casting method is pressed to create a sheet having a thickness of 0.8 mm, and a polymer intermediate film containing a near-infrared absorber having a size of 50 mm × 50 mm × 0.8 mm is produced. did. This polymer intermediate film was sandwiched between white plate glasses of 50 mm × 50 mm × 2 mm to prepare a laminated glass material.
Next, a sample (a laminated glass material fitted with a thermocouple) capable of measuring temperature was prepared by inserting a thermocouple to the center of the polymer intermediate film constituting the laminated glass material.

(Measurement of temperature change by near infrared irradiation)
As a heating lamp, an infrared drying bulb IR100V125WRHE manufactured by Toshiba Corporation was used, and a laminated glass material equipped with the thermocouple was installed at a location 10 cm away. The heating lamp was turned on and near-infrared irradiation was performed. The elapsed time after lighting the lamp and the temperature of the interlayer resin layer were measured. A spectral distribution diagram of an infrared drying bulb IR100V125WRHE manufactured by Toshiba Corporation is shown in FIG.

  As a control, a laminated glass material with a thermocouple made using a polymer intermediate film obtained from polyvinyl butyral containing no near-infrared absorber was also used after the heating lamp was turned on. The temperature change was measured.

The results are shown in FIG.
As is clear from FIG. 2, by using a polymer intermediate film containing a near infrared absorber, the heating time can be shortened compared to the case where the near infrared absorber is not contained, and the polymer intermediate film The temperature of the film can be made higher.

(Creation of laminated glass)
A laminated glass material was prepared in the same manner as described in the above-mentioned section of the method for producing a polymer intermediate film and a laminated glass material. The laminated glass material is not equipped with a thermocouple.

  Next, an infrared drying bulb IR100V125WRHE manufactured by Toshiba Corporation was used as a heating lamp, and the laminated glass material was installed at a location 10 cm away. The heating lamp was turned on, near-infrared irradiation was performed for 5 minutes, and after irradiation, temporary bonding was performed using a pressure roller. Thereafter, as a finishing step, the laminated glass was put in an autoclave, and heated and pressed at 130 ° C. for 20 minutes at a pressure of 1.5 MPa. Thereafter, it was cooled to obtain a laminated glass.

[Example 2]
(Measurement of temperature change by near infrared irradiation)
The same procedure as in Example 1 was conducted except that the distance between the heating lamp and the laminated glass material fitted with the thermocouple was changed from 10 cm to 5 cm. The elapsed time after the lamp was turned on and the temperature of the interlayer resin layer were changed. It was measured.

As a control, a laminated glass material with a thermocouple made using a polymer intermediate film obtained from polyvinyl butyral containing no near-infrared absorber was also used after the heating lamp was turned on. The temperature change was measured.
The results are shown in FIG.

  As apparent from FIG. 3, by using a polymer intermediate film containing a near-infrared absorber, the heating time is shortened compared to the case where the near-infrared absorber is not contained, and the polymer intermediate film The temperature of the film can be made higher.

(Creation of laminated glass)
Laminated glass was manufactured in the same manner as in Example 1 except that the distance between the heating lamp and the laminated glass material not equipped with the thermocouple was changed from 10 cm to 5 cm.

Claims (8)

A method for producing a laminated glass from a laminated glass material (X) in which a polymer intermediate film is sandwiched between two sheet glasses,
The polymer intermediate film contains a near infrared absorber,
The laminated glass material (X) is irradiated with near infrared rays to heat the polymer intermediate film, and the sheet glass is bonded to the polymer intermediate film to bond the plate glass and the polymer intermediate film. A method for producing a laminated glass, comprising obtaining glass.   The method for producing a laminated glass according to claim 1, wherein the near-infrared absorber is a fine particle having an average particle diameter of 200 nm or less having a near-infrared absorption characteristic.   The manufacturing method of the laminated glass of Claim 1 or 2 in which the said near-infrared absorber contains at least 1 sort (s) selected from a copper ion, a metal oxide, a boride, and a tungstic acid derivative. The manufacturing method of the laminated glass of Claim 1 or 2 in which the said near-infrared absorber contains the copper compound obtained by making the phosphonic acid compound represented by following formula (1), and a copper salt react.

[Wherein R ¹ is a monovalent group represented by —CH ₂ CH ₂ —R ¹¹ , and R ¹¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a fluorinated alkyl having 1 to 20 carbon atoms. Indicates a group. ]   The near infrared irradiation is performed by at least one light source selected from a halogen heater, a halogen lamp, an infrared drying lamp, a light emitting diode that emits light in the near infrared region, and a laser that emits light in the near infrared region. The manufacturing method of the laminated glass as described in any one of 1-4.   The method for producing a laminated glass according to any one of claims 1 to 5, wherein the heating of the polymer intermediate film is performed by heating means other than near infrared irradiation in addition to heating by near infrared irradiation.   The manufacturing method of the laminated glass as described in any one of Claims 1-6 whose solar radiation transmittance (JISR3106) of at least one of the said plate glass is 70% or more.   The manufacturing method of the laminated glass as described in any one of Claims 1-6 whose solar radiation transmittance (JISR3106) of at least one of the said plate glass is less than 70%.

Images