JP2019108247A - Laminated glass, and production method thereof - Google Patents

Abstract

To suppress generation of air bubbles on and near the boundary face between an inorganic glass and an interlayer at high temperature and humidity in a laminated glass having the organic glass and the interlayer.SOLUTION: A laminated glass includes a first glass plate 11 and a second glass plate 12 opposite to each other, and an interlayer 5 arranged between them. The first glass plate 11 is an inorganic glass plate having a surface S surface-treated by a coupling agent, the surface S contacting the interlayer 5.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated glass and a method of manufacturing the same.

  Laminated glass is widely used as a glass of a window of a vehicle such as a car, a sunroof, an interior panel and the like. Other applications of laminated glass include windows in trains, aircraft, construction machines, buildings and the like.

  As an example of a laminated glass, there is an integrated film in which an intermediate film made of polyvinyl acetal resin such as polyvinyl butyral resin plasticized with a plasticizer is interposed between at least a pair of glass plates and integrated them (for example, Patent Document 1) ~ 3).

Unexamined-Japanese-Patent No. 1987-100463 JP 2005-206445 A WO 12/091117

  Conventional laminated glass may generate air bubbles at or near the interface between the inorganic glass plate and the intermediate film when left in a high-temperature, high-humidity environment such as a temperature of 85 ° C. and a relative humidity of 85%. .

  An object of one aspect of the present invention is to suppress the generation of air bubbles in the vicinity of the interface between an inorganic glass and an intermediate film under high temperature and high humidity with respect to a laminated glass having an inorganic glass and an intermediate film.

  One aspect of the present invention relates to a laminated glass including opposed first and second glass plates and an intermediate film disposed therebetween. The first glass plate is an inorganic glass plate having a surface surface-treated with a coupling agent, and the surface-treated surface of the inorganic glass plate is in contact with the intermediate film.

  In this laminated glass, since the inorganic glass in contact with the interlayer is surface-treated with the coupling agent, the generation of air bubbles at the interface between the inorganic glass and the interlayer under high temperature and high humidity and the vicinity thereof is sufficiently suppressed. Be done.

  Another aspect of the present invention is the step of surface-treating the surface of a first glass plate which is an inorganic glass plate with a coupling agent, and a first glass plate and a second glass having the surface-treated surface. The plate is bonded with a resin layer interposed, and the first glass plate, the resin layer, and the second glass plate are provided, and the surface-treated surface of the first glass plate is The present invention relates to a method for producing a laminated glass comprising the steps of: obtaining a laminate in contact with the interlayer; and heating and pressing the laminate to obtain laminated glass having the resin layer as an interlayer. .

The interlayer and the resin layer may contain an acrylic polymer. Acrylic polymer is
(A) an alkyl (meth) acrylate monomer which is an ester of an alkyl alcohol having 1 to 18 carbon atoms and (meth) acrylic acid;
(B) Copolymer containing (meth) acrylate monomer containing at least one of carboxyl group or hydroxyl group, and (c) silane compound having radically polymerizable unsaturated group and siloxane chain or alkoxysilyl group as monomer unit It may be

  The coupling agent may be a silane coupling agent. The silane coupling agent may have at least one functional group selected from the group consisting of an epoxy group, an acrylic group, a methacrylic group, an amino group and an isocyanate group.

  The second glass plate may be a transparent plastic plate. According to the findings of the present inventors, if the second glass plate is a transparent plastic plate, many bubbles tend to be easily generated at the interface between the inorganic glass and the interlayer and in the vicinity thereof in a high temperature and high humidity environment. . Therefore, the bubble suppression by the laminated glass of the present invention and the method for producing the same has a particularly high technical significance when the second glass plate is a transparent plastic plate.

  According to the present invention, with regard to laminated glass having an inorganic glass and an intermediate film, it is possible to suppress the generation of air bubbles at the interface of the inorganic glass and the intermediate film under high temperature and high humidity and in the vicinity thereof.

It is a sectional view showing one embodiment of a laminated glass. It is sectional drawing which shows one Embodiment of the film material for intermediate films of laminated glass.

  Hereinafter, some embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  As used herein, "(meth) acrylate" means "acrylate" or the corresponding "methacrylate". Similar expressions such as “(meth) acrylic” are also the same. The content of each component in the composition means, when there is a plurality of substances corresponding to each component in the composition, the total amount of the plurality of substances present in the composition unless otherwise specified.

<Laminated glass>
FIG. 1 is a cross-sectional view showing an embodiment of a laminated glass. The laminated glass 1 shown in FIG. 1 is disposed between, and in contact with, the opposing first and second glass plates 11 and 12 and the first and second glass plates 11 and 12. And an intermediate film 5. In other words, the first glass plate 11, the intermediate film 5, and the second glass plate 12 are stacked in this order.

  The first glass plate 11 may be an inorganic glass plate, and the second glass plate 12 may be a transparent plastic plate or an inorganic glass plate.

  The inorganic glass plate as the first glass plate 11 or the second glass plate 12 can be selected from those generally used as a glass plate constituting laminated glass. By providing the inorganic glass plate, the surface of the laminated glass can have good scratch resistance. The inorganic glass plate may be, for example, a float glass, a tempered glass (air-cooled tempered glass, chemically tempered glass, etc.), or a double-layered glass plate.

  The transparent plastic plate as the second glass plate 12 can be a plastic plate having optical properties such as transparency suitable for laminated glass. Examples of transparent plastic plates include polycarbonate plates (PC plates), polymethyl methacrylate plates (PMMA plates), cyclopolyolefin plates (COP plates), polyethylene terephthalate plates (PET plates), polyethylene plates (PE plates), polypropylene plates ( PP board), polystyrene board (PS board), and triacetyl cellulose board (TAC board) are mentioned.

  The surface S in contact with the intermediate film 5 of the first glass plate 11 which is an inorganic glass plate is surface-treated with a coupling agent. Therefore, a film 7 containing a coupling agent may be formed in the vicinity of the interface between the intermediate film 5 and the first glass plate 11. However, the film 7 containing the coupling agent may not be formed as a film having a clear boundary with the intermediate film 5. Also, the coupling agent may not cover the entire surface S. The presence of the coupling agent in the vicinity of the surface S surface-treated with the coupling agent in the laminated glass 1 is confirmed because, for example, the peel strength between the first glass plate 11 and the intermediate film 5 is improved. Although it is possible, it is technically difficult and not practical to directly analyze the form of distribution of the coupling agent in a minute region near the interface. When the second glass plate 12 is an inorganic glass plate, the surface may be surface-treated with a coupling agent.

  In the present specification, "surface-treating the surface of a glass plate with a coupling agent" refers to attaching the coupling agent to the surface of the glass plate and heating the glass plate and the coupling agent attached to the surface. means. In the surface treated with the coupling agent, usually, at least a part of the coupling agent attached to the surface forms a chemical bond with silicon atoms and the like constituting the glass plate.

  The coupling agent is generally a compound having a reactive group for forming a chemical bond with an inorganic material and a functional group for forming a chemical bond with an organic material. For example, the silane coupling agent has an alkoxysilyl group as a reactive group to form a chemical bond with the inorganic material. Examples of functional groups for forming chemical bonds with organic materials include epoxy groups, acrylic groups, methacrylic groups, amino groups, isocyanate groups, vinyl groups and styryl groups. The coupling agent may have at least one functional group selected from the group consisting of an epoxy group, an acryl group, a methacryl group, an amino group and an isocyanate group. The functional group that the coupling agent has may be a group that reacts with the functional group (for example, hydroxyl group) that the acrylic polymer has. The coupling agent having an epoxy group or an isocyanate group can exhibit a particularly excellent effect in terms of air bubble suppression under high temperature and high humidity.

  The surface of the inorganic glass plate is, for example, attaching a coupling agent solution containing a coupling agent and a solvent to the surface of the inorganic glass, and heating the inorganic glass and the coupling agent solution attached to the surface to make the solvent The surface treatment with the coupling agent can be performed by a method including removing. The concentration of the coupling agent in the coupling agent solution may be, for example, 1 to 10% by mass based on the mass of the coupling agent solution. The solvent may be any solvent that dissolves the coupling agent, and may be, for example, methanol. The coupling agent solution can be adhered to the surface of the inorganic glass by immersing the surface of the inorganic glass at normal temperature (about 23 ° C.), for example, for about 12 to 24 hours. The temperature for heating the inorganic glass and the coupling agent solution attached to the surface thereof is determined in consideration of the boiling point of the solvent and the like, and is, for example, 60 to 120 ° C. The heating time may be 30 minutes to 2 hours.

  The thickness of the intermediate film 5 is not particularly limited because it is appropriately adjusted depending on the use and method, but may be 25 to 200 μm, 25 to 180 μm, or 25 to 150 μm. Thereby, laminated glass can have especially high break resistance.

  The light transmittance to light in the visible light range (wavelength: 380 nm to 780 nm) of the intermediate film 5 may be 80% or more, 90% or more, or 95% or more.

The haze of the laminated glass may be 5% or less. Haze is a value (%) representing turbidity, which is the total transmittance T _t of the light transmitted by the lamp and transmitted through the sample, and the transmittance T _{d of the} light diffused and scattered in the sample From this, it can be obtained as (T _d / T _t ) × 100. These are defined by JIS K 7136 and can be easily measured by a commercially available turbidimeter, for example, NDH 5000 manufactured by Nippon Denshoku Kogyo Co., Ltd.

  The laminated glass is not limited to the form shown in FIG. For example, the laminated glass may have three or more glass plates, and may have functional layers such as an antireflective layer, an antifouling layer, a dye layer, and a hard coat layer, and the like. A glass plate may be these functional layers. An intermediate film similar to the intermediate film 5 can be provided between these glass plates or functional layers. The intermediate film may be a multilayer in which two or more layers of films are stacked. As the film to be laminated, the same film as the intermediate film 5 can be provided.

  The antireflective layer may be a layer exhibiting a visible light reflectance of 5% or less. The antireflective layer may be a transparent substrate (such as a transparent plastic film) that has been treated with known antireflective methods.

  An antifouling layer is a layer which controls the dirt to the surface. The antifouling layer can be, for example, a layer having a low surface tension, which is composed of a fluorine-based resin or a silicone-based resin to lower the surface tension.

  The dye layer is used to increase color purity. The dye layer is used to reduce light of unnecessary wavelengths transmitted by the laminated glass. The dye layer can be obtained by dissolving a dye that absorbs light of unnecessary wavelength in a resin, and forming or laminating it on a base film such as a polyethylene film or a polyester film.

  The hard coat layer is a layer for increasing the surface hardness. The hard coat layer is a laminate having a base film (polyethylene film or the like) and a resin layer formed on the base film and containing a resin such as an acrylic resin (urethane acrylate, epoxy acrylate or the like) or an epoxy resin. It may be It is also possible to use a hard coat layer laminated on a transparent protective plate such as a glass plate, an acrylic resin plate or a polycarbonate plate.

<Method of manufacturing laminated glass>
The laminated glass 1 is, for example, a step of surface-treating the surface S of the first glass plate 11 which is an inorganic glass plate with a coupling agent, and the first glass plate 11 having a surface-treated surface S and a second Bonding the glass plate 12 with the resin layer interposed to obtain a laminate having the first glass plate 11, the resin layer, and the second glass plate 12, and heating and pressing the laminate And a step of obtaining the laminated glass 1 having the resin layer as the intermediate film 5.

  About the detail of the process of surface-treating surface S of the 1st glass plate 11 with a coupling agent, it is as above-mentioned. For the first glass plate 11 and the second glass plate 12, for example, disposing a resin layer on the surface S of the first glass plate 11, and subsequently laminating the second glass plate 12 on the resin layer And bonding can be performed while interposing the resin layer. The resin layer can be provided on the first glass plate 11 using a film material for an intermediate film of laminated glass.

  FIG. 2: is a schematic cross section which shows one Embodiment of the film material for intermediate films of the laminated glass which has a resin layer used as the intermediate film 5. As shown in FIG. The film material 2 for an intermediate film of laminated glass shown in FIG. 2 has a base 21, a resin layer 5 a and a base 22, and these are laminated in this order. The resin layer 5a is a layer to be the intermediate film 5 when sandwiched between two glass plates, and can be a film-like resin composition. The resin layer 5a may have pressure-sensitive adhesiveness which enables easy bonding of the glass plates. According to such a film material, the resin layer 5a can be easily stored and transported.

  The substrates 21 and 22 may be, for example, a film of a polymer selected from polyethylene terephthalate, polypropylene, and polyethylene, and in particular may be a polyethylene terephthalate film (hereinafter sometimes referred to as "PET film") . The end portions of the base members 21 and 22 may protrude outward beyond the outer edge of the resin layer 5a.

  One of the substrates 21 and 22 may be a substrate (a heavy peeling separator) that exhibits relatively high peel strength, and the other may be a substrate (a light peel separator) that exhibits relatively low peel strength. . The peel strength between the light release separator and the resin layer 5a is lower than the peel strength between the heavy release separator and the resin layer 5a. The releasability of the substrate can be appropriately adjusted according to the conditions of the surface treatment that imparts releasability. As a method of surface treatment, for example, a release treatment with a silicone compound or a fluorine compound is mentioned.

  When the interlayer film material 2 is used to manufacture the laminated glass 1, first, the base material as the light release separator is peeled off, and the exposed surface of the resin layer 5 a is attached to the first glass plate 11. You may press by the roller etc. from the base material side as a heavy release separator. Then, the base material as a heavy release separator is peeled from the resin layer 5a. The surface of the exposed resin layer 5 a is attached to the second glass plate 12. By this method, two glass plates can be easily bonded together with the resin layer 5a interposed.

  From the viewpoint of workability, the thickness of the substrate as the heavy release separator may be 50 to 200 μm, 60 to 150 μm, or 70 to 130 μm. From the viewpoint of workability, the thickness of the substrate as the light release separator is 25 to 150 μm, 30 to 100 μm, or 40 to 80 μm.

  The laminate having the first glass plate 11, the resin layer 5a, and the second glass plate 12 is heated and pressurized using, for example, an autoclave. The heating and pressurizing conditions may be, for example, a temperature of 30 to 150 ° C. and a pressure of 0.3 to 1.5 MPa. The temperature may be 50 to 70 ° C., and the pressure may be 0.3 to 0.5 MPa, from the viewpoint of being able to further remove air bubbles caused by rolling. The heating and pressurizing time may be 5 to 60 minutes, or 10 to 30 minutes.

<Resin composition for interlayer film of laminated glass>
The resin composition for forming the intermediate film 5 (or the resin layer 5a) may contain an acrylic polymer.

  The acrylic polymer is a copolymer mainly composed of monomer units derived from a monomer having a (meth) acryloyl group, and, for example, (a) an alkyl alcohol having 1 to 18 carbon atoms and (meth) acrylic acid Ester (alkyl) (meth) acrylate monomer, (b) hydroxyl group-containing (meth) acrylate monomer, and (c) silicon-containing monomer having a radically polymerizable unsaturated group and a siloxane chain or alkoxysilyl group as monomer units The copolymer may be included. The resin composition containing the acrylic polymer has particularly high adhesion to the surface of the glass plate and can form an interlayer having high toughness, thereby further improving the split resistance of the laminated glass. it can.

The (a) alkyl (meth) acrylate monomer has, for example, the following formula:
CH ₂ = CXCOOR
It can be a compound represented by In formula, X shows a hydrogen atom or a methyl group, R shows a C1-C18 alkyl group. Examples of (a) alkyl (meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n- Pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate (n- Examples include lauryl (meth) acrylate) and stearyl (meth) acrylate. The alkyl (meth) acrylate monomer is at least one selected from the group consisting of n-butyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and n-octyl (meth) acrylate It may be 2-ethylhexyl (meth) acrylate. Two or more of these alkyl (meth) acrylate monomers may be combined. The alkyl (meth) acrylate monomer may be an alkyl acrylate.

  (A) The content of the monomer unit derived from the alkyl (meth) acrylate may be 50 to 90% by mass, or 50 to 85% by mass, based on the total mass of the monomer units constituting the acrylic polymer. . When the content of the monomer unit derived from the alkyl (meth) acrylate is in such a range, the adhesion between the intermediate film 5 and the first glass plate 11 and the second glass plate 12 is further improved.

  (B) Examples of (meth) acrylate monomers containing a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate ) Acrylate, 1-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 1-hydroxybutyl (meth) acrylate Be

  (B) The content of the monomer unit derived from the (meth) acrylate monomer having a hydroxyl group is 5 to 30% by mass or 10 to 30% by mass based on the total mass of the monomer units constituting the acrylic polymer. May be When the content of the monomer unit derived from the hydroxyl group-containing (meth) acrylate monomer is within these ranges, the laminated glass tends to maintain particularly high transparency in the reliability test under high temperature and high humidity.

  (C) The silicon-containing monomer may have, for example, one radically polymerizable unsaturated group selected from (meth) acrylic group, styryl group, cinnamate ester group, vinyl group and allyl group.

  Examples of the silicon-containing monomer having a (meth) acrylic group and a siloxane chain include compounds represented by the following formula (a) or (b).

式（ａ）中、Ｒ¹は水素原子又はメチル基を示し、Ｒ^２は２価の炭化水素基、炭化水素基と酸素原子との組み合わせからなる２価の基、又は単結合を示し、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立に水素原子又はメチル基を示し、Ｒ^９は１価の炭化水素基を示し、ｎは１以上の整数を示す。

In formula (a), R ¹ represents a hydrogen atom or a methyl group, R ² represents a divalent hydrocarbon group, a divalent group consisting of a combination of a hydrocarbon group and an oxygen atom, or a single bond, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, R ⁹ represents a monovalent hydrocarbon group, and n represents an integer of 1 or more.

式（ｂ）中、Ｒ¹は水素原子又はメチル基を示し、Ｒ^２及びＲ^９はそれぞれ独立に２価の炭化水素基、炭化水素基と酸素原子との組み合わせからなる２価の基、又は単結合を示し、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立に水素原子又はメチル基を示し、ｎは１以上の整数を示す。

In formula (b), R ¹ represents a hydrogen atom or a methyl group, R ² and R ⁹ each independently represent a divalent hydrocarbon group, a divalent group consisting of a combination of a hydrocarbon group and an oxygen atom, or R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and n represents an integer of 1 or more.

  The weight average molecular weight of the silicon-containing monomer having a (meth) acrylic group and a siloxane chain may be 100 to 20,000.

式（ｃ）中、Ｒ¹は水素原子又は１価の炭化水素基を示し、Ｒ^２は２価の炭化水素基、炭化水素基と酸素原子との組み合わせからなる２価の基、又は単結合を示し、Ｒ^３は水素原子又はメチル基を示す。 Examples of the silicon-containing monomer having a (meth) acrylic group and an alkoxysilyl group include compounds represented by the following formula (c).

In formula (c), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group, and R ² represents a divalent hydrocarbon group, a divalent group consisting of a combination of a hydrocarbon group and an oxygen atom, or a single bond And R ³ represents a hydrogen atom or a methyl group.

  The compounds represented by formulas (a) to (c) can be used alone or in combination of two or more.

  The content of the monomer unit derived from the silicon-containing monomer (c) may be 5 to 20% by mass, or 10 to 20% by mass, based on the total mass of the monomer units constituting the acrylic polymer. When the content of the monomer unit derived from the silicon-containing monomer is within these ranges, a laminated glass having higher split resistance is easily obtained.

  The acrylic polymer may further contain monomer units derived from other monomers having a (meth) acryloyl group. Examples of other monomers include (meth) acrylates having an aromatic ring such as (meth) acrylic acid, benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and di (Meth) acrylates having an alicyclic substituent such as cyclopentanyl (meth) acrylate; tetrahydrofurfuryl (meth) acrylate; N, N-dimethylaminoethyl (meth) acrylate; N, N-dimethylaminopropyl ( (Meth) acrylamide; (meth) acrylamide; N, N- dimethyl (meth) acrylamide, N- isopropyl (meth) acrylamide, N, N- diethyl (meth) acrylamide, N- hydroxyethyl (meth) acrylamide, (meth) acryloyl (Meth) acrylamide derivatives such as morpholine; (meth) acrylates having isocyanate groups such as 2- (2-methacryloyloxyethyloxy) ethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, etc .; alkylene glycol chain-containing (meth) acrylates Can be mentioned.

The alkylene glycol chain-containing (meth) acrylate has, for example, the following formula:
CH ₂ = CXCOO (C _p H 2 _p O) _q R
It can be a compound represented by In the formula, X represents a hydrogen atom or a methyl group, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, p represents an integer of 2 to 4, and q represents an integer of 1 to 10. Examples of the alkylene glycol chain-containing (meth) acrylate include polyethylene such as diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate and hexaethylene glycol mono (meth) acrylate. Glycol mono (meth) acrylate; Polypropylene glycol mono (meth) acrylate such as dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, octapropylene glycol mono (meth) acrylate; Dibutylene glycol mono (meth) Polybutylene glycol mono (meth) acrylates such as acrylate, tributylene glycol mono (meth) acrylate, etc .; methoxytri Tylene glycol (meth) acrylate, methoxytetraethylene glycol (meth) acrylate, methoxyhexaethylene glycol (meth) acrylate, methoxyoctaethylene glycol (meth) acrylate, methoxynona ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate And alkoxypolyalkylene glycol (meth) acrylates such as methoxyheptapropylene glycol (meth) acrylate, ethoxytetraethylene glycol (meth) acrylate, butoxyethylene glycol (meth) acrylate, and butoxydiethylene glycol (meth) acrylate. Two or more compounds selected from these may be combined.

  Other monomers may have polar groups such as morpholino group, amino group, carboxyl group, cyano group, carbonyl group and nitro group. The monomer which has these polar groups can contribute to the adhesion improvement of an intermediate film and a glass plate.

  The acrylic polymer may further contain a monomer unit derived from a monomer having a radically polymerizable unsaturated group other than the (meth) acryloyl group. Examples of such monomers include monofunctional monomers such as acrylonitrile, styrene, vinyl acetate, ethylene and propylene, and difunctional monomers such as divinyl benzene.

  The weight average molecular weight of the acrylic polymer may be 8,000 to 1,000,000. When the weight average molecular weight is 80000 or more, the adhesion of the interlayer to the glass plate tends to be improved, and when the weight average molecular weight is 1,000,000 or less, the viscosity of the resin composition for forming the interlayer or resin layer Is not too high, and the intermediate film or resin layer can be easily formed. From the above viewpoints, the weight average molecular weight of the acrylic polymer may be 10000 to 900,000. The weight average molecular weight here means a conversion value by a calibration curve of standard polystyrene, which is measured by gel permeation chromatography (GPC).

  The method for obtaining the acrylic polymer is not particularly limited, and the acrylic polymer can be obtained by a general polymerization method such as solution polymerization, emulsion polymerization, suspension polymerization, bulk polymerization and the like. As a polymerization initiator for the polymerization reaction, a compound which generates radicals by heat can be used. Examples thereof include organic peroxides such as benzoyl peroxide, lauroyl peroxide and the like; 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile) and the like Azo compounds can be mentioned.

  The resin composition for forming the intermediate film 5 (or the resin layer 5a) may contain a crosslinking agent. When the resin composition contains a crosslinking agent, at least a part of the acrylic polymer is usually crosslinked by the crosslinking agent in the intermediate film 5 and the resin layer 5a. The crosslinking agent enhances the cohesion of the resin composition.

  The crosslinking agent is a compound that crosslinks the acrylic polymer by photoreaction and / or thermal reaction. The crosslinking agent which crosslinks the acrylic polymer by photoreaction may be a compound having two or more (meth) acryloyl groups, and examples thereof include the following formulas (1), (2), (3), The compound represented by (4), (5) or (6) is mentioned. S in formulas (1), (2) and (3) represents an integer of 1 to 20, and m and n in formulas (4) and (5) each independently represent an integer of 1 to 10.

  A urethane di (meth) acrylate having a urethane bond may be used as a crosslinking agent. The urethane di (meth) acrylate may have a polyalkylene glycol chain from the viewpoint of good compatibility with other components. From the viewpoint of securing transparency, the urethane di (meth) acrylate may have an alicyclic group. If the compatibility between the crosslinking agent and the acrylic polymer is high, the intermediate film is likely to have high transparency without becoming cloudy.

  The crosslinking agent that crosslinks the acrylic polymer by thermal reaction may be a compound having two or more isocyanate groups or epoxy groups, and may be a melamine compound. This crosslinking agent may be a polyfunctional crosslinking agent such as trifunctional or tetrafunctional in order to form a loosely spread network structure in the intermediate film.

  The crosslinking agent may be a compound having an isocyanate group. Examples include multifunctional hexamethylene diisocyanate derivatives. Examples of polyfunctional hexamethylene diisocyanate derivatives include trimers of hexamethylene diisocyanate, and triols such as trimethylolpropane, reaction products of monofunctional alcohols or diols with hexamethylene diisocyanate.

  The weight average molecular weight of the crosslinking agent may be 100,000 or less, 300 to 100,000, or 500 to 80,000 from the viewpoint of being able to further suppress the occurrence of air bubbles and peeling under high temperature or high temperature and high humidity.

  The content of the crosslinking agent may be 15% by mass or less, 10% by mass or less, or 7% by mass or less based on the total mass of the resin composition. When the content is in these ranges, an intermediate film having higher adhesion is easily formed. The lower limit of the content of the crosslinking agent is not particularly limited, but may be 0.1% by mass or more, 2% by mass or more, or 3% by mass or more from the viewpoint of film formation.

  The resin composition for forming the intermediate film 5 or the resin layer 5a may contain a photopolymerization initiator for promoting the reaction between the acrylic polymer and the crosslinking agent. The photopolymerization initiator promotes the curing reaction by irradiation of active energy rays. Here, the active energy rays refer to ultraviolet rays, electron beams, α rays, β rays, γ rays and the like.

  The photopolymerization initiator is not particularly limited, and known materials such as benzophenone type, anthraquinone type, benzoyl type, sulfonium salt, diazonium salt and onium salt can be used. Examples thereof include benzophenone, N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4. 4,4'-Dimethylaminobenzophenone, α-hydroxyisobutylphenone, 2-ethylanthraquinone, t-butylanthraquinone, 1,4-dimethylanthraquinone, 1-chloroanthraquinone, 2,3-dichloroanthraquinone, 3-chloro-2-methyl 2-methylanthraquinone Anthraquinone, 1,2-benzoanthraquinone, 2-phenylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1 , 2- Aromatic ketone compounds such as phenylethan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2,2-diethoxyacetophenone; benzoin compounds such as benzoin, methylbenzoin, ethylbenzoin; Benzoin ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin phenyl ether; benzyl compounds such as benzyl and benzyl dimethyl ketal; ester compounds such as β- (acridin-9-yl) (meth) acrylic acid; Acridine compounds such as 9-phenyl acridine, 9-pyridyl acridine, 1,7-diacridinoheptane, etc .; 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4 , 5 Di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) 5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4 2,4,5-Triarylimidazole dimers such as 5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer; 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -1-butanone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-pro Emissions; bis (2,4,6-trimethylbenzoyl) - phenyl phosphine oxide; oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone) and the like. These compounds may be used in combination of two or more.

  From the viewpoint of suppressing the coloration of the interlayer, the photopolymerization initiator is 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) Α-hydroxyalkylphenone compounds such as) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one; bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2) Acylphosphine oxide compounds such as 2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentyl phosphine oxide and 2,4,6-trimethyl benzoyl-diphenyl phosphine oxide; or oligo (2-hydroxy-2) -Methyl-1- (4- (1-methylvinyl) phenyl) propanone) It may be. In particular, two or more selected from these may be combined.

  In order to form a particularly thick interlayer or resin layer, the photopolymerization initiator may be bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4 Acyl phosphine oxide compounds such as 2,4-trimethyl-pentyl phosphine oxide and 2,4,6-trimethyl benzoyl-diphenyl phosphine oxide may be included.

  The content of the photopolymerization initiator may be 0.05 to 5% by mass, 0.1 to 3% by mass, or 0.1 to 0.5% by mass based on the mass of the resin composition. When the content of the photopolymerization initiator is 5% by mass or less, the transmittance is high, the yellowish color is not easily obtained, and the interlayer film having excellent transparency can be easily formed.

  The resin composition may contain various additives in addition to the crosslinking agent. Specific examples thereof include a polymerization inhibitor such as paramethoxyphenol which is added for the purpose of enhancing the storage stability of the resin composition, a resin composition Antioxidants such as triphenyl phosphite added for the purpose of enhancing the heat resistance of the adhesive layer obtained by light curing, and HALS added for the purpose of enhancing the resistance of the adhesive resin composition to light such as ultraviolet rays (Hindered Amine And light stabilizers such as Light Stabilizer.

  The resin composition may contain a surfactant such as a polydimethylsiloxane surfactant or a fluorosurfactant in order to control the releasability of the film material from the substrate.

  The film material 2 for intermediate films of laminated glass can be obtained, for example, by forming a resin composition for forming the resin layer 5 a on the substrate 21. The film formation can be performed by a conventional method. For example, an intermediate film is formed by a method including applying a coating liquid prepared by diluting the resin composition with a solvent on the substrate 21 and drying the solvent from the coating film to form the resin layer 5a. Film material can be obtained. Examples of the coating method include a flow coating method, a roll coating method, a gravure coating method, a wire bar coating method, and a lip die coating method.

  As a solvent for preparing the said coating liquid, solvents, such as 2-butanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, toluene, can be used, for example. From the viewpoint of coatability, the solid content concentration of the coating liquid (the concentration of components other than the solvent) may be 30% by mass or more, or 40% by mass or more based on the mass of the coating liquid. It may be 70% by mass or less, or 60% by mass or less. The viscosity of the coating liquid may be 1 Pa · s or more, or 5 Pa · s or more, or 30 Pa · s or less, 5 Pa · s or less, or 15 Pa · s or less at the coating temperature.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to these examples.

Example 1
1. Preparation of film material for interlayer film of laminated glass Synthesis of acrylic polymer 85.0 g of 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate in a reaction vessel equipped with a condenser, thermometer, stirrer, dropping funnel and nitrogen introduction pipe Add 10.0 g, one end methacryloyl modified polysiloxane compound (Shin-Etsu Chemical Co., Ltd., X-22-2426, product name, weight average molecular weight 12000) 5.0 g and 145.0 g of ethyl acetate, air volume of 100 mL / min The flask was heated from normal temperature (25.degree. C.) to 65.degree. C. over 15 minutes while purging with nitrogen.
Thereafter, while maintaining the temperature at 65 ° C., a solution prepared by dissolving 0.1 g of lauroyl peroxide in 5.0 g of ethyl acetate is charged, and a polymerization reaction is allowed to proceed for 8 hours to obtain an acrylic polymer (weight average molecular weight 700,000 Solution (solid content 40% by mass) was obtained.
The weight average molecular weight was determined as a conversion value determined by a standard polystyrene calibration curve by gel permeation chromatography using the following apparatus and conditions.
Device: Hitachi High-Tech Science RI Detector: L-3350
Solvent used: THF
Column: Hitachi Chemical Co., Ltd. Gelpac GL-R420 + R430 + R440
Column temperature: 40 ° C
Flow rate: 2.0 mL / min

Preparation of resin composition for interlayer film of laminated glass A solution of an acrylic polymer and a polyisocyanate compound ("Coronate HL" manufactured by Tosoh Corp.) which is a hexamethylene diisocyanate derivative as a crosslinking agent are mixed and stirred, A resin composition for interlayer film of laminated glass was obtained. The amount of Coronate HL was 0.2% by mass with respect to the mass of the acrylic polymer.

Film material for interlayer film of laminated glass The resin composition for interlayer film of laminated glass was applied to the surface of the polyethylene terephthalate film (heavy release separator) on which the release treatment was performed using a bar coater. The coated film was dried by heating at 100 ° C. for 15 minutes to form a resin layer with a thickness of 100 μm. The resin layer was covered with a polyethylene terephthalate film (light release separator) in the direction in which the surface subjected to mold release treatment was in contact with the resin layer, and attached with a 1.0 kgf hand roller to obtain a film material for interlayer film of laminated glass.

A silane coupling agent having a laminated glass epoxy group was dissolved in methanol to prepare a silane coupling agent solution having a concentration of 1.8% by mass. The surface of float glass having a length of 110 mm, a width of 110 mm, and a thickness of 2.7 mm was immersed in this silane coupling agent solution for about 15 hours. Thereafter, the silane coupling agent solution attached to the surface of the float glass was dried by heating at 100 ° C. for 1 hour to obtain float glass having a surface treated with a silane coupling agent.
On the surface of the float glass surface-treated with the silane coupling agent, an intermediate film of an interlayer film material of laminated glass exposed by peeling off the light release separator was attached, and the film material was pressed against the float glass by a roller. The heavy release separator was peeled from the intermediate film to expose the surface of the intermediate film, and a 25 mm wide polyester adhesive tape (Nitto 31B, manufactured by Nitto Denko Corporation) was attached thereto and pressed with a roller. The laminated body on which the float glass, the interlayer and the polyester adhesive tape were laminated was heated and pressurized in an autoclave at a temperature of 50 ° C. and a pressure of 0.5 MPa for 30 minutes to obtain a laminated glass sample.

Example 2
A sample of laminated glass was obtained in the same manner as in Example 1 except that the silane coupling agent having an epoxy group was changed to a silane coupling agent having an isocyanate group.

Comparative Example 1
A sample of laminated glass was obtained in the same manner as in Example 1 except that the surface of the float glass was not surface-treated with a silane coupling agent.

Comparative example 2
A solution of the same acrylic polymer as in Example 1, a polyisocyanate compound ("Coronate HL" manufactured by Tosoh Corp.), which is a hexamethylene diisocyanate derivative as a crosslinking agent, and a silane coupling agent having an epoxy group are mixed. The mixture was stirred to obtain a laminated glass resin composition for an interlayer. The amount of Coronate HL was 0.2% by mass with respect to the mass of the acrylic polymer. The amount of the silane coupling agent was 2% by mass with respect to the mass of the acrylic polymer. Using the obtained resin composition, a sample of laminated glass was obtained in the same manner as in Example 1 except that the surface of the float glass was not surface-treated with a silane coupling agent.

Comparative example 3
A sample of laminated glass was obtained in the same manner as in Comparative Example 2 except that the silane coupling agent having an epoxy group was changed to a silane coupling agent having an isocyanate group.

3. Evaluation The sample of each produced laminated glass was attached to the jig | tool of the lower side of a table-top-type precision universal testing machine (ASG-X made from Shimadzu Corporation). The intermediate film of a portion of about 60 mm in length to which a width 25 mm polyester adhesive tape was attached was peeled off from the float glass, and the peeled portion was attached to the upper jig of the bench-top precision universal testing machine. Subsequently, the intermediate film was peeled off from the float glass at a tensile speed of 10 mm / min and a tensile angle of 180 °, and the stress at that time was measured. The obtained stress was divided by 25 mm of the test piece width to obtain an initial peel strength (unit: N / 25 mm).
Each sample prepared separately from the sample for the initial peel strength measurement was subjected to a high temperature and high humidity test in which the sample was left at a temperature of 85 ° C. and a humidity of 85% RH for 24 hours. The peel strength after the high temperature and high humidity test was measured in the same manner as described above. Further, each sample after the high temperature and high humidity test was observed, and the number of air bubbles generated inside the float glass was counted in a section of 2 cm × 2 cm float glass to obtain the number of air bubbles per 1 cm ² .

  Table 1 shows the evaluation results. The samples of the laminated glass of Examples 1 and 2 in which the interlayer was attached to float glass having a surface surface-treated with a silane coupling agent are the same as those of Comparative Examples 2 and 3 in which the same silane coupling agent was blended in the interlayer. The generation of air bubbles after the high temperature and high humidity test was less than that of the laminated glass sample.

  DESCRIPTION OF SYMBOLS 1 ... Laminated glass, 2 ... Film material for intermediate films of laminated glass, 5 ... Intermediate film, 7 ... Film containing a coupling agent, 5a ... Resin layer, 11 ... 1st glass plate, 12 ... 2nd glass plate 21, 22 ... base material, S ... surface treated with a coupling agent.

Claims (12)

A laminated glass comprising: opposing first and second glass plates; and an intermediate film disposed therebetween,
Laminated glass, wherein the first glass plate is an inorganic glass plate having a surface surface-treated with a coupling agent, and the surface-treated surface of the inorganic glass plate is in contact with the intermediate film.   The laminated glass of claim 1, wherein the interlayer comprises an acrylic polymer. The acrylic polymer is
(A) an alkyl (meth) acrylate monomer which is an ester of an alkyl alcohol having 1 to 18 carbon atoms and (meth) acrylic acid;
The copolymer of (b) a hydroxyl group-containing (meth) acrylate monomer, and (c) a silicon-containing monomer having a radically polymerizable unsaturated group and a siloxane chain or an alkoxysilyl group as a monomer unit. Laminated glass as described in.   The laminated glass according to any one of claims 1 to 3, wherein the coupling agent is a silane coupling agent.   The laminated glass according to any one of claims 1 to 4, wherein the coupling agent has at least one functional group selected from the group consisting of an epoxy group, an acryl group, a methacryl group, an amino group and an isocyanate group. .   The laminated glass according to any one of claims 1 to 5, wherein the second glass plate is a transparent plastic plate. Surface-treating the surface of the first glass plate, which is an inorganic glass plate, with a coupling agent;
The first glass plate and the second glass plate are pasted with a resin layer interposed, and the first glass plate, the resin layer, and the second glass plate are included, Obtaining a laminate in which the surface-treated surface of the glass plate is in contact with the resin layer;
Heating and pressing the laminate to obtain a laminated glass having the resin layer as an intermediate film;
A method of manufacturing a laminated glass, comprising:   8. The method of claim 7, wherein the resin layer comprises an acrylic polymer. The acrylic polymer is
(A) an alkyl (meth) acrylate monomer which is an ester of an alkyl alcohol having 1 to 18 carbon atoms and (meth) acrylic acid;
(B) Copolymer comprising (meth) acrylate monomer containing at least one of carboxyl group or hydroxyl group, and (c) silicon-containing monomer having radically polymerizable unsaturated group and siloxane chain or alkoxysilyl group as monomer unit 9. The method of claim 8, wherein the method is coalescing.   The method according to any one of claims 7 to 9, wherein the coupling agent is a silane coupling agent.   The method according to any one of claims 7 to 10, wherein the coupling agent has at least one functional group selected from the group consisting of an epoxy group, an acryl group, a methacryl group, an amino group and an isocyanate group.   The method according to any one of claims 7 to 11, wherein the second glass plate is a transparent plastic plate.

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