JP7402136B2 - laminated glass - Google Patents

Description

The present invention relates to laminated glass.

It is known that laminated glass, which is a combination of glass and a resin interlayer film, is useful for the purpose of preventing fragments from scattering when glass is broken and improving security. The resin interlayer film preferably has excellent adhesion to glass, transparency, penetration resistance, and flexibility. Polyvinyl acetal, represented by polyvinyl butyral (PVB), is widely used as a resin that can provide such a resin interlayer film. Although PVB can provide excellent performance as a resin interlayer film, it has low bending rigidity not only at high temperatures (e.g., 50°C) but also around room temperature (e.g., 25°C), so the resin interlayer film may wrinkle during the lamination process with glass. occurs and the yield tends to decrease. To avoid this problem, the lamination process must be performed at low temperatures. Further, when a resin interlayer film containing PVB is used in a laminated glass, the resin interlayer film is likely to soften and undergo creep deformation, and as a result, a problem may occur in which misalignment occurs in the laminated glass. As a means to solve these problems, a resin interlayer film in which urethane resin is laminated on both sides of a polycarbonate base material has been proposed (see, for example, Patent Documents 1 and 2). However, such resin interlayer films are still required to have improved transparency and heat creep resistance.

Japanese Patent Application Publication No. 6-321587 International Publication No. 2015/93352 pamphlet

Therefore, an object of the present invention is to provide a laminated glass with excellent transparency, which is manufactured by laminating glass with a resin interlayer film that is easy to handle when manufacturing the laminated glass.

で示される積層体の２５℃における曲げ剛性は、６Ｎ・ｍｍ以上、６０Ｎ・ｍｍ以下である、合わせガラス。
［２］下記式（２）：

で示される前記積層体の５０℃における曲げ剛性は、４Ｎ・ｍｍ以上、６０Ｎ・ｍｍ以下である、前記［１］に記載の合わせガラス。
［３］前記積層体において接着層（ＩＩ）の一方または両方に含有されるアクリル系ブロック共重合体（Ｘ）は、下記条件（ｉ）～（ｉｉｉ）：
（ｉ）アクリル系ブロック共重合体（Ｘ）は、アクリル酸エステル単位を主構成単位とする重合体ブロック（ａ１）の片末端または両末端にメタクリル酸エステル単位を主構成単位とする重合体ブロック（ａ２）が結合した構造を有すること、
（ｉｉ）重量平均分子量は５０，０００～１５０，０００であること、および
（ｉｉｉ）重合体ブロック（ａ２）の含有量は、アクリル系ブロック共重合体（Ｘ）を構成する全構成単位に対して１０～６０質量％であること
を満たす、前記［１］または［２］に記載の合わせガラス。
［４］前記積層体において接着層（ＩＩ）の一方または両方に含有されるアクリル系ブロック共重合体（Ｘ）は、アクリル酸エステル単位を主構成単位とする重合体ブロック（ａ１）の両末端にそれぞれメタクリル酸エステル単位を主構成単位とする重合体ブロック（ａ２）が結合した構造を有する、前記［１］～［３］のいずれかに記載の合わせガラス。
［５］前記樹脂中間膜（Ａ）は２以上の前記積層体を含む、前記［１］～［４］のいずれかに記載の合わせガラス。
［６］ＪＩＳ Ｋ７１３６：２０００に準拠して測定した前記積層体のヘイズは５％以下である、前記［１］～［５］のいずれかに記載の合わせガラス。
［７］ＪＩＳ Ｚ８７２２：２００９に準拠して測定した前記積層体の黄色度は３以下である、前記［１］～［６］のいずれかに記載の合わせガラス。



In order to solve the above-mentioned problems, the present inventors conducted intensive studies on laminated glass, and as a result, completed the present invention. That is, the present invention includes the following preferred embodiments.
[1] A laminated glass in which inorganic glass, resin interlayer film (A), and inorganic glass are laminated in this order,
The resin interlayer film (A) includes a laminate including an adhesive layer (II) containing an acrylic block copolymer (X) on both sides of a base layer (I) containing a polycarbonate resin,
The following formula (1):

The laminated glass has a bending rigidity at 25° C. of 6 N·mm or more and 60 N·mm or less.
[2] The following formula (2):

The laminated glass according to [1] above, wherein the laminate has a bending rigidity at 50° C. of 4 N·mm or more and 60 N·mm or less.
[3] The acrylic block copolymer (X) contained in one or both of the adhesive layers (II) in the laminate meets the following conditions (i) to (iii):
(i) The acrylic block copolymer (X) is a polymer block having a methacrylate ester unit as a main constituent unit at one or both ends of the polymer block (a1) having an acrylate ester unit as a main constituent unit. Having a structure in which (a2) is combined,
(ii) The weight average molecular weight is 50,000 to 150,000, and (iii) the content of the polymer block (a2) is relative to all the constituent units constituting the acrylic block copolymer (X). The laminated glass according to [1] or [2] above, wherein the laminated glass satisfies the condition that the amount of laminated glass is 10 to 60% by mass.
[4] The acrylic block copolymer (X) contained in one or both of the adhesive layers (II) in the laminate has both ends of the polymer block (a1) having acrylic acid ester units as its main constituent units. The laminated glass according to any one of [1] to [3] above, wherein the laminated glass has a structure in which a polymer block (a2) having a methacrylic acid ester unit as a main constitutional unit is bonded to each.
[5] The laminated glass according to any one of [1] to [4], wherein the resin interlayer film (A) includes two or more of the laminates.
[6] The laminated glass according to any one of [1] to [5], wherein the laminate has a haze of 5% or less as measured in accordance with JIS K7136:2000.
[7] The laminated glass according to any one of [1] to [6], wherein the laminate has a yellowness of 3 or less as measured in accordance with JIS Z8722:2009.

According to the present invention, it is possible to provide a laminated glass with excellent transparency, which is manufactured by laminating glass with a resin interlayer film that is easy to handle when manufacturing the laminated glass.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram showing one aspect of the laminated glass of this invention. FIG. 2 is a schematic diagram illustrating a compression shear test. It is a schematic diagram showing the test sample used for the heat resistance creep test of laminated glass. It is a schematic diagram showing the heat resistance creep test of laminated glass.

で示される積層体の２５℃における曲げ剛性は、６Ｎ・ｍｍ以上、６０Ｎ・ｍｍ以下である。 The present invention relates to a laminated glass in which an inorganic glass, a resin interlayer film (A), and an inorganic glass are laminated in this order. The resin interlayer film (A) includes a laminate having adhesive layers (II) containing an acrylic block copolymer (X) on both sides of a base layer (I) containing a polycarbonate resin, and having the following formula: (1):

The bending rigidity at 25° C. of the laminate shown by is 6 N·mm or more and 60 N·mm or less.

[Base material layer (I)]
In the present invention, the base layer (I) is made of polycarbonate resin or a polycarbonate resin composition.
<Polycarbonate resin>
The polycarbonate resin is not particularly limited. As the polycarbonate resin, known resins obtained by reacting a polyfunctional hydroxy compound and a carbonate-forming compound can be used alone or in combination of two or more. Examples of such resins include aromatic polycarbonate resins, aliphatic polycarbonate resins, and branched polycarbonate resins obtained by branching these resins.
Examples of aromatic polycarbonate resins include aromatic polycarbonate resins derived from 2,2-bis(4-oxyphenyl)propane (also known as bisphenol A), and resins containing polycarbonate components made of poly(ester carbonate). can be mentioned. These resins are copolyesters having carbonate groups, carboxylate groups and aromatic carbocyclic groups repeating in the linear polymer chain.
Examples of aliphatic polycarbonate resins include aliphatic polycarbonate resins composed of carbonic acid and aliphatic diols or alicyclic diols. This may be a copolymer containing multiple aliphatic diols or alicyclic diols, with structural units derived from aliphatic compounds typified by aliphatic diols or alicyclic diols in the molecular chain and It may also be a copolymer having a structural unit derived from an aromatic compound.

Examples of the polyfunctional hydroxy compound include linear aliphatic diols, branched aliphatic diols, alicyclic diols, other diols, and aromatic dihydroxy compounds. One polyfunctional hydroxy compound may be used alone, or two or more may be used in combination. These compounds are not particularly limited, but aromatic dihydroxy compounds are preferred from the viewpoint of easily obtaining superior heat resistance or mechanical strength.

Examples of aromatic dihydroxy compounds include 4,4'-dihydroxybiphenyls, bis(hydroxyphenyl) alkanes, bis(4-hydroxyphenyl) ethers, bis(4-hydroxyphenyl) sulfides, and bis(4- hydroxyphenyl) sulfoxides, bis(4-hydroxyphenyl) sulfones, bis(4-hydroxyphenyl) ketones, bis(hydroxyphenyl)fluorenes, dihydroxy-p-terphenyls, dihydroxy-p-quarterphenyls, Examples include bis(hydroxyphenyl)pyrazines, bis(hydroxyphenyl)menthanes, bis[2-(4-hydroxyphenyl)-2-propyl]benzenes, dihydroxynaphthalenes, and dihydroxybenzenes.

Among these, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl) ) diphenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3-phenyl) phenyl)propane, 4,4'-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfone, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 3,3-bis(4-hydroxyphenyl) ) Pentane, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, bis(4-hydroxyphenyl)ether, 4,4'-dihydroxybenzophenone, 2,2-bis(4-hydroxy-3-methoxy) phenyl) 1,1,1,3,3,3-hexafluoropropane, α,ω-bis[3-(2-hydroxyphenyl)propyl]polydimethylsiloxane, resorcinol, and 2,7-dihydroxynaphthalene are preferred; 2,2-bis(4-hydroxyphenyl)propane is more preferred.

The carbonate ester-forming compound is not particularly limited. Examples of carbonate-forming compounds include various carbonyl dihalides such as phosgene; haloformates such as chloroformate; and carbonate compounds such as bisaryl carbonate. The carbonate ester-forming compounds may be used alone or in combination of two or more.

In addition to polycarbonate units, the polycarbonate resin may contain one or more polyester units, polyurethane units, polyether units, polystyrene units, polysiloxane units, monomers, oligomers, or polymers having phosphorus atoms as copolymerization components.

The method for producing polycarbonate resin is not particularly limited, and conventionally known production methods can be used. Moreover, a commercially available product may be used as the polycarbonate resin. An example of such a commercial product is "SDPOLYCA 301-4" (manufactured by Sumika Polycarbonate Co., Ltd., melt volume flow rate (hereinafter abbreviated as "MVR") at 300°C and 1.2 kg load: 4 cm ³ /10 minutes), "SDPOLYCA 301-6" (manufactured by Sumika Polycarbonate Co., Ltd., MVR: 6 cm ³ /10 minutes), "SDPOLYCA 301-10" (manufactured by Sumika Polycarbonate Co., Ltd., MVR: 6 cm ³ /10 minutes) , "Iupilon H-3000" (manufactured by Mitsubishi Engineering Plastics Corporation, MVR: 28 cm ³ /10 minutes), "Iupilon S-2000" (manufactured by Mitsubishi Engineering Plastics Corporation, MVR: 9 cm ³ /10 minutes), etc. can be mentioned.

The viscosity average molecular weight of the polycarbonate resin is not particularly limited. The viscosity average molecular weight is usually 10,000 to 60,000, preferably 15,000 to 35,000, and more preferably 18,000 to 30,000 from the viewpoint of moldability into the base material and mechanical properties. . When producing such a polycarbonate resin, the viscosity average molecular weight can be adjusted by using a molecular weight regulator, a catalyst, or the like as necessary. Alternatively, two or more polycarbonate resins having different viscosity average molecular weights may be prepared in advance and blended to adjust the desired viscosity average molecular weight.

The MVR of the polycarbonate resin is not particularly limited. MVR at 300° C. and 1.2 kg load is usually 1 to 200 cm ³ /10 min. Here, MVR is measured in accordance with ISO1133. From the viewpoint of moldability and penetration resistance, the MVR of the polycarbonate resin is preferably 2 to 30 cm ³ /10 minutes, more preferably 3 to 10 cm ³ /10 minutes. When producing such a polycarbonate resin, MVR can be adjusted by using a molecular weight regulator, a catalyst, or the like as necessary. Alternatively, two or more polycarbonate resins having different MVRs may be prepared in advance and blended to adjust the desired MVR.

The glass transition temperature of the polycarbonate resin is not particularly limited. The glass transition temperature is preferably 100 to 180°C, more preferably 110 to 160°C. When the glass transition temperature is equal to or higher than the lower limit, deformation of the base material (I) during laminated glass production can be easily prevented. When the glass transition temperature is below the upper limit value, it is easy to prevent defects such as sink marks during extrusion molding due to the high melt viscosity of the polycarbonate resin. The glass transition temperature can be adjusted within the above range, for example, by adjusting the viscosity average molecular weight or the blending ratio of polycarbonate resins having different viscosity average molecular weights.

The Charpy impact strength of the polycarbonate resin is not particularly limited. Charpy impact strength is preferably 5 kJ/m ² or more, more preferably 10 kJ/m ² or more, still more preferably 30 kJ/m ² or more, particularly preferably from the viewpoint of penetration resistance when a flying object collides with laminated glass. is 60 kJ/ ^m2 or more. In this specification, Charpy impact strength is the value obtained by notching a 3 mm thick test piece and measuring the notched Charpy impact strength (unit: kJ/m ² ) at 23°C in accordance with ISO179. do. The Charpy impact strength can be adjusted to be equal to or higher than the lower limit by adjusting, for example, the viscosity average molecular weight distribution or the combination of the polyfunctional hydroxy compound and the carbonate-forming compound.

The total light transmittance of the polycarbonate resin is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, particularly preferably 89% or more. When the total light transmittance is equal to or higher than the lower limit, the transparency when the base layer (I) is used within the thickness range described below tends to be high, and the transparency of the resulting laminated glass is also likely to be high. The total light transmittance can be measured by a haze meter using a molded product having a thickness of 3 mm or less (for example, 3 mm) obtained by press-molding a polycarbonate resin by the measuring method described in JIS K7361-1. . The total light transmittance can be adjusted to be equal to or higher than the lower limit value by, for example, selecting a polyfunctional hydroxy compound and a carbonate ester-forming compound to adjust the refractive index of the polycarbonate resin.

<Polycarbonate resin composition>
The base layer (I) may be made of a polycarbonate resin as described above, or may be made of a polycarbonate resin composition containing additives as necessary, as long as the objects and effects of the present invention are not hindered. good.
Examples of additives include antioxidants, heat deterioration inhibitors, ultraviolet absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dyes and pigments, light diffusion agents, Organic dyes, matting agents, impact modifiers, phosphors, etc. may be mentioned. When using additives, one may be used alone or two or more may be used in combination. When using an additive, the amount added is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total mass of the polycarbonate resin composition.

The method for producing the polycarbonate resin composition is not particularly limited, and a wide variety of known methods for producing polycarbonate resin compositions can be adopted. An example of such a manufacturing method is to mix the polycarbonate resin and optional additives in advance using various mixers such as a tumbler or Henschel mixer, and then mix the polycarbonate resin with a Banbury mixer, roll, Brabender, etc. Examples include a method of melt-kneading using a mixer such as a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. The melt-kneading temperature is not particularly limited, and may be appropriately selected depending on the type of polycarbonate resin. The melt-kneading temperature is usually 220 to 320°C.

Properties such as viscosity average molecular weight, MVR, glass transition temperature, and Charpy impact strength of the polycarbonate resin composition are not particularly limited. It is preferred that the polycarbonate resin composition has properties similar to those of the polycarbonate resin described above.

[Method for manufacturing base layer (I)]
The method for manufacturing the base layer (I) is not particularly limited, and any known film or sheet manufacturing method can be employed. From the viewpoint of easy adjustment to a suitable thickness, it is preferable to use an extruder.
Examples of the extruder include a single-screw extruder, a co-directional intermeshing twin-screw extruder, a co-directional non-intermeshing twin-screw extruder, a different-direction non-intermeshing twin-screw extruder, and a multi-screw extruder. can. Among these, a single-screw extruder is preferable because thermal deterioration of the resin can be suppressed during extrusion due to a small resin retention area, and equipment costs are low. The screw used in a single-screw extruder etc. may be a screw with a general full-flight configuration with a compression ratio of about 2 to 3, or a screw equipped with a special kneading mechanism such as a barrier flight to prevent the presence of unmelted materials. A screw may also be used. Furthermore, an extruder having a vent mechanism may be used to remove residual volatile components in the polycarbonate resin or polycarbonate resin composition or volatile components generated by heating in the extruder.
In addition, when using a polycarbonate resin composition as the material for the base layer (I), the polycarbonate resin composition may be prepared in advance and put into an extruder and extruded, or the polycarbonate resin and the polycarbonate resin may be blended as necessary. The additives may be put into an extruder and extruded.

It is preferable that the surface of the base material layer (I) is smooth. The smoother the base layer (I) is, the easier it is to produce a laminate of the base layer (I) and the adhesive layer (II). Further, when laminated glass is manufactured using such a laminate as the resin interlayer film (A), the appearance quality of the laminated glass is likely to be improved. The method of obtaining a smooth surface is not particularly limited. A smooth surface can be obtained, for example, by extruding a melt-kneaded product of polycarbonate resin or a polycarbonate resin composition in a molten state from a T-die, and molding the extruded melt-kneaded product by bringing both sides of the extruded melt-kneaded product into contact with a mirror roll surface or a mirror belt surface. It can be obtained by a method including, and such a method is preferred. The rolls or belts used in this case are preferably made of metal or silicone rubber.

It is preferable that the base layer (I) has penetration resistance. Therefore, the penetration energy of the base layer (I) in a falling weight impact test is preferably 5 J or more, more preferably 10 J or more, and still more preferably 13 J or more. When the penetration energy of the base layer (I) is equal to or higher than the lower limit value, the durability of the laminated glass manufactured using the laminate of the base layer (I) and the adhesive layer (II) as the resin interlayer film (A) increases. Easy to adjust penetration to a sufficient value. The penetration energy of the base material layer (I) was measured by cutting out a test piece from the base material layer (I) to a size of 60 mm in length x 60 mm in width, using a falling weight impact tester (CEAST9350 manufactured by Instron), and measuring it according to ASTM D3763. In accordance with It can be measured by calculating the penetration energy from the area of the SS curve until the test force returns to zero. The penetration energy can be adjusted to be equal to or higher than the lower limit value by, for example, selecting bisphenol A as the polycarbonate resin contained in the base layer (I) and/or adjusting the thickness of the base layer (I). .

The storage modulus of the base layer (I) measured by tensile dynamic viscoelasticity measurement at 25° C. and a frequency of 1 Hz is preferably 1,000 to 3,500 MPa, more preferably 1,300 to 3,000 MPa, and further Preferably it is 1,500 to 2,500 MPa. When the storage elastic modulus is equal to or higher than the lower limit value, it is easy to ensure sufficient bending rigidity even if the base layer (I) is thin within a moldable range, and when it is equal to or less than the upper limit value, it is possible to obtain the roll shape described below. It is easy to obtain good formability. The storage elastic modulus can be measured using a viscoelasticity measuring device. For example, a sheet measuring 20 mm long x 5 mm wide x 0.4 mm thick is prepared and a viscoelastic spectrometer "Rheogel-E4000" (UBM Co., Ltd.) is used to measure the storage elastic modulus. It can be measured by performing dynamic viscoelasticity measurement using a 1Hz frequency and a measurement temperature of -50 to 250°C. The storage modulus can be adjusted within the above range by, for example, selecting bisphenol A as the polycarbonate resin contained in the base layer (I) and/or adjusting the thickness of the base layer (I). .

It is preferable that the base layer (I) has high total light transmittance. Therefore, the total light transmittance of the base layer (I) at the thickness described below is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, particularly preferably 89% or more. When the total light transmittance is equal to or higher than the lower limit, the resulting laminated glass tends to have high transparency. The total light transmittance can be measured using a haze meter using the base layer (I) according to the measuring method described in JIS K7361-1. The total light transmittance can be determined by selecting a resin having a high total light transmittance as described above as the polycarbonate resin contained in the base layer (I), and/or reducing the surface roughness of the base layer (I). It can be adjusted to be equal to or higher than the lower limit by selecting additives or adjusting the dispersibility of additives in the polycarbonate resin composition constituting the base layer (I).

The thickness T(I) of the base layer (I) is preferably 0.70 mm or less from the viewpoint of handleability of the laminate of the base layer (I) and the adhesive layer (II). The thickness T(I) is preferably 0.20 mm or more, more preferably 0.30 mm or more, and preferably from the viewpoint of easily obtaining the desired penetration energy, storage modulus, and bending rigidity of the laminate described below. It is 0.60 or less, more preferably 0.50 mm or less. Thickness T(I) can be measured with a thickness meter.

The surface of the base layer (I) may be subjected to adhesion-facilitating treatment as long as it does not interfere with the purpose and effects of the present invention. Examples of adhesion-promoting treatments include surface treatments such as corona treatment, plasma treatment, and low-pressure ultraviolet ray treatment.

Further, an easily adhesive layer may be provided on the base layer (I) as long as it does not interfere with the purpose and effects of the present invention. Examples of the resin contained in the easily adhesive layer include urethane resin, polyester, polyvinyl acetate, epoxy resin, and silicone.

The easily adhesive layer can be formed on the base layer (I) by a known method. An example of such a method is a method comprising applying the resin described above to the base layer (I) and drying it. The thickness of the easily bonding layer in a dry state is preferably 1 to 100 nm, more preferably 10 to 50 nm. The resin used for coating may be diluted with a solvent. Although such a solvent is not particularly limited, alcohols can be used, for example. The dilution concentration (mass percentage of solid content relative to the total mass of the coating liquid) is not particularly limited, but is preferably 1 to 5% by mass, more preferably 1 to 3% by mass.

The surface of the adhesive layer may be subjected to surface treatment such as low-pressure ultraviolet treatment, corona treatment, or plasma treatment, if necessary, for the purpose of increasing the adhesive force with the adhesive layer (II).

[Adhesive layer (II)]
The laminate consists of a base layer (I) and two adhesive layers (II) present on both sides of the base layer (I). The materials constituting the two adhesive layers (II) may be the same or different. The materials constituting the two adhesive layers (II) are preferably the same.
The material constituting the adhesive layer (II) is an acrylic block copolymer (X) or a composition containing the acrylic block copolymer (X).

<Acrylic block copolymer (X)>
The acrylic block copolymer (X) in the present invention is a polymer block having a methacrylic ester unit as a main structural unit at one or both ends of a polymer block (a1) having an acrylic ester unit as a main structural unit. It has a structure in which (a2) is bonded, ie, a structure of (a1)-(a2) or (a2)-(a1)-(a2) (in the structure, "-" indicates a chemical bond). That the acrylic block copolymer (X) has the above structure can be confirmed by, for example, NMR measurement or infrared spectroscopy.
The acrylic block copolymer (X) contained in the adhesive layer (II) may be an acrylic block copolymer (X) alone as exemplified below, or a combination of two or more thereof. It may be. For example, it may be an acrylic block copolymer (X) having a structure of (a2)-(a1)-(a2), or an acrylic block copolymer (X) having a structure of (a1)-(a2). and the acrylic block copolymer (X) having the structure (a2)-(a1)-(a2). It may also be a combination of two acrylic block copolymers (X) having a (a2)-(a1)-(a2) structure having different contents of a2).

<Polymer block (a1)>
The content of acrylic ester units in the polymer block (a1) is usually 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass. Examples of the acrylic ester constituting the acrylic ester unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, isobornyl acrylate, phenyl acrylate, benzyl acrylate, Examples include phenoxyethyl acrylate, 2-hydroxyethyl acrylate, and 2-methoxyethyl acrylate. Among these acrylic esters, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and phenoxyethyl acrylate are preferred from the viewpoint of easily obtaining improved flexibility. , acrylic acid alkyl esters such as 2-methoxyethyl acrylate are preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferred. The polymer block (a1) may be composed of one kind of these acrylic esters, or may be composed of two or more kinds.

As long as it does not interfere with the purpose and effect of the present invention, the polymer block (a1) is a structural unit derived from an acrylic ester having a reactive group such as glycidyl acrylate and allyl acrylate; or the following methacrylic ester, Constituent units derived from polymerizable monomers other than acrylic esters such as methacrylic acid, acrylic acid, aromatic vinyl compounds, acrylonitrile, methacrylonitrile, and olefins; etc. may be included as copolymerization components. These structural units derived from the acrylic ester having a reactive group or the structural units derived from other polymerizable monomers are preferably in small amounts from the viewpoint of facilitating the expression of the effects of the present invention. When the polymer block (a1) contains these structural units, the total content thereof is preferably 10% by mass or less, more preferably 2% by mass, based on all the structural units constituting the polymer block (a1). % or less.

The acrylic ester used in preparing the polymer block (a1) having acrylic ester units as the main constituent units may be one type of monomer or a combination of two or more types. Alternatively, a mixture of two or more monomers may be used. From the viewpoint of improving transparency, the mixed monomer is preferably a mixed monomer of an acrylic acid alkyl ester and an acrylic acid aromatic ester. In this case, it is preferable to use a mixed monomer of 50 to 90% by mass of alkyl acrylate and 50 to 10% by mass of aromatic acrylate, and 60 to 80% by mass of alkyl acrylate and 40% by mass of aromatic acrylate. More preferably, the amount of mixed monomers is 20% by mass.

<Polymer block (a2)>
The content of methacrylic acid ester units in the polymer block (a2) is usually 60% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and may be 100% by mass. Examples of the methacrylic ester constituting the methacrylic ester unit include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, Examples include phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, and 2-methoxyethyl methacrylate. Among these methacrylic acid esters, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, and methacrylic acid are preferred from the viewpoint of easily improving transparency and heat resistance. Methacrylic acid alkyl esters such as isobornyl are preferred, and methyl methacrylate is more preferred. The polymer block (a2) may be composed of one type of these methacrylic acid esters, or may be composed of two or more types.

As long as the objects and effects of the present invention are not hindered, the polymer block (a2) is a structural unit derived from a methacrylic ester having a reactive group such as glycidyl methacrylate and allyl methacrylate; Constituent units derived from polymerizable monomers other than methacrylic acid esters, such as methacrylic acid, acrylic acid, aromatic vinyl compounds, acrylonitrile, methacrylonitrile, and olefins; etc. may be included as copolymerization components. These structural units derived from methacrylic acid ester having a reactive group or structural units derived from other polymerizable monomers are preferably in small amounts from the viewpoint of facilitating the expression of the effects of the present invention. When the polymer block (a2) contains these structural units, the total content thereof is preferably 10% by mass or less, more preferably 2% by mass, based on all the structural units constituting the polymer block (a2). % or less.

The molecular chain form of the acrylic block copolymer (X) is not particularly limited as long as it has at least one structure in the molecule in which the polymer block (a2) is bonded to the end of the polymer block (a1). For example, any molecular chain form such as linear, branched, or radial may be used, but from the viewpoint of easily obtaining the desired adhesive strength, a triblock body represented by (a2)-(a1)-(a2) is used. preferable. Therefore, in a preferred embodiment of the present invention, the acrylic block copolymer (X) contained in one or both of the adhesive layers (II), preferably both of the adhesive layers (II) in the laminate has acrylic ester units. It has a structure in which a polymer block (a2) having a methacrylic acid ester unit as a main structural unit is bonded to both ends of a polymer block (a1) having a methacrylic acid ester unit as a main structural unit. Here, the molecular weight, composition, etc. of the polymer blocks (a2) at both ends of the polymer block (a1) may be the same or different.

As long as the objects and effects of the present invention are not hindered, the acrylic block copolymer (X) may be used as a polymer block other than polymer blocks (a1) and (a2), such as acrylic ester and methacrylic ester. The polymer block (c) may be derived from other monomers. The form of bonding between the polymer block (c) and the polymer block (a1) and the polymer block (a2) is not particularly limited, and examples thereof include (a2)-((a1)-(a2)) Examples include _n -(c) and (c)-(a2)-((a1)-(a2)) _n -(c). Here, n is an integer from 1 to 20.

Examples of monomers constituting the polymer block (c) include olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as 1,3-butadiene, isoprene and myrcene; styrene; Aromatic vinyls such as α-methylstyrene, p-methylstyrene and m-methylstyrene; and vinyl acetate, vinylpyridine, acrylonitrile, methacrylonitrile, vinyl ketone, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylamide, methacrylamide, Examples include ε-caprolactone and valerolactone.

The weight average molecular weight (Mw) of the acrylic block copolymer (X) is determined from the viewpoint of the shock absorbing property of the resulting adhesive layer (II) and the adhesiveness between the adhesive layer (II) and the base layer (I). It is preferably 50,000 to 150,000, more preferably 55,000 to 120,000, particularly preferably 60,000 to 100,000. When the weight average molecular weight of the acrylic block copolymer (X) is equal to or higher than the lower limit, sufficient adhesive strength between the base layer (I) and the inorganic glass can be easily maintained, and a good laminated glass can be easily obtained. Furthermore, it is easy to obtain superior mechanical strength such as breaking strength of the resulting laminated glass. On the other hand, if the weight average molecular weight of the acrylic block copolymer (X) is below the above upper limit, fine grain-like irregularities or unevenness may appear on the surface of the molded product of the adhesive layer (II) obtained by extrusion molding etc. It is difficult to generate lumps caused by the melt (high molecular weight acrylic block copolymer), and it is easy to obtain laminated glass with excellent appearance.

The molecular weight distribution represented by the ratio (Mw/Mn) of the number average molecular weight (Mn) to the weight average molecular weight (Mw) of the acrylic block copolymer (X) is not particularly limited. Mw/Mn is preferably within the range of 1.01 or more and less than 10, more preferably from the viewpoint of easily suppressing or preventing the content of unmelted substances that may cause lumps in the adhesive layer (II) It is within the range of 1.01 or more and 3.0 or less.
Note that the weight average molecular weight (Mw) and number average molecular weight (Mn) in this specification are polystyrene equivalent molecular weights measured by gel permeation chromatography, and are measured by the method described in the Examples below. be able to.

The content of the polymer block (a2) in the acrylic block copolymer (X) is preferably 10% by mass or more, from the viewpoint of transparency, shock absorption, and adhesiveness with the base layer (I). The content is more preferably 20% by mass or more, particularly preferably 25% by mass or more, preferably 60% by mass or less, more preferably 50% by mass or less, particularly preferably 45% by mass or less. In a preferred embodiment of the present invention, the content of the polymer block (a2) is 10 to 60% by mass based on the total structural units constituting the acrylic block copolymer (X). Acrylic block copolymer When the content of the polymer block (a2) in (X) is equal to or higher than the lower limit, the feeling of stickiness of the acrylic block copolymer (X) is difficult to increase, and such acrylic block copolymer (X) ) is more preferable as a material constituting the adhesive layer (II). On the other hand, if the content of the polymer block (a2) in the acrylic block copolymer (X) is below the above-mentioned upper limit, the acrylic block copolymer (X) will be difficult to harden, and when producing laminated glass. It is easy to avoid the tendency that the heating time required to obtain sufficient adhesive strength with the glass and the base material layer (I) becomes longer.

The method for producing the acrylic block copolymer (X) is not particularly limited, and any known method can be employed. For example, a method of living polymerization of monomers constituting each block is generally used. An example of such a living polymerization method is a method of anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of a mineral salt such as an alkali metal or alkaline earth metal salt (Japanese Patent Application Laid-Open No. 7-25859). (see JP-A-11-335432), anionic polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound (see JP-A-11-335432), polymerization using an organic rare earth metal complex as a polymerization initiator. A method of radical polymerization in the presence of a copper compound using an α-halogenated ester compound as an initiator (Macromolecular Chemical Physics, Vol. 201, pp. 1108-1114, 2000) ), etc. In addition, a method of producing a mixture containing an acrylic block copolymer by polymerizing monomers constituting each block using a polyvalent radical polymerization initiator and a polyvalent radical chain transfer agent may also be mentioned. can. Among these methods, organic alkali metal compounds are particularly preferred because they yield highly pure acrylic block copolymers, are easy to control the molecular weight and composition ratio of each polymer block, and are economical. A method of anionic polymerization in the presence of an organoaluminum compound using it as a polymerization initiator is preferred.

The total light transmittance of the acrylic block copolymer (X) is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, particularly preferably 89% or more. When the total light transmittance is equal to or higher than the lower limit value, the transparency when the adhesive layer (II) is used within the thickness range described below tends to be high, and the transparency of the obtained laminated glass is also likely to be high. The total light transmittance can be measured by a haze meter using a molded product having a thickness of 3 mm or less (for example, 3 mm) obtained by press-molding a polycarbonate resin by the measuring method described in JIS K7361-1. . The total light transmittance can be adjusted to be equal to or higher than the lower limit value by, for example, selecting the compounds constituting the polymer blocks (a1) and (a2) and adjusting the refractive index of the acrylic block copolymer (X). .

The melt flow rate (hereinafter abbreviated as "MFR") of the acrylic block copolymer (X) is not particularly limited, and is usually 1 to 200 g/10 minutes. Here, MFR is measured at 190° C. under a load of 2.16 kg in accordance with ISO1133. From the viewpoint of moldability, it is preferably 2 to 100 g/10 minutes, more preferably 3 to 80 g/10 minutes. When producing such an acrylic block copolymer (X), the MFR can be adjusted by using a molecular weight regulator, a catalyst, or the like as necessary. Alternatively, two or more acrylic block copolymers (X) having different MFRs may be prepared in advance and blended to adjust the desired MFR.

The A hardness of the acrylic block copolymer (X) at 23° C. is preferably 20 to 99, more preferably 30 to 90, even more preferably 50 to 80. When the A hardness is within the above range, it is easy to obtain an adhesive layer (II) with excellent flexibility and peel strength from the base material (I) when the adhesive layer (II) is manufactured with the thickness described below. .

<Composition containing acrylic block copolymer (X)>
The adhesive layer (II) may be made of the acrylic block copolymer (X) as described above, or may be made of an acrylic block copolymer as necessary as long as it does not interfere with the purpose and effects of the present invention. It may be an acrylic block copolymer (X)-containing composition containing components other than (X).
The types of such components are not particularly limited. For example, various polymers and additives as described below can be mentioned. When such components are used, one may be used alone or two or more may be used in combination. When such a component is used, the amount added is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 30% by mass or less, based on the total mass of the composition containing the acrylic block copolymer (X). It is preferably 20% by mass or less, particularly preferably 10% by mass or less.

As components other than the acrylic block copolymer (X) in the composition containing the acrylic block copolymer (X), an acrylic polymer having a methacrylic acid ester unit as a main constituent unit is preferable.
Such an acrylic polymer is preferably an acrylic polymer containing methacrylic acid ester units in an amount of 80% by mass or more based on the total structural units constituting the acrylic polymer, more preferably an acrylic polymer. It is an acrylic polymer containing methacrylic acid ester units in an amount of 90% by mass or more based on all the constituent units. Examples of the methacrylic ester constituting the methacrylic ester unit include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, Examples include 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, norbornenyl methacrylate, and isobornyl methacrylate. Among them, methyl methacrylate is particularly preferred.

The acrylic polymer having methacrylic acid ester units as its main constituent units may contain other monomer units other than methacrylic acid ester units. Examples of monomers constituting such other monomer units include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid sec-butyl, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, pentadecyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, acrylic Acrylic acid esters such as phenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, cyclohexyl acrylate, norbornenyl acrylate and isobornyl acrylate; acrylic acid, methacrylic acid , unsaturated carboxylic acids such as maleic anhydride, maleic acid and itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated dienes such as butadiene, isoprene and myrcene; styrene, α-methylstyrene , p-methylstyrene and m-methylstyrene; and acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, vinyl acetate, vinylpyridine, vinyl ketone, vinyl chloride, vinylidene chloride and vinylidene fluoride, etc. I can do it.

The method for producing an acrylic polymer having methacrylic acid ester units as the main constituent unit is not particularly limited. Moreover, you may use a commercial item as such an acrylic polymer. Examples of such commercial products include "Parapet H1000B" (MFR: 22g/10 minutes (230°C, 37.3N)), "Parapet GF" (MFR: 15g/10min (230°C, 37.3N)), "Parapet EH" (MFR: 1.3g/10min (230℃, 37.3N)), "Parapet HRL" (MFR: 2.0g/10min (230℃, 37.3N)), "Parapet HRS" (MFR: 2.4g/10min (230℃, 37.3N)) and "Parapet G" (MFR: 8.0g/10min (230℃, 37.3N)) [Both are product names, Kuraray Co., Ltd. [manufactured]] etc.

When the composition containing the acrylic block copolymer (X) contains the acrylic polymer, the content is preferably 1 to 45% by mass, more preferably 3 to 30% by mass. , more preferably 5 to 15% by mass.

In addition to the acrylic polymer that may be optionally included, examples of polymers that may be included in the acrylic block copolymer (X)-containing composition include polyethylene, polypropylene, polybutene-1, and poly-4-methyl. Olefin resins such as pentene-1 and polynorbornene; ethylene ionomers; polystyrene, styrene-maleic anhydride copolymers, high impact polystyrene, AS resins, ABS resins, AES resins, AAS resins, ACS resins, MBS resins, etc. Styrenic resins; methyl methacrylate-styrene copolymers; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polylactic acid; polyamide resins such as nylon 6, nylon 66, and polyamide elastomers; ester-based polyurethane elastomers, ether-based polyurethane elastomers, Polyurethane resins such as yellowing ester polyurethane elastomers and non-yellowing carbonate polyurethane elastomers; polycarbonates, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyacetals, polyvinylidene fluoride, modified polyphenylene ethers , polyphenylene sulfide, and silicone rubber modified resins. One of these polymers may be included alone, or a combination of two or more may be included. Among these, AS resin and polyvinylidene fluoride are preferred from the viewpoint of compatibility with the acrylic block copolymer (X).

Examples of additives that may be optionally included in the acrylic block copolymer (X)-containing composition include rubber, lubricant, antioxidant, light stabilizer, colorant, antistatic agent, flame retardant, and adhesion modifier. , fillers can be mentioned. When these additives are included, one may be included alone or a combination of two or more may be included.
Examples of the rubber include acrylic rubber; silicone rubber; styrene thermoplastic elastomer such as SEPS, SEBS, and SIS; olefin rubber such as IR, EPR, and EPDM.
Examples of non-rubber additives include mineral oil softeners such as paraffinic oils and naphthenic oils (these can improve fluidity during molding processes); calcium carbonate, talc, carbon black, oxidation Inorganic fillers such as titanium, silica, clay, barium sulfate, and magnesium carbonate (these are added mainly for the purpose of improving or increasing heat resistance or weather resistance); inorganic fibers such as glass fibers and carbon fibers; Organic fibers (these are mainly added for reinforcement purposes); heat stabilizers; antioxidants; light stabilizers; adhesives; tackifiers; plasticizers; antistatic agents; blowing agents; colorants; dyeing Agents, etc. can be mentioned.
Among these additives, in order to further improve heat resistance and weather resistance, it is practically preferable to add a heat stabilizer and/or an antioxidant.

The method for producing the composition containing the acrylic block copolymer (X) is not limited, and a wide variety of known production methods can be employed. As an example of such a production method, the acrylic block copolymer (X) and other components added as necessary are mixed in advance using various mixers such as a tumbler or Henschel mixer, and then Examples include a method of melt-kneading using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader. The melt-kneading temperature is not particularly limited, and may be appropriately selected depending on the acrylic block copolymer (X) and other components added as necessary. The melt-kneading temperature is usually 160 to 240°C.

The properties of the composition containing the acrylic block copolymer (X), such as MFR, A hardness at 23° C., and transparency, are not particularly limited. It is preferable that the composition containing the acrylic block copolymer (X) has properties similar to those of the acrylic block copolymer (X) described above.

[Method for manufacturing adhesive layer (II)]
The method for producing the adhesive layer (II) containing the acrylic block copolymer (X) is not particularly limited. For example, it can be obtained by molding the material constituting the adhesive layer (II) into a sheet using a known device such as a hot press molding machine, a calendar roll, or an extruder. Alternatively, the material constituting the adhesive layer (II) may be dissolved or dispersed in an organic solvent or an organic dispersion medium to obtain a coating liquid, and after applying the coating liquid to a release film, the organic solvent or organic dispersion medium may be removed. It may be manufactured by From the viewpoint of degassing properties, an uneven structure such as melt fracture or embossing may be formed on the surface of the adhesive layer (II) by a conventionally known method, and is preferably formed. The shape of such an uneven structure is not particularly limited, and may be a conventionally known structure.

The storage modulus of the adhesive layer (II) measured by tensile dynamic viscoelasticity measurement at 25° C. and a frequency of 1 Hz is preferably 0.1 to 1000 MPa, more preferably 1 to 500 MPa, and still more preferably 10 to 200 MPa. . When the storage elastic modulus is equal to or higher than the lower limit, even if the adhesive layer (II) is thin, the laminate of the base layer (I) and the adhesive layer (II) can be easily rolled up without breaking. Cheap. When the storage modulus is below the upper limit, it is easy to prevent cracking due to stress generated during laminated glass production, and it is easy to obtain laminated glass with excellent appearance. The storage elastic modulus can be measured using a viscoelasticity measuring device. For example, a sheet measuring 20 mm long x 5 mm wide x 0.2 mm thick is prepared and a viscoelastic spectrometer "Rheogel-E4000" (manufactured by UBM Co., Ltd.) is used. ) using dynamic viscoelasticity measurement under the measurement conditions of a frequency of 1 Hz and a measurement temperature of -50 to 250°C. The storage modulus can be determined, for example, by adjusting the composition ratio of polymer blocks (a1) and (a2) in the acrylic block copolymer (X) contained in the adhesive layer (II), and/or by adjusting the composition ratio of the polymer blocks (a1) and (a2) in the acrylic block copolymer (X) contained in the adhesive layer (II). ) can be adjusted within the above range by adjusting the thickness.

The thickness T (II) of one layer of adhesive layer (II) is preferably 0.30 mm or less, more preferably 0.30 mm or less, from the viewpoint of easily obtaining good rigidity against compressive shear and good adhesion to glass, and from an economic viewpoint. It is 0.010 to 0.30 mm, more preferably 0.020 to 0.25 mm, particularly preferably 0.030 to 0.20 mm. The thicknesses of the two adhesive layers (II) included in one laminate may be the same or different. The thicknesses of the two adhesive layers (II) are preferably the same. Thickness T(II) can be measured with a thickness meter.

The ratio T(I)/T(II) of the thickness T(I) of the base layer (I) to the thickness T(II) of the adhesive layer (II) is the material constituting the base layer (I), Although it depends on the material constituting the adhesive layer (II) and the intended use, from the viewpoint of adhesion and penetration resistance of each layer when laminated glass is made, and from the viewpoint of easily obtaining the desired bending rigidity of the laminate, Preferably it is 1.3 or more, more preferably 1.5 or more, still more preferably 2.0 or more, preferably 26 or less, and more preferably 20 or less.

[Resin interlayer film (A)]
The resin interlayer film (A) in the laminated glass of the present invention includes a laminate including the above-mentioned adhesive layer (II) on both sides of the above-mentioned base layer (I). In one aspect of the present invention, the resin interlayer film (A) includes one of the laminates. The resin interlayer film (A) may consist of one of the above-mentioned laminates. In another aspect of the present invention, the resin interlayer film (A) includes two or more of the laminates. The resin interlayer film (A) may be composed of two or more of the above-mentioned laminates.

The thickness of one laminate is preferably 0.95 mm or less, more preferably 0.90 mm or less, still more preferably 0.85 mm or less, while satisfying the above-mentioned thickness ranges of each layer. When the thickness of one laminate is equal to or less than the above upper limit, it is easy to provide a laminate having the above-mentioned thickness ratio as a roll, and it is easy to obtain a laminate having sufficient handleability, transparency, and heat resistance. . Further, the thickness of one laminate is preferably 0.30 mm or more, more preferably 0.40 mm or more, and even more preferably 0.45 mm or more, while satisfying the above-mentioned thickness ranges of each layer. When the thickness of one laminate is equal to or greater than the lower limit, it is easy to obtain a resin interlayer film (A) that provides the penetration resistance required for laminated glass.

The method for producing the resin interlayer film (A) includes a laminate having adhesive layers (II) on both sides of a base layer (I), that is, adhesive layer (II)-base layer (I)-adhesive layer (II). The method is not particularly limited as long as it can produce a laminate in which the layers are stacked in the following order. Examples of such methods include laminating the base layer (I) and the adhesive layer (II) by a known method such as a thermal lamination method or a pressure bonding method, and laminating the material constituting the adhesive layer (II) with an organic material. A coating liquid is obtained by dissolving or dispersing in a solvent or an organic dispersion medium, and this coating liquid is applied to one side of the base layer (I).The organic solvent or organic dispersion medium is removed, and the coating liquid is further coated on one side of the base layer (I). ) After applying a coating liquid to the other side of the substrate, the organic solvent or organic dispersion medium is removed, and the material constituting the base layer (I) and the material constituting the adhesive layer (II) are coextruded. Here are some ways to do it.

The flexural modulus of the laminate at 25° C. is preferably 30 MPa or more, more preferably 100 MPa or more, still more preferably 200 MPa or more, particularly preferably 220 MPa or more, from the viewpoint of easily obtaining good mechanical strength of the resulting laminated glass. . Although the upper limit of this flexural modulus is not particularly limited, the flexural modulus of the laminate at 25° C. is usually 2000 MPa or less. The flexural modulus of elasticity of the laminate at 25°C is, for example, the ratio T(I)/T(II) of the thickness T(I) of the base material layer (I) to the thickness T(II) of the adhesive layer (II). By increasing , it is possible to adjust the value to be equal to or higher than the lower limit value.
The flexural modulus of the laminate at 50° C. is preferably 20 MPa or more, more preferably 100 MPa or more, still more preferably 200 MPa or more, particularly preferably 220 MPa or more, from the viewpoint of easily obtaining good mechanical strength of the resulting laminated glass. . Although the upper limit of this flexural modulus is not particularly limited, the flexural modulus of the laminate at 50° C. is usually 1500 MPa or less. The flexural modulus of the laminate at 50° C. is determined by, for example, the ratio T(I)/T(II) of the thickness T(I) of the base layer (I) to the thickness T(II) of the adhesive layer (II). By increasing , it is possible to adjust the value to be equal to or higher than the lower limit value.
The flexural modulus can be measured by the method described in Examples below.

The bending rigidity of the laminate at 25° C. is 6 N·mm or more and 60 N·mm or less. If the laminate does not have this specific bending rigidity, it is difficult for the laminate to have excellent handling properties during laminated glass production.
The resin interlayer film (A) has excellent handling properties during the production of laminated glass, so the laminate contained in the resin interlayer film is not wrinkled in the process of sandwiching the laminate between glasses, making it easy to handle. Laminated glass can be manufactured. Furthermore, because the laminate has this specific bending rigidity, the laminate can be wound well even with a relatively thin winding core (for example, a winding core with a diameter of 6 inches (approximately 15.24 cm)). Since the roll body of the obtained laminate is less likely to be bent, the work efficiency during transportation can also be improved. Furthermore, curling curls are less likely to remain in the laminate after it is unwound from the roll.
The bending rigidity is preferably 8 N.mm or more, more preferably 10 N.mm or more, still more preferably 12 N.mm or more, particularly preferably 14 N.mm or more. When the bending rigidity is equal to or greater than the lower limit, better handling properties can be easily obtained during laminated glass production.
The bending rigidity is preferably 55 N/mm or less, more preferably 50 N/mm or less, more preferably 45 N/mm or less, more preferably 40 N/mm or less, more preferably 35 N/mm or less, and even more preferably 30 N/mm. It is particularly preferably 28 N·mm or less. When the bending rigidity is less than or equal to the upper limit value, it is easier to wind even a relatively thin winding core, and it is less likely that curls will remain in the laminate after unwinding from the roll body.
The bending rigidity can be adjusted to the lower limit value by, for example, laminating a specific base material layer (I) and a specific adhesive layer (II) at an appropriate thickness ratio, or by adjusting the bending elastic modulus of each layer. It can be adjusted to be above and below the upper limit value.

The bending rigidity of the laminate at 50° C. is preferably 4 N.mm or more, more preferably 6 N.mm or more, and even more preferably 8 N.mm from the viewpoint of easy handling during laminated glass production even at high temperatures. mm or more, more preferably 10 N.mm or more, even more preferably 12 N.mm or more, particularly preferably 13 N.mm or more, preferably 60 N.mm or less, more preferably 55 N.mm or less, more preferably 50 N.mm. Below, it is more preferably 45 N.mm or less, particularly preferably 40 N.mm or less. In one aspect of the present invention, the bending rigidity of the laminate at 50° C. is 4 N·mm or more and 60 N·mm or less. When the bending rigidity is equal to or higher than the lower limit, it is easy to obtain better handling properties during laminated glass production even at high temperatures. When the bending rigidity is less than or equal to the upper limit value, even at high temperatures, it is easier to roll the roll even on a relatively thin winding core, and curling is less likely to remain in the laminate after unwinding from the roll body.
The bending rigidity can be determined, for example, by laminating a specific base material layer (I) and a specific adhesive layer (II) at an appropriate thickness ratio, or by determining the thickness T(II) of the adhesive layer (II). By increasing the ratio T(I)/T(II) of the thickness T(I) of the material layer (I), the thickness can be adjusted to be greater than or equal to the lower limit value and less than or equal to the upper limit value.

積層体の曲げ弾性率として、基材層（Ｉ）を構成する樹脂および接着層（ＩＩ）を構成する樹脂の公知のヤング率から求めた値を用いてもよいし、上述したように後述の実施例に記載の方法により実験的に測定した値を用いてもよい。なお、本発明において、ポアソン比としては０．３８を用いている。 The bending rigidity of the laminate at 25°C or 50°C is determined by the following formula (1) or (2).

As the flexural modulus of the laminate, a value obtained from the known Young's modulus of the resin constituting the base layer (I) and the resin constituting the adhesive layer (II) may be used, or as mentioned above, the value determined from the known Young's modulus of the resin constituting the adhesive layer (II) may be used. Values experimentally measured by the method described in Examples may also be used. Note that in the present invention, 0.38 is used as Poisson's ratio.

The laminated glass of the present invention can have excellent transparency due to the resin interlayer film (A). Therefore, even if the type of inorganic glass that is the outer layer is changed depending on the application, the laminated glass of the present invention can have excellent transparency.
From the viewpoint of easily bringing superior transparency to the laminated glass, the haze of one laminate included in the resin interlayer film (A) is preferably 5% or less, more preferably 2% or less, and even more preferably 1% or less. It is. The lower limit value of haze is not particularly specified. The haze of one laminate is usually 0.01% or more. The haze can be reduced to the upper limit by using a highly transparent copolymer as the acrylic block copolymer (X) contained in the adhesive layer (II) or by reducing the thickness of the resin interlayer film (A). It can be adjusted below the value. The haze can be measured in accordance with JIS K7136:2000 using a haze meter SH7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) using, for example, a laminate having a thickness of 0.8 mm or less (for example, 0.8 mm).

The laminated glass of the present invention can have extremely low coloration due to the resin interlayer film (A) and can be as colorless as possible.
From the viewpoint of easily bringing lower coloration to the laminated glass, the yellowness index (YI) of one laminate included in the resin interlayer film (A) is preferably 3 or less, more preferably 2 or less, and still more preferably 1 or less. , particularly preferably 0.5 or less. The yellowness is 0 or more. The yellowness can be adjusted by using a copolymer showing a low yellowness as the acrylic block copolymer (X) contained in the adhesive layer (II), or by reducing the thickness of the resin interlayer film (A). It can be adjusted to below the upper limit value. The yellowness can be measured in accordance with JIS Z8722:2009 using a haze meter SH7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) using, for example, a laminate with a thickness of 0.8 mm or less (for example, 0.8 mm). .

The laminated glass of the present invention can have excellent transparency due to the resin interlayer film (A), so inorganic glass can be selected depending on the application while ensuring sufficient transparency of the laminated glass. I can do it. The haze of the laminated glass of the present invention is not particularly limited, and is preferably similar to the haze of the laminate described above.

The laminated glass of the present invention can have extremely low coloring properties due to the resin interlayer film (A), so it is necessary to select an inorganic glass according to the application while ensuring sufficient transparency of the laminated glass. I can do it. The yellowness of the laminated glass of the present invention is not particularly limited, and is preferably similar to the yellowness of the laminate described above.

<Inorganic glass>
As the two inorganic glasses to be laminated with the resin interlayer film (A), for example, inorganic glasses such as float glass, polished plate glass, patterned glass, wired plate glass, or heat ray absorbing plate glass can be used. Inorganic glass may be colorless or colored. The types and thicknesses of the two inorganic glasses may be the same or different.

[Laminated glass]
The laminated glass of the present invention has a structure in which inorganic glass is laminated on both sides of a resin interlayer film (A). The resin interlayer film (A) includes a laminate having adhesive layers (II) on both sides of a base layer (I).
When there is one laminate included in the resin interlayer film (A), the laminated glass has a configuration as shown in FIG. 1. That is, in one embodiment of the present invention, the laminated glass has a structure in which an inorganic glass 11, a resin interlayer film (A) 31, and an inorganic glass 11 are laminated in this order, and the resin interlayer film (A) 31 is a base material layer. It consists of a laminate having adhesive layers (II) 21 on both sides of (I) 22. Note that in FIG. 1 and FIGS. 2 to 4 described later, the dimensions and proportions of each component are appropriately different in order to make the drawings easier to see.
The resin interlayer film (A) may contain two or more laminates. For example, when there are two laminates included in the resin interlayer film (A), the laminated glass consists of inorganic glass/adhesive layer (II)/base material layer (I)/adhesive layer (II)/adhesive layer (II)/base material. It has a structure of material layer (I)/adhesive layer (II)/inorganic glass. When the resin interlayer film (A) contains two or more laminates, it can also be preferably used in applications that require particularly excellent penetration resistance, such as bulletproof glass. When there are two or more laminates contained in the resin interlayer film (A), the materials and thicknesses of the base layer (I) and adhesive layer (II) constituting the plurality of laminates may be the same. It's okay and it can be different.

The resin interlayer film (A) may include a structure other than the above-mentioned laminate on the entire surface or a part of the resin interlayer film (A), if necessary, as long as it does not interfere with the purpose and effects of the present invention. Examples of such structures may include electrically conductive structures, sound-insulating structures, designs or design layers, and combinations thereof.

The laminated glass may be used alone or in a combination of two or more pieces. When used in a combination of two or more sheets, the laminated glass is, for example, glass/adhesive layer (II)/base layer (I)/adhesive layer (II)/glass/adhesive layer (II)/base layer ( It has a structure of I)/adhesive layer (II)/glass. When two or more pieces of laminated glass are used in combination, the materials and thicknesses of the laminated glasses may be the same or different.

[Method for manufacturing laminated glass]
The laminated glass of the present invention can be manufactured by a conventionally known method. Examples of such methods include using a vacuum laminator device, using a vacuum bag, using a vacuum ring, and using nip rolls. Another method that can be mentioned is a method in which after temporary pressure bonding is performed by the above method, the material is placed in an autoclave and main bonding is performed.

When using a vacuum laminator device, inorganic glass, resin interlayer film (A), and inorganic glass are laminated at 60 to 200°C, particularly 80 to 160°C, under a reduced pressure of 1 x ^{10 -6} to 3 x 10 ^-2 MPa, for example. By this, laminated glass can be manufactured.

When using a vacuum bag or a vacuum ring, for example, as described in European Patent No. 1235683, inorganic glass, resin interlayer film (A), and inorganic glass are heated under a pressure of about 2×10 ⁻² MPa to Laminated glass can be produced by laminating at ~160°C.

When using nip rolls, the inorganic glass, the resin interlayer film (A), and the inorganic glass are degassed with rolls at a temperature below the flow start temperature of the resin interlayer film (A), and then the resin interlayer film (A) is degassed with a roll. A laminated glass can be manufactured by heating the inorganic glass, the resin interlayer film (A), and the inorganic glass to a temperature close to the flow start temperature of the laminated glass. More specifically, for example, inorganic glass, resin interlayer film (A), and inorganic glass are heated to 30 to 70°C with an infrared heater or the like in a stacked state, and then degassed with a roll, and then heated to 50 to 150°C. After heating, a laminated glass can be manufactured by pressing the inorganic glass, the resin interlayer film (A), and the inorganic glass with a roll.

When the laminated glass is subjected to temporary pressure bonding by the above method and then put into an autoclave for main pressure bonding, the operating conditions of the autoclave step may be appropriately selected depending on the thickness or structure of the laminated glass. The autoclave step can be carried out, for example, under a pressure of 0.5 to 1.5 MPa and at 100 to 160° C. for 0.5 to 3 hours.

As is well known, the safety of laminated glass depends on the adhesive strength between the resin interlayer and the outer layer of glass. This adhesion force should preferably be high enough to ensure that the glass fragments remain adhered to the resin interlayer upon mechanical breakage of the glass, and to prevent sharp glass fragments from peeling off. . However, if the adhesive strength between the resin interlayer film and the glass is too high, a collided object may penetrate the laminated glass. If the adhesion of the resin interlayer film to the glass is low, the resin interlayer film will be stretched at the impact point, partially peeled off from the glass, and deformed, which will attenuate the impact energy and prevent the object from penetrating. suppressed. That is, the adhesion between the glass and the resin interlayer in laminated glass is high enough to ensure that glass fragments remain adhered to the resin interlayer when the glass is broken, and high enough to not reduce penetration resistance. It is preferable that it is not too much.
From this point of view, the adhesiveness between the inorganic glass and the adhesive layer (II) of the laminated glass of the present invention evaluated by a compression shear test is preferably 5 MPa or more and 35 MPa or less, more preferably 10 MPa or more and 30 MPa or less, More preferably, it is 15 MPa or more and 25 MPa or less. The adhesion between the inorganic glass and the adhesive layer (II) can be determined by, for example, the selection of the acrylic block copolymer (X) contained in the adhesive layer (II), or the adhesion modifier or filler to the adhesive layer (II). Alternatively, it can be adjusted within the above range by adding additives such as adhesiveness regulators. The adhesion between the inorganic glass and the adhesive layer (II) can be measured, for example, by a compression shear test described in JP-A No. 2006-13505.

If the adhesive strength between the resin interlayer film (A) and the glass and the heat resistance of the resin interlayer film (A) are insufficient, the heat resistance creep property of the laminated glass is likely to decrease. The laminated glass of the present invention can have excellent heat-resistant creep properties due to the specific resin interlayer film (A). The heat-resistant creep property of the laminated glass can be evaluated by measuring the distance of displacement that occurs in the laminated glass when an accelerated test is conducted for one week under the conditions of a load of 37 kg/m ² and an ambient temperature of 100°C. Specifically, it can be evaluated by the method described in Examples below. The heat-resistant creep property of the laminated glass of the present invention is preferably 1 mm or less, more preferably 0.5 mm or less. When the heat resistance creep property is below the upper limit value, it is easy to prevent the problem of the installed glass falling off or moving due to thermal displacement in the laminated glass. The heat-resistant creep property can be adjusted to below the upper limit value by increasing the storage modulus or MFR of the adhesive layer (II).

When broken, it is preferable that the base layer (I) included in the laminated glass does not form large pieces like inorganic glass alone. Therefore, sufficient adhesive force is required between the base layer (I) and the adhesive layer (II). The adhesive force between the base layer (I) and the adhesive layer (II) can be evaluated by measuring peel strength, for example, according to JIS K6854-2. Specifically, it can be measured by the method described in Examples below. The peel strength measured under the conditions of a peel angle of 180°, a tensile speed of 100 mm/min, and an environmental temperature of 23° C. is preferably more than 10 N/25 mm, more preferably more than 12 N/25 mm, and still more preferably more than 20 N/25 mm. When the peel strength is greater than the lower limit value, it is easy to obtain a strong adhesive force, for example, such strong adhesive force that a thin (for example, 0.2 mm thick) adhesive layer will break before it is peeled off, and it will be difficult to obtain a strong adhesive force when manufacturing laminated glass. Alternatively, the problem of peeling between the base layer (I) and the adhesive layer (II) in the manufactured laminated glass is less likely to occur.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, each physical property in Examples and Comparative Examples was measured or evaluated by the following method.

<Weight average molecular weight (Mw) and number average molecular weight (Mn)>
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the acrylic block copolymer (X) were determined as polystyrene equivalent molecular weight by gel permeation chromatography (hereinafter abbreviated as GPC). Details are as follows.
・Equipment: GPC device “HLC-8020” manufactured by Tosoh Corporation
・Separation column: “TSKgel GMHXL”, “G4000HXL” and “G5000HXL” manufactured by Tosoh Corporation are connected in series ・Eluent: tetrahydrofuran ・Eluent flow rate: 1.0 mL/min ・Column temperature: 40°C
・Detection method: Differential refractive index (RI)

<Content of each polymer block>
The content of each polymer block in the acrylic block copolymer (X) was determined by ¹ H-NMR ( ¹ H-nuclear magnetic resonance) measurement. Details are as follows.
・Device: Nuclear magnetic resonance apparatus “JNM-LA400” manufactured by JEOL Ltd.
・Heavy solvent: deuterated chloroform

<Haze>
For each laminate produced in the Examples or Comparative Examples described below, haze was measured in accordance with JIS K7136:2000 using a haze meter SH7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). In addition, the haze of each laminate was measured at three locations, and the average value was adopted as the haze of the laminate.

<Yellowness>
The degree of yellowness of each laminate produced in the Examples or Comparative Examples described below was measured using a haze meter SH7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS Z8722:2009. The yellowness of each laminate was measured at three locations, and the average value was taken as the yellowness of the laminate.

<Bending rigidity>
A sheet having a length of 40 mm, a width of 30 mm, and a thickness of 0.8 mm was produced by cutting out a laminate produced in an example or a comparative example described below. Three test pieces each measuring 40 mm x 10 mm x 0.8 mm were cut out from each of the prepared sheets, with reference to JIS-7017. A three-point bending test was performed on each of the obtained test pieces using an Autograph (manufactured by Shimadzu Corporation), and the bending elastic modulus at 25° C. and 50° C. was measured when the distance between the supporting points was 16 mm. For each laminate, the average value of the flexural modulus obtained by measurement was adopted as the flexural modulus of the laminate. Using the flexural modulus and thickness, the flexural stiffness of each laminate was calculated according to equations (1) and (2). 0.38 was used as Poisson's ratio.

<Adhesiveness between base layer (I) and adhesive layer (II)>
Using the base material layer and adhesive layer used in Examples 1 to 4 and Comparative Examples 2 to 3, which will be described later, three test pieces were each prepared for measuring interlayer peel strength according to the following procedure.
A base material layer and an adhesive layer measuring 150 mm long x 75 mm wide were stacked, and a PET film (MRF38, manufactured by Mitsubishi Plastics Co., Ltd., 75 mm long x 75 mm wide, 38 μm thick) that had been subjected to a release treatment with silicone was inserted between them. . The PET film was inserted by thermally laminating the stacked layers and PET film by passing them between a 130°C roll and a 40°C roll using a thermal lamination device (VAII-700 model manufactured by Taisei Laminator Co., Ltd.). The base material layer and the adhesive layer in the non-bonded area were bonded (area of bonded area: 75 mm long x 75 mm wide, area of non-bonded area: 75 mm long x 75 mm wide). After conditioning the resulting partially bonded product for 24 hours in a constant temperature and humidity chamber (20°C - 65% RH), it was placed between two flat pieces of float glass (300 mm long x 300 mm wide x 3.0 mm thick). placed near the center of the After placing this in a rubber bag, it was subjected to temporary pressure bonding using a vacuum laminator and compression using an autoclave under the conditions described in the <Handleability> paragraph below.
The glass and PET film were removed from the test piece that had gone through the above process, and three test pieces measuring 150 mm long x 25 mm wide (bonded area area: 75 mm long x 25 mm wide, area of non-bonded area: 75 mm long x 25 mm wide) were cut out. A test piece for measuring delamination strength was obtained.
The base material layer (I) side of each of the prepared test pieces was fixed to a stainless steel plate with strong adhesive tape (Hyper Joint H9004, manufactured by Nitto Denko Corporation). Using a tabletop precision universal testing machine (Shimadzu Corporation: AGS-X), the base material was tested in accordance with JIS K6854-2 at a peeling angle of 180°, a tensile speed of 100 mm/min, and an environmental temperature of 23°C. The peel strength between layer (I) and adhesive layer (II) was measured. Adhesive strength (unit: N/25 mm) was determined from the average value of the measured values, and evaluated according to the following criteria.
A: The maximum value of peel strength is more than 20 N/25 mm, and the adhesive layer (II) is material destroyed. B: The maximum value of peel strength is more than 12 N/25 mm, but not more than 20 N/25 mm. C: The maximum value of peel strength is 10 N/25 mm. Super, 12N/25mm or less D: Maximum peel strength is 10N/25mm or less

<Ease of handling>
Each resin interlayer film produced in Examples or Comparative Examples described below was cut into a size of 300 mm x 300 mm. After conditioning each cut resin interlayer film in a constant temperature and humidity chamber (20°C - 65% RH) for 24 hours, it was placed between two flat float glasses (300 mm long x 300 mm wide x 3.0 mm thick). were placed respectively. After placing this in a rubber bag, it was placed in a vacuum laminator (Nisshinbo Mechatronics Co., Ltd. 1522N), and for the resin interlayer film (A-7) using thermoplastic polyurethane resin, the heating plate temperature was 100°C and the vacuum evacuation time was 12 minutes. , a press pressure of 50 kPa and a press time of 17 minutes were used.For other resin interlayer films, float glass was degassed under the conditions of a hot plate temperature of 165°C, a vacuum evacuation time of 12 minutes, a press pressure of 50 kPa, and a press time of 17 minutes. and a resin interlayer film were temporarily bonded. Next, the temporarily pressed product taken out from the rubber bag was compressed in an autoclave to obtain a flat laminated glass. The autoclave conditions were 6 bar pressure and 100°C for a total of 90 minutes or less for the resin interlayer film (A-7), and 12 bar pressure and 140°C for a total of 90 minutes or less for the other resin interlayer films.
The handling properties during laminated glass production were evaluated according to the following criteria.
A: Can be manufactured without any problems B: There is a problem in manufacturing (deflection or wrinkles in the resin interlayer film, or poor shaping)

<Adhesion between inorganic glass and adhesive layer (II) (compressive shear test)>
A compressive shear test described in JP-A-2006-13505 was performed on each resin interlayer film produced in the Examples or Comparative Examples described below to evaluate the adhesive strength between the inorganic glass and the adhesive layer (II). Specifically, evaluation was performed according to the following procedure.
The resin interlayer film was cut into a size of 100 mm x 100 mm. After conditioning the cut resin interlayer film in a constant temperature and humidity chamber (20°C - 65% RH) for 24 hours, it was placed between two pieces of flat float glass (100 mm long x 100 mm wide x 3.0 mm thick). , and were placed in such a way that the tin surface of the glass was in contact with the resin interlayer film. After putting this in a rubber bag, it was put into a vacuum laminator (1522N manufactured by Nisshinbo Mechatronics Co., Ltd.), and for the resin interlayer film (A-7), the hot plate temperature was 100°C, the evacuation time was 12 minutes, the press pressure was 50 kPa, and the press time was For the other resin interlayer films, the float glass and the resin interlayer film were temporarily bonded by degassing under the conditions of a hot plate temperature of 165°C, evacuation time of 12 minutes, press pressure of 50 kPa, and press time of 17 minutes. . Next, the temporarily pressed product taken out from the rubber bag was compressed using an autoclave at a pressure of 12 bars and a temperature of 140° C. for a total of 90 minutes or less, thereby obtaining a flat laminated glass.
The obtained laminated glass was cut to obtain three test samples measuring 25 mm in length and 25 mm in width. Each test sample was inserted into the test apparatus shown in FIG. 2 at an angle of 45°. By applying force in the vertical direction to the test device, shear is generated in the test sample, and the maximum shear force required to separate the glass and resin interlayer film is determined, and the average value of the three test samples is calculated. Calculated. The compressive shear force (MPa) was obtained by dividing the obtained average value by sample area (25 mm x 25 mm) x √2. The smaller the value of the compressive shear force, the smaller the adhesive force between the glass and the resin interlayer film.

<Evaluation of heat-resistant creep properties of laminated glass>
Each resin interlayer film produced in the Examples or Comparative Examples described below was cut into a size of 135 mm in length x 50 mm in width. Next, as shown in FIG. 3, between float glasses 41 and 42 of 165 mm long x 50 mm wide x 3 mm thick, 135 mm of the 165 mm long float glasses are placed on both sides of the base layer (I) 52. A laminated glass 40 was manufactured by sandwiching a resin interlayer film (A) 61 such that the resin interlayer film (A) 61 made of a laminate including an adhesive layer (II) 51 was attached to the laminate. Note that the manufacturing procedure for laminated glass is the same as the manufacturing procedure described in the previous <Handling> paragraph.
Subsequently, as shown in FIG. 4, an iron plate 71 weighing 250 g was attached to the glass 41 side of the laminated glass 40 using an instant adhesive 81 to produce a laminated glass 90 with the iron plate attached. A laminated glass 90 to which iron plates were bonded was placed against a stand 101 and left in a chamber at 100° C. for one week. After standing, the distance that the glass 41 slipped down was measured, and the distance was evaluated based on the following criteria, and this evaluation was taken as an evaluation of heat-resistant creep property.
A: The distance by which the glass 41 slipped down was 1 mm or less.
B: The distance by which the glass 41 slipped exceeds 1 mm.

In the following synthesis example, the compound used was purified by drying in a conventional manner and degassed with nitrogen. In addition, the transfer and supply of compounds were performed under a nitrogen atmosphere.

[Synthesis Example 1: Synthesis of acrylic block copolymer (A1)]
735 g of dry toluene, 0.4 g of hexamethyltriethylenetetramine, and isobutylbis(2,6-di-t-butyl-4-methylphenoxy)aluminum are placed in a three-necked flask whose interior has been degassed and replaced with nitrogen at room temperature. 39.4 g of a toluene solution containing 20 mmol was introduced, and further 1.8 mmol of sec-butyllithium was added. The first 43.0 g of methyl methacrylate was added to the resulting mixture, and the mixture was reacted at room temperature for 1 hour. When the polymer contained in the reaction solution was sampled and its weight average molecular weight was measured, it was found to be 24,000. This methyl methacrylate polymer becomes the polymer block (a2) in the acrylic block copolymer (A1) described below.

Next, the temperature of the reaction solution was lowered to -25°C, and 61.0 g of n-butyl acrylate was added dropwise over 0.5 hours. Immediately after the completion of the dropwise addition, the polymer contained in the reaction solution was sampled and its weight average molecular weight was measured and found to be 58,000. As mentioned above, the weight average molecular weight of the methyl methacrylate polymer that becomes the polymer block (a2) was 24,000, so the acrylic ester polymer block (a1) consisting of n-butyl acrylate copolymer The weight average molecular weight was determined to be 34,000.

Subsequently, 18.0 g of methyl methacrylate was added to the reaction solution for the second time, the temperature of the reaction solution was returned to room temperature, and the second methacrylate ester polymer block (a2) was formed by stirring for 8 hours. did. Thereafter, 4 g of methanol was added to the reaction solution to stop the polymerization, and then the reaction solution was poured into a large amount of methanol to precipitate an acrylic block copolymer (A1), which is a triblock copolymer, and was filtered. The acrylic block copolymer (A1) collected by filtration was dried and isolated at 80° C. and 1 torr (about 133 Pa) for 12 hours. The weight average molecular weight of the obtained acrylic block copolymer (A1) was 68,000. Since the weight average molecular weight of the diblock copolymer was 58,000, the weight average molecular weight of the second methyl methacrylate polymer block (a2) was determined to be 10,000. This acrylic block copolymer (A1) was pelletized using a single screw extruder to obtain pellets of the acrylic block copolymer (A1).
The structure of the obtained acrylic block copolymer (A1) is a triblock of methyl methacrylate polymer block (PMMA) - n-butyl acrylate polymer block (PnBA) - methyl methacrylate polymer block (PMMA). It was a copolymer. The PMMA content (content of polymer block (a2)) with respect to all structural units constituting this triblock copolymer is 50.0% by mass, and the weight average molecular weight of the triblock copolymer is 68,000 ( 24,000-34,000-10,000), and the molecular weight distribution (weight average molecular weight/number average molecular weight) was 1.12.

[Synthesis Example 2: Synthesis of acrylic block copolymer (A2)]
An acrylic block copolymer was produced in the same manner as in Synthesis Example 1, except that the amount of methyl methacrylate added in the first step was changed to 18.0 g, and the amount of n-butyl acrylate added dropwise was changed to 79.0 g. Pellets of (A2) were obtained.
The structure of the obtained acrylic block copolymer (A2) is a triblock of methyl methacrylate polymer block (PMMA)-n-butyl acrylate polymer block (PnBA)-methyl methacrylate polymer block (PMMA). It was a copolymer. The PMMA content (content of polymer block (a2)) with respect to all structural units constituting this triblock copolymer is 30.5% by mass, and the weight average molecular weight of the triblock copolymer is 64,000 ( 10,500-44,000-9,500), and the molecular weight distribution (weight average molecular weight/number average molecular weight) was 1.15.

[Synthesis Example 3: Synthesis of acrylic block copolymer (A3)]
An acrylic block copolymer was produced in the same manner as in Synthesis Example 2, except that the amount of methyl methacrylate added in the first addition was changed to 19.0 g, and the amount of methyl methacrylate added in the second addition was changed to 28.0 g. Pellets of (A3) were obtained.
The structure of the obtained acrylic block copolymer (A3) is a triblock of methyl methacrylate polymer block (PMMA) - n-butyl acrylate polymer block (PnBA) - methyl methacrylate polymer block (PMMA). It was a copolymer. The PMMA content (content of polymer block (a2)) with respect to all structural units constituting this triblock copolymer is 38.5% by mass, and the weight average molecular weight of the triblock copolymer is 69,000 ( 10,000-44,000-15,000), and the molecular weight distribution (weight average molecular weight/number average molecular weight) was 1.10.

[Synthesis Example 4: Synthesis of acrylic block copolymer (A4)]
Except that the amount of methyl methacrylate added in the first addition was changed to 36.0 g, the amount of n-butyl acrylate added dropwise was changed to 170 g, and the amount of methyl methacrylate added in the second addition was changed to 36.0 g. Pellets of acrylic block copolymer (A4) were obtained in the same manner as in Synthesis Example 1.
The structure of the obtained acrylic block copolymer (A4) is a triblock of methyl methacrylate polymer block (PMMA)-n-butyl acrylate polymer block (PnBA)-methyl methacrylate polymer block (PMMA). It was a copolymer. The PMMA content (content of polymer block (a2)) with respect to all structural units constituting this triblock copolymer is 30.0% by mass, and the weight average molecular weight of the triblock copolymer is 131,000 ( 19,000-93,000-19,000), and the molecular weight distribution (weight average molecular weight/number average molecular weight) was 1.17.

[Preparation of adhesive layer (II-1)]
The resin obtained in Synthesis Example 1 (acrylic block copolymer (A1)), which had been dried in advance at 60°C for 24 hours, was processed using a 25 mφ single screw extruder "VGM25-28EX" (manufactured by G&M Engineering Company Limited). The adhesive layer (II-1) was extruded from a single layer T-die at a resin temperature of 220° C. and taken off with a roll having a surface temperature of 60° C. to obtain an adhesive layer (II-1) with a width of 300 mm and a thickness of 0.20 mm.

[Preparation of adhesive layer (II-2)]
The adhesive layer ( An adhesive layer (II-2) having a width of 300 mm and a thickness of 0.20 mm was obtained in the same manner as in the production method of II-1).

[Preparation of adhesive layer (II-3)]
The adhesive layer ( An adhesive layer (II-3) with a width of 300 mm and a thickness of 0.20 mm was obtained in the same manner as in the production method of II-1).

[Preparation of adhesive layer (II-4)]
The adhesive layer ( An adhesive layer (II-4) with a width of 300 mm and a thickness of 0.20 mm was obtained in the same manner as in the production method of II-1).

[Preparation of adhesive layer (II-5)]
The adhesive layer ( An adhesive layer (II-5) with a width of 300 mm and a thickness of 0.80 mm was obtained in the same manner as in the production method of II-1).

[Preparation of adhesive layer (II-6)]
Instead of the acrylic block copolymer (A1), polyvinyl butyral manufactured by Kuraray Co., Ltd. (viscosity average degree of polymerization of raw material polyvinyl alcohol 1700, acetal constituent unit content 74 mol%, vinyl alcohol unit content 19 mol%, vinyl acetate) The adhesive layer (II- An adhesive layer (II-6) having a width of 300 mm and a thickness of 0.20 mm was obtained in the same manner as in 1).

[Preparation of adhesive layer (II-7)]
Argotec ST6050 (manufactured by SWM), a non-yellowing thermoplastic polyurethane resin sheet, was placed between two stainless steel plates (35 cm long x 35 cm wide) in a formwork (30 cm long x 30 cm wide x 0.80 mm high). ). This was set in a heat press machine (AYS.10 manufactured by Shinto Metal Industry Co., Ltd.). The resin was heated at 130° C. for 3 minutes without applying pressure to the non-yellowing thermoplastic polyurethane resin sheet. The resin sheet was then hot pressed for 180 seconds at a pressure of 90 kgf/cm ² (about 8.8 MPa). Thereafter, the stainless steel plate and mold were immediately set in a cooling press at 23°C. Pressure was applied to the resin sheet while cooling the resin sheet using a cooling press. By cutting out the resin sheet in the mold, an adhesive layer (II-7) measuring 30 cm long x 30 cm wide x 0.20 mm thick was obtained.

[Preparation of base layer (I)]
Polycarbonate resin “SDPOLYCA 301-4” (manufactured by Sumika Polycarbonate Co., Ltd.), which had been dried in advance at 100°C for 24 hours, was heated to It was extruded from a single-layer T-die at a resin temperature of 140° C. and taken off with a roll having a surface temperature of 140° C. to obtain a base layer (I) having a width of 300 mm and a thickness of 0.40 mm.

[Example 1]
A base layer (I) made of a polycarbonate resin and two adhesive layers (II-1) made of an acrylic block copolymer are bonded using a thermal lamination device (Model VAII-700 manufactured by Taisei Laminator Co., Ltd.). A long roll body of the laminate was produced by thermally laminating the laminate by passing it between rolls at 130°C and 40°C. The conveyance speed was 1.0 m/min, and the pressure was 0.15 MPa.
Next, a laminated glass (A-1) was produced using the laminate unwound from the long roll as a resin interlayer film (A-1) according to the procedure described in the previous paragraph of <Handling properties>. Note that the adhesiveness between the inorganic glass and the adhesive layer (II-1) was as good as 16.1 MPa.

[Examples 2 to 4]
A long roll body of the laminate, a resin interlayer film ( A-2) to (A-4) and laminated glasses (A-2) to (A-4) were produced, respectively. Note that the adhesiveness between the inorganic glass and the adhesive layer (II-2) was 15.6 MPa, and the adhesiveness between the inorganic glass and the adhesive layer (II-3) was 15 MPa, both of which were good.

[Comparative example 1]
A resin intermediate was prepared in the same manner as in Example 1, except that only the adhesive layer (II-5) obtained in the previous [Preparation of adhesive layer (II-5)] was used instead of the long roll of the laminate. A membrane (A-5) and a laminated glass (A-5) were produced. Note that the adhesiveness between the inorganic glass and the adhesive layer (II-5) was 4.4 MPa.

[Comparative example 2]
A long roll body of the laminate, a resin interlayer film (A-6) and a laminated glass were prepared in the same manner as in Example 1 except that the adhesive layer (II-6) was used instead of the adhesive layer (II-1). (A-6) was produced.

[Comparative example 3]
A 30 cm x 30 cm laminate, a resin interlayer film (A-7) and a laminated glass ( A-7) was produced.

Table 1 shows the configurations of the resin interlayer films produced in Examples and Comparative Examples, and the evaluation results of the resin interlayer films and laminated glass.

As shown in Table 1, due to the excellent transparency of the acrylic block copolymer (X), the resin interlayer films in Examples 1 to 4 could not be used even when combined with the base layer (I). It had low haze and low yellowness. This shows that when laminated glasses are manufactured using the resin interlayer films in Examples 1 to 4, the laminated glasses have excellent transparency.
Further, by laminating the specific base material layer (I) and the specific adhesive layer (II) at an appropriate thickness ratio, the bending rigidity of the laminate was satisfied at both 25° C. and 50° C. Therefore, the laminate can be wound well around a commonly used core with a diameter of 6 inches (approximately 15.24 cm), and the long roll of the laminate is less prone to bending during transportation. The work efficiency of laminated glass can be improved, and there is no curl remaining in the laminate after unwinding.Furthermore, as shown in the handling test results, laminated glass can be easily manufactured without wrinkles. could be manufactured. This shows that the resin interlayer film has extremely excellent handling properties during the production of laminated glass not only at room temperature (25°C) but also at high temperatures of 50°C.
Further, the laminated glasses of Examples 1 to 4 had excellent adhesion between the base layer (I) and the adhesive layer (II), and also had excellent heat-resistant creep properties. Furthermore, the laminated glasses of Examples 1 to 3 also had very excellent adhesion between the inorganic glass and the adhesive layer (II) (compressive shear peel strength). From this, it was also confirmed that the laminated glasses of Examples 1 to 3 maintained extremely excellent compressive shear peel strength over a long period of time.

On the other hand, in Comparative Example 1, the haze and yellowness were excellent, but the bending rigidity was insufficient, so the work efficiency of conveying the long roll was poor, and wrinkles also occurred when laminated with glass.
In Comparative Examples 2 and 3, the handling properties during laminated glass production were good, but the haze and yellowness were poor. Moreover, in Comparative Example 3, the heat resistance creep property was also poor.

The laminated glass of the present invention has extremely excellent transparency (low haze and low yellowing degree), and is also extremely easy to handle when manufacturing the laminated glass. It also has excellent adhesion between the base layer (I) and the adhesive layer (II), very excellent adhesion between the inorganic glass and the adhesive layer (II), and excellent heat-resistant creep properties. Therefore, the laminated glass of the present invention is suitable for laminated glass for vehicle use (e.g., car windshield, car side glass, car sunroof, car rear glass, head-up display glass, etc.) or architectural use (e.g., facade, exterior wall glass, etc.). Or as laminated glass for roof laminates, panels, doors, windows, walls, roofs, sunroofs, soundproof walls, display windows, balconies, handrails, etc., conference room partition glass members, solar panels, etc.), especially in architecture. It can be suitably used as a laminated glass for various purposes.

11 Inorganic glass 21 Adhesive layer (II) containing acrylic block copolymer (X)
22 Base layer containing polycarbonate resin (I)
31 Resin interlayer film (A)
40 Laminated glass used for evaluation of heat-resistant creep property 41 Float glass 42 Float glass 51 Adhesive layer (II) containing acrylic block copolymer (X)
52 Base layer containing polycarbonate resin (I)
61 Resin interlayer film (A)
71 Iron plate 81 Instant adhesive 90 Laminated glass with iron plates bonded together 101 Stand

Claims (7)

A laminated glass in which inorganic glass, resin interlayer film (A), and inorganic glass are laminated in this order,
The resin interlayer film (A) includes a laminate including an adhesive layer (II) containing an acrylic block copolymer (X) on both sides of a base layer (I) containing a polycarbonate resin,
The following formula (1):

The laminated glass has a bending rigidity at 25° C. of 6 N·mm or more and 60 N·mm or less. The following formula (2):

The laminated glass according to claim 1, wherein the flexural rigidity of the laminate at 50°C, represented by , is 4 N·mm or more and 60 N·mm or less. The acrylic block copolymer (X) contained in one or both of the adhesive layers (II) in the laminate meets the following conditions (i) to (iii):
(i) The acrylic block copolymer (X) is a polymer block having a methacrylate ester unit as a main constituent unit at one or both ends of the polymer block (a1) having an acrylate ester unit as a main constituent unit. Having a structure in which (a2) is combined,
(ii) The weight average molecular weight is 50,000 to 150,000, and (iii) the content of the polymer block (a2) is relative to all the constituent units constituting the acrylic block copolymer (X). The laminated glass according to claim 1 or 2, which satisfies the condition of 10 to 60% by mass. In the laminate, the acrylic block copolymer (X) contained in one or both of the adhesive layers (II) has methacrylate at both ends of the polymer block (a1) whose main constituent unit is an acrylic ester unit. The laminated glass according to any one of claims 1 to 3, having a structure in which polymer blocks (a2) whose main constituent units are acid ester units are bonded. The laminated glass according to any one of claims 1 to 4, wherein the resin interlayer film (A) includes two or more of the laminates. The laminated glass according to any one of claims 1 to 5, wherein the laminate has a haze of 5% or less as measured in accordance with JIS K7136:2000. The laminated glass according to any one of claims 1 to 6, wherein the laminate has a yellowness of 3 or less as measured in accordance with JIS Z8722:2009.