JP2022042345A - Glass laminate - Google Patents

Abstract

To provide a glass laminate of high transparency that is a laminate of glass and a resin intermediate film, which has good handleability in the production of the glass laminate.SOLUTION: A glass laminate has inorganic glass, a resin intermediate film (A), and inorganic glass laminated in this order. The resin intermediate film (A) includes a laminate having an adhesive layer (II) containing an acrylic block copolymer (X) on each side of a substrate layer (I) containing a polycarbonate resin. The laminate, represented by the formula (1), shows a flexural rigidity of 6 N mm or more and 60 N mm or less at 25°C.SELECTED DRAWING: Figure 1

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 the scattering of debris when the glass is broken and improving the crime prevention property. The resin interlayer film is preferably excellent in adhesion to glass, transparency, penetration resistance and flexibility. As a resin that can bring about such a resin interlayer film, polyvinyl acetal typified by polyvinyl butyral (PVB) is widely used. Although PVB can provide excellent performance as a resin interlayer film, it has low bending rigidity not only at high temperature (for example, 50 ° C.) but also near room temperature (for example, 25 ° C.), so that the resin interlayer film is wrinkled in the process of laminating with glass. Is likely to occur and the yield is likely to decrease. In order to avoid this problem, it is necessary to carry out the laminating process at a low temperature. Further, when the resin interlayer containing PVB is used in the laminated glass, the resin interlayer is softened and easily creep-deformed, and as a result, there may be a problem that the laminated glass is displaced. As a means for solving 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, in such a resin interlayer film, improvement in transparency and heat-resistant creep property are still required.

Japanese Unexamined Patent Publication No. 6-321587 International Publication No. 2015/93352 Pamphlet

Therefore, an object of the present invention is to provide a laminated glass having excellent transparency, which is produced by laminating a resin interlayer film having excellent handleability at the time of producing laminated glass with 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。 The present inventors have completed the present invention as a result of diligent studies on laminated glass in order to solve the above-mentioned problems. That is, the present invention includes the following preferred embodiments.
[1] 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) contains a laminate having an adhesive layer (II) containing an acrylic block copolymer (X) on both sides of a base material layer (I) containing a polycarbonate resin.
The following formula (1):

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

The laminated glass according to the above [1], wherein the flexural rigidity of the laminated body at 50 ° C. is 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 laminated body has the following conditions (i) to (iii):
(I) The acrylic block copolymer (X) is a polymer block having a methacrylic acid ester unit as a main constituent unit at one end or both ends of a polymer block (a1) having an acrylic acid ester unit as a main constituent unit. Having a structure in which (a2) is bonded,
(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 the above [1] or [2], which satisfies the above content of 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 an acrylic acid ester unit as a main constituent unit. The laminated glass according to any one of [1] to [3] above, which has a structure in which a polymer block (a2) having a methacrylic acid ester unit as a main constituent unit is bonded thereto.
[5] The laminated glass according to any one of [1] to [4], wherein the resin interlayer film (A) contains two or more of the laminated bodies.
[6] The laminated glass according to any one of [1] to [5] above, wherein the haze of the laminated body measured in accordance with JIS K7136: 2000 is 5% or less.
[7] The laminated glass according to any one of [1] to [6] above, wherein the yellowness of the laminated body measured in accordance with JIS Z8722: 2009 is 3 or less.

According to the present invention, it is possible to provide a laminated glass having excellent transparency, which is produced by laminating a resin interlayer film having excellent handleability at the time of producing laminated glass with glass.

It is a schematic schematic diagram which shows one aspect of the laminated glass of this invention. It is a schematic schematic diagram which shows the compression shear test. It is a schematic diagram which shows the test sample used for the heat-resistant creep property test of laminated glass. It is a schematic schematic diagram which shows the heat-resistant creep property 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 an adhesive layer (II) containing an acrylic block copolymer (X) on both sides of a base material layer (I) containing a polycarbonate resin, and has the following formula. (1):

The flexural rigidity of the laminate shown in 1 at 25 ° C. is 6 N · mm or more and 60 N · mm or less.

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

Examples of the polyfunctional hydroxy compound include linear aliphatic diols, branched aliphatic diols, alicyclic diols, other diols, aromatic dihydroxy compounds and the like. 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 preferable from the viewpoint of easily obtaining better 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, bis (4-). Hydroxyphenyl) sulfoxides, bis (4-hydroxyphenyl) sulfones, bis (4-hydroxyphenyl) ketones, bis (hydroxyphenyl) fluorenes, dihydroxy-p-terphenyls, dihydroxy-p-quarterphenyls, Examples thereof include bis (hydroxyphenyl) pyrazines, bis (hydroxyphenyl) mentans, bis [2- (4-hydroxyphenyl) -2-propyl] benzenes, dihydroxynaphthalenes, dihydroxybenzenes and the like.

Among these, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, and bis (4-hydroxyphenyl) are easy to obtain better heat resistance or mechanical strength. ) 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) ) Pentan, 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, resorcin, and 2,7-dihydroxynaphthalene are preferred. 2,2-Bis (4-hydroxyphenyl) propane is more preferred.

The carbonic acid ester-forming compound is not particularly limited. Examples of the carbonic acid ester-forming compound include various dihalogenated carbonyls such as phosgene; halohomates such as chlorohomet; and carbonic acid ester compounds such as bisaryl carbonate. One carbonic acid ester-forming compound may be used alone, or two or more may be used in combination.

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

The method for producing the polycarbonate resin is not particularly limited, and a conventionally known production method can be used. Further, a commercially available product may be used as the polycarbonate resin. As an example of such a commercially available product, "SDPOLYCA 301-4" (manufactured by Sumika Polycarbonate Limited, melt volume flow rate at 300 ° C. and 1.2 kg load (hereinafter abbreviated as "MVR"): 4 cm ³ / 10 minutes), "SDPOLYCA 301-6" (manufactured by Sumika Polycarbonate Limited, MVR: 6 cm ^3/10 minutes), "SDPOLYCA 301-10" (manufactured by Sumika Polycarbonate Limited, MVR: 6 cm ^3/10 minutes) , "UPILON H-3000" (manufactured by Mitsubishi Engineering Plastics Co., Ltd., MVR: 28 cm ^3/10 minutes), "UPILON S-2000" (manufactured by Mitsubishi Engineering Plastics Co., Ltd., 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 to a substrate and mechanical properties. .. In producing such a polycarbonate resin, the viscosity average molecular weight can be adjusted by using a molecular weight adjusting agent, a catalyst, or the like, if necessary. Further, 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. The MVR at 300 ° C. and a 1.2 kg load is usually 1 to 200 cm ^3/10 min. Here, MVR is measured according to 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. In producing such a polycarbonate resin, the MVR can be adjusted by using a molecular weight adjusting agent, a catalyst, or the like, if necessary. Further, 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, it is easy to prevent the base material (I) from being deformed during the production of laminated glass. When the glass transition temperature is not more than the upper limit value, it is easy to prevent the occurrence of 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 by, for example, adjusting the viscosity average molecular weight or the blending ratio of the polycarbonate resins having different viscosity average molecular weights.

The Charpy impact strength of the polycarbonate resin is not particularly limited. The 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 30 kJ / m 2 or more, from the viewpoint of penetration resistance when a flying object collides with the laminated glass. Is 60 kJ / m ² or more. In the present specification, the Charpy impact strength is the value obtained by notching a 3 mm thick test piece in accordance with ISO179 and measuring the notched Charpy impact strength (unit: kJ / m ² ) at 23 ° C. do. The Charpy impact strength can be adjusted to the lower limit or higher by adjusting, for example, the viscosity average molecular weight distribution or the combination of the polyfunctional hydroxy compound and the carbonic acid ester-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, and particularly preferably 89% or more. When the total light transmittance is at least the lower limit value, the transparency of the base material layer (I) when used in the thickness range described later tends to be high, and the transparency of the obtained laminated glass tends to be high. The total light transmittance can be measured by a haze meter by the measuring method described in JIS K7361-1 using, for example, a molded product having a thickness of 3 mm or less (for example, 3 mm) obtained by press molding a polycarbonate resin. .. The total light transmittance can be adjusted to the lower limit or higher by, for example, selecting a polyfunctional hydroxy compound and a carbonic acid ester-forming compound and adjusting the refractive index of the polycarbonate resin.

<Polycarbonate resin composition>
The base material 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 it does not interfere with the object and effect of the present invention. good.
Examples of additives include antioxidants, heat deterioration inhibitors, UV absorbers, light stabilizers, lubricants, mold release agents, polymer processing aids, antistatic agents, flame retardants, dye pigments, light diffusers, etc. Examples thereof include organic dyes, matting agents, impact resistance modifiers and phosphors. When an additive is used, one may be used alone, or two or more may be used in combination. When an additive is used, the amount of the additive 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 known method for producing the polycarbonate resin composition can be widely adopted. As an example of such a manufacturing method, a polycarbonate resin and an additive to be blended as needed are premixed using various mixers such as a tumbler or a Henschel mixer, and then a Banbury mixer, a roll, a brabender, and the like. Examples thereof include a method of melt-kneading with 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 the 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 preferable that the polycarbonate resin composition has the same characteristics as those of the polycarbonate resin described above.

[Manufacturing method of base material layer (I)]
The method for producing the base material layer (I) is not particularly limited, and a known method for producing a film or sheet can be adopted. 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 meshing twin-screw extruder, a co-directional non-meshing twin-screw extruder, a non-directional non-meshing twin-screw extruder, a multi-screw extruder and the like. can. Among them, a single-screw extruder is preferable because the resin retention portion is small, so that thermal deterioration of the resin can be suppressed during extrusion, and the equipment cost is low. The screw used in a single-screw extruder or the like may be a screw having a general full-flight configuration with a compression ratio of about 2 to 3, and is equipped with a special kneading mechanism such as a barrier flight so that unmelted material does not exist. It may be a screw. Further, in order to remove the residual volatile components in the polycarbonate resin or the polycarbonate resin composition or the volatile components generated by heating in the extruder, an extruder having a venting mechanism may be used.
When the polycarbonate resin composition is used as the material of the base material layer (I), the polycarbonate resin composition may be prepared in advance and put into an extruder to be extruded, or may be blended with the polycarbonate resin and if necessary. Additives may be added to the extruder and extruded.

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

The base material layer (I) preferably has penetration resistance. Therefore, the penetration energy of the base material layer (I) in the drop-weight impact test is preferably 5 J or more, more preferably 10 J or more, still more preferably 13 J or more. When the penetration energy of the base material layer (I) is equal to or higher than the lower limit, the resistance of the laminated glass produced by using the laminated body of the base material layer (I) and the adhesive layer (II) as the resin interlayer film (A). It is easy to adjust the penetration to a sufficient value. A test piece is cut out from the base material layer (I) so that the penetration energy of the base material layer (I) is 60 mm in length × 60 mm in width, and an ASTM D3763 is used with a drop weight type impact tester (CEAST9350 manufactured by Instron). The test was conducted under the conditions of a measurement temperature of 23 ° C., a load of 2 kg, and a collision speed of 9 m / sec. 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 by selecting bisphenol A as the polycarbonate resin contained in the base material layer (I) and / or adjusting the thickness of the base material layer (I). ..

The storage elastic modulus of the base material layer (I) measured at 25 ° C. and a frequency of 1 Hz by tensile dynamic viscoelasticity measurement is preferably 1,000 to 3,500 MPa, more preferably 1,300 to 3,000 MPa, and further. It is preferably 1,500 to 2,500 MPa. When the storage elastic modulus is at least the lower limit value, it is easy to secure sufficient bending rigidity even if the base material layer (I) is thin as long as it can be molded, and when it is at least the upper limit value, the roll shape described later is obtained. It is easy to obtain good shapeability. The storage elastic modulus can be measured by a viscoelasticity measuring device. For example, a sheet having a length of 20 mm, a width of 5 mm, and a thickness of 0.4 mm is produced, and a viscoelasticity spectrometer "Rheogel-E4000" (UBM Co., Ltd.) is produced. It can be measured by performing dynamic viscoelasticity measurement under the measurement conditions of a frequency of 1 Hz and a measurement temperature of -50 to 250 ° C. The storage elastic modulus can be adjusted within the above range by, for example, selecting bisphenol A as the polycarbonate resin contained in the base material layer (I) and / or adjusting the thickness of the base material layer (I). ..

The substrate layer (I) preferably has a high total light transmittance. Therefore, the total light transmittance of the base material layer (I) at the thickness described later is preferably 70% or more, more preferably 80% or more, still more preferably 85% or more, and particularly preferably 89% or more. When the total light transmittance is at least the above lower limit value, the transparency of the obtained laminated glass tends to be high. The total light transmittance can be measured by a haze meter by the measuring method described in JIS K7361-1 using the base material layer (I). For the total light transmittance, a resin having a high total light transmittance as described above is selected as the polycarbonate resin contained in the base material layer (I), and / or the surface roughness of the base material layer (I) is reduced. The lower limit value or more can be adjusted by selecting the additive and / or adjusting the dispersibility of the additive in the polycarbonate resin composition constituting the base material layer (I).

The thickness T (I) of the base material layer (I) is preferably 0.70 mm or less from the viewpoint of handleability of the laminated body of the base material 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 0.30 mm or more, from the viewpoints of easily obtaining desired penetration energy, storage elastic modulus, and flexural rigidity of the laminate described later. It is 0.60 or less, more preferably 0.50 mm or less. The thickness T (I) can be measured with a thickness gauge.

The surface of the base material layer (I) may be subjected to an easy-adhesion treatment as long as it does not interfere with the object and effect of the present invention. Examples of the easy-adhesion treatment include surface treatments such as corona treatment, plasma treatment, and low-pressure ultraviolet treatment.

Further, an easy-adhesion layer may be provided on the base material layer (I) as long as it does not interfere with the object and effect of the present invention. Examples of the resin contained in the easy-adhesion layer include urethane resin, polyester, polyvinyl acetate, epoxy resin, silicone and the like.

The easy-adhesive layer can be formed on the base material layer (I) by a known method. As an example of such a method, a method including applying the above-mentioned resin to the base material layer (I) and drying it can be mentioned. The thickness of the easy-adhesion layer is preferably 1 to 100 nm, more preferably 10 to 50 nm in a dry state. The resin used for coating may be diluted with a solvent. Such a solvent is not particularly limited, but alcohols can be used, for example. The dilution concentration (percentage of the mass of the solid content with respect 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 easy-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 enhancing the adhesive strength with the adhesive layer (II).

[Adhesive layer (II)]
The laminate is composed of a base material layer (I) and two adhesive layers (II) existing on both sides thereof. The materials constituting the two adhesive layers (II) may be the same or different from each other. 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 an acrylic block copolymer (X).

<Acrylic block copolymer (X)>
The acrylic block copolymer (X) in the present invention is a polymer block having a methacrylic acid ester unit as a main constituent unit at one end or both ends of a polymer block (a1) having an acrylic acid ester unit as a main constituent unit. It has a structure in which (a2) is bonded, that is, a structure of (a1)-(a2) or (a2)-(a1)-(a2) (where "-" in the structure indicates a chemical bond). It can be confirmed by, for example, NMR measurement or infrared spectroscopy that the acrylic block copolymer (X) has the above-mentioned structure.
The acrylic block copolymer (X) contained in the adhesive layer (II) may be the acrylic block copolymer (X) alone as exemplified below, or a combination of two or more thereof. May be. For example, an acrylic block copolymer (X) having a structure of (a2)-(a1)-(a2) may be used, or an acrylic block copolymer (X) having a structure of (a1)-(a2) may be used. And may be a combination with an acrylic block copolymer (X) having a structure of (a2)-(a1)-(a2), or may be a combination of physical properties (for example, weight average molecular weight and / or polymer block (for example)). It may be a combination of two (a2)-(a1)-(a2) structured acrylic block copolymers (X) having different contents) of a2).

<Polymer block (a1)>
The content of the acrylic acid ester unit 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 acid ester constituting the acrylic acid ester unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, and the like. 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 thereof include phenoxyethyl acrylate, 2-hydroxyethyl acrylate, and 2-methoxyethyl acrylate. Among these acrylic acid esters, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, and phenoxyethyl acrylate from the viewpoint of easily obtaining improved flexibility. , Acrylic acid alkyl ester such as 2-methoxyethyl acrylate is preferable, and n-butyl acrylate and 2-ethylhexyl acrylate are more preferable. The polymer block (a1) may be composed of one kind of these acrylic acid esters, or may be composed of two or more kinds.

The polymer block (a1) is a structural unit derived from an acrylic acid ester having a reactive group such as glycidyl acrylate and allyl acrylate; or the following methacrylic acid ester, as long as it does not interfere with the object and effect of the present invention. Constituent units derived from other polymerizable monomers other than acrylic acid esters such as methacrylic acid, acrylic acid, aromatic vinyl compounds, acrylonitrile, methacrylonitrile and olefins; and the like may be contained as a copolymerization component. The amount of the structural unit derived from the acrylic acid ester having a reactive group or the structural unit derived from other polymerizable monomers is preferably small from the viewpoint of easily exhibiting 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 acid ester used when preparing the polymer block (a1) having an acrylic acid ester unit as a main constituent unit is a monomer obtained by combining one kind or a combination of two or more kinds. It may be a mixed monomer in which two or more kinds are mixed in advance. The mixed monomer is preferably a mixed monomer of an acrylic acid alkyl ester and an acrylic acid aromatic ester from the viewpoint of enhancing transparency. In this case, it is preferable that it is a mixed monomer of 50 to 90% by mass of acrylic acid alkyl ester and 50 to 10% by mass of acrylic acid aromatic ester, and 60 to 80% by mass of acrylic acid alkyl ester and acrylic acid aromatic ester 40. More preferably, it is a mixed monomer of about 20% by mass.

<Polymer block (a2)>
The content of the methacrylic acid ester unit 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 acid ester constituting the methacrylic acid ester unit include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, and the like. 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 thereof 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 from the viewpoint of easily improving transparency and heat resistance. A methacrylic acid alkyl ester such as isobornyl is preferable, and methyl methacrylate is more preferable. The polymer block (a2) may be composed of one of these methacrylic acid esters, or may be composed of two or more of them.

The polymer block (a2) is a structural unit derived from a methacrylic acid ester having a reactive group such as glycidyl methacrylate and allyl methacrylate; or the acrylic acid ester, as long as it does not interfere with the object and effect of the present invention. Constituent units derived from polymerizable monomers other than methacrylic acid esters such as methacrylic acid, acrylic acid, aromatic vinyl compounds, acrylonitrile, methacrylonitrile, and olefins; and the like may be contained as a copolymerization component. The amount of these structural units derived from the methacrylic acid ester having a reactive group or the structural unit derived from other polymerizable monomers is preferably small from the viewpoint of easily exhibiting 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 which the polymer block (a2) is bonded to the end of the polymer block (a1). For example, the molecular chain form may be linear, branched, radial, or the like, but from the viewpoint of easily obtaining the desired adhesive strength, the 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 layer (II), preferably both of the adhesive layer (II) in the laminated body is an acrylic acid ester unit. It has a structure in which a polymer block (a2) having a methacrylic acid ester unit as a main constituent unit is bonded to both ends of the polymer block (a1) having the above as a main constituent unit. Here, the molecular weights and compositions of the polymer blocks (a2) at both ends of the polymer block (a1) may be the same or different from each other.

As long as it does not interfere with the object and effect of the present invention, the acrylic block copolymer (X) may be used as a polymer block separate from the polymer blocks (a1) and (a2) as an acrylic acid ester and a methacrylic acid ester. It may have a polymer block (c) derived from a monomer other than the above. The form of the bond 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)). _n- (c) and (c)-(a2)-((a1)-(a2)) _n- (c) and the like can be mentioned. Here, n is an integer of 1 to 20.

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

The weight average molecular weight (Mw) of the acrylic block copolymer (X) is determined from the viewpoint of the impact absorption of the obtained adhesive layer (II) and the adhesiveness between the adhesive layer (II) and the base material layer (I). It is preferably 50,000 to 150,000, more preferably 55,000 to 120,000, and particularly preferably 60,000 to 100,000. When the weight average molecular weight of the acrylic block copolymer (X) is at least the above lower limit value, it is easy to maintain sufficient adhesive strength with the base material layer (I) and the inorganic glass, and it is easy to obtain a good laminated glass. In addition, it is easy to obtain mechanical strength such as better breaking strength of the obtained laminated glass. On the other hand, when the weight average molecular weight of the acrylic block copolymer (X) is not more than the above upper limit value, the surface of the molded body of the adhesive layer (II) obtained by extrusion molding or the like has fine grain-like unevenness or no unevenness. It is easy to obtain laminated glass with excellent appearance because it is less likely to generate lumps due to melts (high molecular weight acrylic block copolymer).

The molecular weight distribution represented by the ratio (Mw / Mn) of the number average molecular weight (Mn) of the acrylic block copolymer (X) to the weight average molecular weight (Mw) is not particularly limited. Mw / Mn is preferably in the range of 1.01 or more and less than 10 from the viewpoint of easily suppressing or preventing the content of unmelted material that may cause lumps in the adhesive layer (II), and more preferably. It is within the range of 1.01 or more and 3.0 or less.
The weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present specification are polystyrene-equivalent molecular weights measured by gel permeation chromatography, and are measured by the methods described in Examples described later. 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 adhesion to the base material layer (I). It 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, and 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 all the constituent units constituting the acrylic block copolymer (X). When the content of the polymer block (a2) in (X) is at least the above lower limit value, the sticking feeling of the acrylic block copolymer (X) is unlikely to increase, and such an acrylic block copolymer (X). ) Is more preferable as a material constituting the adhesive layer (II). On the other hand, when the content of the polymer block (a2) in the acrylic block copolymer (X) is not more than the above upper limit value, the acrylic block copolymer (X) is less likely to become hard, and when the laminated glass is manufactured. It is easy to avoid the tendency that the heating time required to obtain sufficient adhesive force between the glass and the substrate layer (I) becomes long.

The method for producing the acrylic block copolymer (X) is not particularly limited, and a known method can be adopted. For example, a method of living-polymerizing the monomers constituting each block is generally used. As an example of such a living polymerization method, an organic alkali metal compound is used as a polymerization initiator, and anionic polymerization is carried out in the presence of a mineral salt such as an alkali metal or an alkaline earth metal salt (Japanese Patent Laid-Open No. 7-25859). (Refer to No. 11-335432), a method of anion polymerization using an organic alkali metal compound as a polymerization initiator in the presence of an organic aluminum compound (see JP-A-11-335432), and polymerization using an organic rare earth metal complex as a polymerization initiator. (Refer to JP-A-6-93060), a method of radically polymerizing in the presence of a copper compound using an α-halogenated ester compound as an initiator (Macromolecular Chemical Physics, Vol. 201, pp. 1108 to 1114, 2000). See) and the like. Further, a method of polymerizing the monomers constituting each block using a polyvalent radical polymerization initiator and a polyvalent radical chain transfer agent to produce a mixture containing an acrylic block copolymer can be mentioned. can. Among these methods, an organic alkali metal compound is particularly suitable because an acrylic block copolymer can be obtained with high purity, the molecular weight and the composition ratio of each polymer block can be easily controlled, and it is economical. A method of anionic polymerization in the presence of an organic aluminum compound, which is used as a polymerization initiator, is preferable.

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, and particularly preferably 89% or more. When the total light transmittance is at least the lower limit value, the transparency of the adhesive layer (II) when used in the thickness range described later tends to be high, and the transparency of the obtained laminated glass tends to be high. The total light transmittance can be measured by a haze meter by the measuring method described in JIS K7361-1 using, for example, a molded product having a thickness of 3 mm or less (for example, 3 mm) obtained by press molding a polycarbonate resin. .. The total light transmittance can be adjusted to the lower limit or higher 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 of the acrylic block copolymer (X) (hereinafter abbreviated as "MFR") is not particularly limited, and is usually 1 to 200 g / 10 minutes. Here, the 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. In producing such an acrylic block copolymer (X), the MFR can be adjusted by using a molecular weight adjusting agent, a catalyst, or the like, if necessary. Further, 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, and even more preferably 50 to 80. When the A hardness is within the above range, it is easy to obtain an adhesive layer (II) having excellent flexibility and peel strength from the base material (I) when the adhesive layer (II) is manufactured with a thickness described later. ..

<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 an acrylic block copolymer as needed as long as it does not interfere with the object and effect of the present invention. It may be an acrylic block copolymer (X) -containing composition containing a component other than (X).
The type of such an ingredient is not particularly limited. For example, various polymers and additives as described later can be mentioned. When such a component is used, one may be used alone, or two or more may be used in combination. When such a component is used, the addition amount thereof is preferably 50% by mass or less, more preferably 30% by mass or less, and further, the total mass of the composition containing the acrylic block copolymer (X). It is preferably 20% by mass or less, and particularly preferably 10% by mass or less.

As the component 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 80% by mass or more of methacrylic acid ester units with respect to all the constituent units constituting the acrylic polymer, and more preferably an acrylic polymer. It is an acrylic polymer containing 90% by mass or more of methacrylic acid ester units with respect to all the constituent units constituting the above. Examples of the methacrylic acid ester constituting the methacrylic acid ester unit include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, and the like. Tert-butyl methacrylate, amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, pentadecyl methacrylate, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, Examples thereof include 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate, glycidyl methacrylate, allyl methacrylate, cyclohexyl methacrylate, norbornenyl methacrylate and isobornyl methacrylate. Of these, methyl methacrylate is particularly preferable.

The acrylic polymer having a methacrylic acid ester unit as a main constituent unit may contain a monomer unit other than the methacrylic acid ester unit. Examples of monomers constituting such other monomer units include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, and acrylic acid. sec-butyl, tert-butyl acrylate, amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethyl hexyl acrylate, pentadecyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, acrylic Acrylic acid esters such as phenoxyethyl acid, 2-hydroxyethyl acrylate, 2-ethoxyethyl acrylate, glycidyl acrylate, allyl acrylate, cyclohexyl acrylate, norbornenyl acrylate and isobornyl acrylate; acrylic acid, methacrylic acid. , Saturated carboxylic acids such as maleic anhydride, maleic acid and itaconic acid; olefins such as ethylene, propylene, 1-butene, isobutylene and 1-octene; conjugated diene such as butadiene, isoprene and milsen; styrene, α-methylstyrene , P-Methylstyrene and aromatic vinyl compounds such as m-methylstyrene; as well as acrylamide, methacrylicamide, acrylonitrile, methacrylnitrile, vinyl acetate, vinylpyridine, vinyl ketone, vinyl chloride, vinylidene chloride and vinylidene fluoride. Can be done.

The method for producing an acrylic polymer having a methacrylic acid ester unit as a main constituent unit is not particularly limited. Further, a commercially available product may be used as such an acrylic polymer. Examples of such commercially available products include "Parapet H1000B" (MFR: 22 g / 10 minutes (230 ° C., 37.3N)), "Parapet GF" (MFR: 15 g / 10 minutes (230 ° C., 37.3N)). "Parapet EH" (MFR: 1.3 g / 10 minutes (230 ° C, 37.3N)), "Parapet HRL" (MFR: 2.0 g / 10 minutes (230 ° C, 37.3N)), "Parapet HRS" (MFR: 2.4 g / 10 minutes (230 ° C, 37.3 N)) and "Parapet G" (MFR: 8.0 g / 10 minutes (230 ° C, 37.3 N)) [Both are trade names, Kuraray Co., Ltd. Made] and the like.

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

Examples of polymers that may be contained in the acrylic block copolymer (X) -containing composition other than the acrylic polymer that may be optionally contained include polyethylene, polypropylene, polybutene-1, and poly-4-methyl. Olefin-based resins such as Penten-1 and polynorbornene; Ethylene-based ionomers; Polystyrene, styrene-maleic anhydride copolymers, high-impact polystyrene, AS resin, ABS resin, AES resin, AAS resin, ACS resin, MBS resin, etc. Stylite-based resin; Methylmethacrylate-styrene copolymer; Polyester resin such as polyethylene terephthalate, polybutylene terephthalate and polylactic acid; Polyamide resin such as nylon 6, nylon 66 and polyamide elastomer; Ester-based polyurethane elastomer, ether-based polyurethane elastomer, none Polyurethane resins such as yellowing ester polyurethane elastomers and non-yellowing carbonate polyurethane elastomers; as well as polycarbonate, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, ethylene-vinyl alcohol copolymers, polyacetals, vinylidene fluoride, modified polyphenylene ethers. , Polyphenylene sulfide, silicone rubber modified resin and the like. One of these polymers may be contained alone, or a combination of two or more thereof may be contained. Among these, AS resin and polyvinylidene fluoride are preferable from the viewpoint of compatibility with the acrylic block copolymer (X).

Examples of additives that can be optionally contained in the acrylic block copolymer (X) -containing composition include rubbers, lubricants, antioxidants, light stabilizers, colorants, antistatic agents, flame retardants, and adhesive modifiers. , 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-based thermoplastic elastomers such as SEPS, SEBS, and SIS; and olefin-based rubbers such as IR, EPR, and EPDM.
Examples of additives other than rubber are mineral oil softeners such as paraffin oils and naphthenic oils (which can improve fluidity during molding); calcium carbonate, talc, carbon black, oxidation. Inorganic fillers such as titanium, silica, clay, barium sulfate, magnesium carbonate (these are mainly added for the purpose of improving or increasing heat resistance or weather resistance); inorganic fibers such as glass fiber and carbon fiber or Organic fibers (these are mainly added for reinforcement); heat stabilizers; antioxidants; photostabilizers; adhesives; tackifiers; plasticizers; antistatic agents; foaming agents; colorants; dyeing Agents and the like can be mentioned.
Among these additives, it is practically preferable to add a heat stabilizer and / or an antioxidant or the like in order to further improve the heat resistance and the weather resistance.

The method for producing the composition containing the acrylic block copolymer (X) is not limited, and a known production method can be widely adopted. As an example of such a production method, the acrylic block copolymer (X) and other components added as necessary are premixed using various mixers such as a tumbler or a Henshell mixer, and then the mixture is then mixed. Examples thereof include a method of melt-kneading with 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 characteristics 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 the same characteristics as those of the acrylic block copolymer (X) described above.

[Manufacturing method of adhesive layer (II)]
The method for producing the adhesive layer (II) containing the acrylic block copolymer (X) is not particularly limited. For example, the material constituting the adhesive layer (II) can be obtained by molding into a sheet using a known device such as a hot press molding machine, a calendar roll or an extruder. Further, the material constituting the adhesive layer (II) is dissolved or dispersed in an organic solvent or an organic dispersion medium to obtain a coating liquid, the coating liquid is applied to the release film, and then the organic solvent or the organic dispersion medium is removed. May be manufactured by. From the viewpoint of degassing, 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 it is preferable to form the adhesive layer (II). The shape of such an uneven structure is not particularly limited, and may be a conventionally known structure.

The storage elastic modulus of the adhesive layer (II) measured at 25 ° C. and a frequency of 1 Hz by the tensile dynamic viscoelasticity measurement is preferably 0.1 to 1000 MPa, more preferably 1 to 500 MPa, and further preferably 10 to 200 MPa. .. When the storage elastic modulus is at least the lower limit value, even if the adhesive layer (II) is thin, the laminate of the base material layer (I) and the adhesive layer (II) can be easily wound up without breaking. Cheap. When the storage elastic modulus is not more than the upper limit value, it is easy to prevent cracking due to stress generated during the production of laminated glass, and it is easy to obtain laminated glass having an excellent appearance. The storage elastic modulus can be measured by a viscoelasticity measuring device. For example, a sheet having a length of 20 mm, a width of 5 mm and a thickness of 0.2 mm is produced, and a viscoelasticity spectrometer "Rheogel-E4000" (manufactured by UBM Co., Ltd.) is produced. ), And the dynamic viscoelasticity can be measured under the measurement conditions of a frequency of 1 Hz and a measurement temperature of −50 to 250 ° C. The storage elastic modulus can be adjusted, for example, by adjusting the composition ratio of the polymer blocks (a1) and (a2) in the acrylic block copolymer (X) contained in the adhesive layer (II), and / or the adhesive layer (II). ) Can be adjusted within the above range by adjusting the thickness.

The thickness T (II) of the one adhesive layer (II) is preferably 0.30 mm or less, more preferably 0.30 mm or less, from the viewpoint of obtaining good rigidity against compressive shearing and good adhesiveness to glass and economically. It is 0.010 to 0.30 mm, more preferably 0.020 to 0.25 mm, and particularly preferably 0.030 to 0.20 mm. The thicknesses of the two adhesive layers (II) contained in one laminate may be the same or different from each other. The thicknesses of the two adhesive layers (II) are preferably the same. The thickness T (II) can be measured with a thickness gauge.

The ratio of the thickness T (I) of the base material layer (I) to the thickness T (II) of the adhesive layer (II) T (I) / T (II) is a material constituting the base material layer (I). Depending on the material constituting the adhesive layer (II) and the intended use, from the viewpoint of the adhesiveness and penetration resistance of each layer when made into laminated glass, and from the viewpoint of easily obtaining the bending rigidity of the desired laminated body. It is preferably 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 having the above-mentioned adhesive layer (II) on both sides of the above-mentioned base material layer (I). In one aspect of the present invention, the resin interlayer film (A) includes one of the above-mentioned laminates. The resin interlayer film (A) may be made of one of the above laminated bodies. Further, in another aspect of the present invention, the resin interlayer film (A) contains two or more of the above-mentioned 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, after satisfying the above-mentioned range of thickness of each layer. When the thickness of one laminate is not more than the upper limit, it is easy to provide the laminate having the 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 laminated body is preferably 0.30 mm or more, more preferably 0.40 mm or more, still more preferably 0.45 mm or more, after satisfying the above-mentioned range of thickness of each layer. When the thickness of one laminated body is at least the above lower limit value, it is easy to obtain the resin interlayer film (A) that provides the penetration resistance required for laminated glass.

The method for producing the resin interlayer film (A) is a laminate having an adhesive layer (II) on both sides of the base material layer (I), that is, an adhesive layer (II) -base material layer (I) -adhesive layer (II). The method is not particularly limited as long as it is a method capable of producing a laminated body in the order of. Examples of such a method include a method of laminating a base material layer (I) and an adhesive layer (II) by a known method such as a thermal laminating method or a pressure bonding method, and an organic material constituting the adhesive layer (II). A coating liquid is obtained by dissolving or dispersing in a solvent or an organic dispersion medium, the coating liquid is applied to one side of the base material layer (I), the organic solvent or the organic dispersion medium is removed, and the base material layer (I) is further removed. After applying the coating liquid to the other surface of), the method of removing the organic solvent or the organic dispersion medium, and the coextrusion of the material constituting the base material layer (I) and the material constituting the adhesive layer (II). You can mention how to do it.

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

The bending rigidity of the laminated body at 25 ° C. is 6 N · mm or more and 60 N · mm or less. If the laminate does not have this particular flexural rigidity, it is difficult for the laminate to have excellent handleability during the production of laminated glass.
Since the resin interlayer film (A) has excellent handleability during the production of laminated glass, the laminate is not wrinkled in the process of sandwiching the laminate contained in the resin interlayer between the glasses, and the laminate can be easily handled. Laminated glass can be manufactured. Further, since the laminated body has this specific bending rigidity, the laminated body can be wound well even with a relatively thin winding core (for example, a winding core having a diameter of 6 inches (about 15.24 cm)). Since the roll body of the obtained laminated body is less likely to bend, it is possible to improve the work efficiency during transportation. Further, after rewinding from the roll body, the winding habit is unlikely to remain in the laminated body.
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, and particularly preferably 14 N · mm or more. When the bending rigidity is at least the lower limit value, it is easy to obtain better handleability at the time of manufacturing laminated glass.
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, still more preferably 30 N · mm. Below, it is particularly preferably 28 N · mm or less. When the flexural rigidity is not more than the upper limit value, it is easier to wind the core relatively thinly, and the winding habit is less likely to remain in the laminated body after rewinding from the roll body.
The flexural rigidity is the lower limit value, for example, by laminating a specific base material layer (I) and a specific adhesive layer (II) at an appropriate thickness ratio, or by adjusting the flexural modulus of each layer. It can be adjusted to the above and below the upper limit.

The bending rigidity of the laminate at 50 ° C. is preferably 4 N · mm or more, more preferably 6 N · mm or more, more preferably 8 N · · from the viewpoint of easily obtaining excellent handleability at the time of manufacturing laminated glass even at a high temperature. mm or more, more preferably 10 N · mm or more, still 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, and particularly preferably 40 N · mm or less. In one aspect of the present invention, the flexural rigidity of the laminated body at 50 ° C. is 4 N · mm or more and 60 N · mm or less. When the bending rigidity is at least the lower limit value, it is easy to obtain better handleability at the time of manufacturing laminated glass even at a high temperature. When the bending rigidity is not more than the upper limit value, even at a high temperature, it is easier to turn the ticket better even on a relatively thin winding core, and the winding habit is less likely to remain on the laminated body after rewinding from the roll body.
The flexural rigidity is determined by, for example, laminating a specific base material layer (I) and a specific adhesive layer (II) at an appropriate thickness ratio, or a group of the adhesive layer (II) with respect to the thickness T (II). By increasing the ratio T (I) / T (II) of the thickness T (I) of the material layer (I), it can be adjusted to be equal to or higher than the lower limit value and lower than 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 flexural rigidity of the laminated body 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 material layer (I) and the resin constituting the adhesive layer (II) may be used, and as described above, it will be described later. Values experimentally measured by the method described in Examples may be used. In the present invention, 0.38 is used as the Poisson's ratio.

The laminated glass of the present invention can have excellent transparency due to the resin interlayer film (A). Therefore, the laminated glass of the present invention can have excellent transparency even when the type of the inorganic glass as the outer layer is changed according to the application.
From the viewpoint of easily bringing more excellent transparency to the laminated glass, the haze of one laminate contained in the resin interlayer film (A) is preferably 5% or less, more preferably 2% or less, still more preferably 1% or less. Is. The lower limit of haze is not specified. The haze of one laminate is usually 0.01% or more. The upper limit of the haze is obtained 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 according to 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 coloring property due to the resin interlayer film (A), and can be as colorless as possible.
The yellowness (YI) of one laminate contained in the resin interlayer film (A) is preferably 3 or less, more preferably 2 or less, still more preferably 1 or less, from the viewpoint of easily bringing a lower colorability to the laminated glass. , Particularly preferably 0.5 or less. The yellowness is 0 or more. The yellowness can be determined by using the acrylic block copolymer (X) contained in the adhesive layer (II) with a copolymer showing a low yellowness, or by reducing the thickness of the resin interlayer film (A). It can be adjusted below the upper limit. The yellowness can be measured according to JIS Z8722: 2009 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). ..

Since the laminated glass of the present invention can have excellent transparency due to the resin interlayer film (A), the inorganic glass should be selected according to the application while ensuring sufficient transparency of the laminated glass. Can be done. The haze of the laminated glass of the present invention is not particularly limited, and it is preferable that the haze is similar to the haze of the above-mentioned laminated glass.

Since the laminated glass of the present invention can have extremely low coloring property due to the resin interlayer film (A), the inorganic glass should be selected according to the application while ensuring sufficient transparency of the laminated glass. Can be done. The yellowness of the laminated glass of the present invention is not particularly limited, and is preferably the same as the yellowness of the above-mentioned laminated glass.

<Inorganic glass>
As the two pieces of inorganic glass laminated with the resin interlayer film (A), for example, an inorganic glass such as a float glass, a polished plate glass, a template glass, a meshed plate glass, or a heat ray absorbing plate glass can be used. The inorganic glass may be colorless or colored. The types and thicknesses of the two pieces of inorganic glass may be the same or different from each other.

[Laminated glass]
The laminated glass of the present invention has a structure in which inorganic glass is laminated on both sides of the resin interlayer film (A). The resin interlayer film (A) includes a laminate having an adhesive layer (II) on both sides of the base material layer (I).
When one laminated body is contained in the resin interlayer film (A), the laminated glass has a structure as shown in FIG. That is, in one aspect of the present invention, the laminated glass has a structure in which the inorganic glass 11, the resin interlayer film (A) 31, and the inorganic glass 11 are laminated in this order, and the resin interlayer film (A) 31 is a base material layer. (I) It is composed of a laminated body having an adhesive layer (II) 21 on both sides of 22. In addition, in FIG. 1 and FIGS. 2 to 4 described later, the dimensions and ratios of the constituent elements are appropriately different in order to make the drawings easier to see.
The number of laminates contained in the resin interlayer film (A) may be two or more. For example, when the resin interlayer film (A) contains two laminates, the laminated glass is an inorganic glass / adhesive layer (II) / base material layer (I) / adhesive layer (II) / adhesive layer (II) / group. It has a structure of a material layer (I) / adhesive layer (II) / inorganic glass. When the resin interlayer film (A) contains two or more laminates, it can be preferably used for applications that require particularly excellent penetration resistance such as bulletproof glass. When the resin interlayer film (A) contains two or more laminates, the materials and thicknesses of the base material layer (I) and the adhesive layer (II) constituting the plurality of laminates may be the same as each other. It may or may not be different.

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

The laminated glass may be used as a single piece or in a state where two or more pieces are combined. When used in a state where two or more sheets are combined, the laminated glass is, for example, glass / adhesive layer (II) / base material layer (I) / adhesive layer (II) / glass / adhesive layer (II) / base material layer ( It has a structure of I) / adhesive layer (II) / glass. When two or more laminated glasses are used in combination, the materials and thicknesses constituting the laminated glasses may be the same or different from each other.

[Manufacturing method of laminated glass]
The laminated glass of the present invention can be produced by a conventionally known method. Examples of such a method include a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, and a method using a nip roll. Further, a method of temporarily crimping by the above method and then putting it into an autoclave for main bonding can also be mentioned.

When using a vacuum laminator device, for example, the inorganic glass, the resin interlayer film (A), and the inorganic glass are laminated at 60 to 200 ° C., particularly 80 to 160 ° C. under a reduced pressure of 1 × 10 ^-6 to 3 × 10 ⁻² MPa. This makes it possible to manufacture laminated glass.

When a vacuum bag or a vacuum ring is used, for example, as described in European Patent No. 1235683, 100 inorganic glass, resin interlayer film (A), and inorganic glass are used under a pressure of about 2 × 10 ⁻² MPa. Laminated glass can be manufactured by laminating at ~ 160 ° C.

When a nip roll is used, the inorganic glass, the resin interlayer film (A), and the inorganic glass are degassed by a roll at a temperature equal to or lower than the flow start temperature of the resin interlayer film (A), and then the resin interlayer film (A) is used. Laminated glass can be manufactured by heating the glass to a temperature close to the flow start temperature of the above and crimping the inorganic glass, the resin interlayer film (A), and the inorganic glass. More specifically, for example, the inorganic glass, the resin interlayer film (A), and the inorganic glass are laminated and heated to 30 to 70 ° C. with an infrared heater or the like, then degassed with a roll, and then 50 to 150 ° C. Laminated glass can be manufactured by pressure-bonding the inorganic glass, the resin interlayer film (A), and the inorganic glass with a roll.

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

As is known, the safety of laminated glass depends on the adhesive force between the resin interlayer film and the outer layer glass. This adhesive strength is preferably high enough to ensure that the glass shards remain adhered to the resin interlayer during mechanical breakage of the glass and that the sharp-edged glass shards cannot be peeled off. .. However, if the adhesive force between the resin interlayer film and the glass is too high, the colliding object may penetrate the laminated glass. When the adhesive force of the resin interlayer film to the glass is low, the resin interlayer film is partially peeled off from the glass and deformed while being stretched at the collision point, so that the collision energy is attenuated and the collision object is penetrated. It is suppressed. That is, the adhesive strength between the glass and the resin interlayer in the laminated glass is high enough to guarantee that the glass fragments remain adhered to the resin interlayer when the glass is broken, and the penetration resistance is not deteriorated. It is preferable not to be too much.
From this point of view, the adhesiveness between the inorganic glass evaluated by the compression shear test and the adhesive layer (II) of the laminated glass of the present invention 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 adhesiveness between the inorganic glass and the adhesive layer (II) is, for example, the selection of the acrylic block copolymer (X) contained in the adhesive layer (II), or the adhesiveness adjusting agent or filler to the adhesive layer (II). Alternatively, it can be adjusted within the above range by adding an additive such as an adhesiveness adjusting agent. The adhesiveness between the inorganic glass and the adhesive layer (II) can be measured, for example, by the compression shear test described in JP-A-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-resistant creep property of the laminated glass tends to decrease. The laminated glass of the present invention can have excellent heat-resistant creep property 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 the deviation generated in the laminated glass when the accelerated test is carried out under the conditions of a load of 37 kg / m ² and an atmospheric temperature of 100 ° C. for one week. Specifically, it can be evaluated by the method described in Examples described later. 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-resistant creep property is not more than the above upper limit value, it is easy to prevent the problem that the installed glass falls off or moves due to heat displacement in the laminated glass. The heat-resistant creep property can be adjusted to the above upper limit value or less by increasing the storage elastic modulus or MFR of the adhesive layer (II).

When broken, it is preferable that the base material layer (I) contained in the laminated glass does not form large fragments unlike the inorganic glass alone. Therefore, a sufficient adhesive force is required between the base material layer (I) and the adhesive layer (II). The adhesive strength between the base material layer (I) and the adhesive layer (II) can be evaluated by measuring the peel strength according to, for example, JIS K6854-2. Specifically, it can be measured by the method described in Examples described later. 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, still more preferably more than 20 N / 25 mm. When the peel strength is larger than the lower limit, it is easy to obtain a strong adhesive force, for example, a thin (for example, 0.2 mm thick) adhesive layer that breaks before peeling, and it is easy to obtain a strong adhesive force at the time of manufacturing laminated glass. Alternatively, in the laminated glass after production, the problem of peeling between the base material layer (I) and the adhesive layer (II) is unlikely to occur.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. 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 the number average molecular weight (Mn) of the acrylic block copolymer (X) were determined as polystyrene-equivalent molecular weights by gel permeation chromatography (hereinafter abbreviated as GPC). The details are as follows.
-Device: 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 refractometer (RI)

<Contents 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. The details are as follows.
・ Equipment: Nuclear magnetic resonance equipment "JNM-LA400" manufactured by JEOL Ltd.
-Deuterated solvent: Deuterated chloroform

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

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

<Flexural rigidity>
The laminate prepared in the Examples or Comparative Examples described later was cut out to prepare a sheet having a length of 40 mm, a width of 30 mm, and a thickness of 0.8 mm. From each of the prepared sheets, three test pieces having a size of 40 mm × 10 mm × 0.8 mm were cut out 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 flexural modulus at 25 ° C. and 50 ° C. was measured when the distance between the fulcrums was 16 mm. For each laminated body, the average value of the bending elastic modulus obtained by the measurement was adopted as the bending elastic modulus of the laminated body. The flexural rigidity of each laminate was calculated according to equations (1) and (2) using the flexural modulus and thickness. A Poisson's ratio of 0.38 was used.

<Adhesiveness between the base material layer (I) and the adhesive layer (II)>
Using the base material layer and the adhesive layer used in Examples 1 to 4 and Comparative Examples 2 to 3 described later, three test pieces for measuring delamination strength were prepared by the following procedure.
A base material layer having a length of 150 mm and a width of 75 mm and an adhesive layer were laminated, and a PET film (MRF38, manufactured by Mitsubishi Plastics Co., Ltd., 75 mm in length × 75 mm in width, 38 μm in thickness) subjected to a peeling treatment with silicone was inserted between them. .. The PET film is inserted by passing the stacked layers and PET film between a roll at 130 ° C and a roll at 40 ° C using a thermal laminating device (VAII-700 type manufactured by Taisei Laminator Co., Ltd.) and thermally laminating them. The base material layer and the adhesive layer in the non-bonded region were bonded (the area of the bonded region: length 75 mm × width 75 mm, the area of the non-bonded region: length 75 mm × width 75 mm). The obtained partially bonded product was humidity-controlled in a constant temperature and humidity chamber (20 ° C.-65% RH) for 24 hours, and then between two flat float glasses (length 300 mm × width 300 mm × thickness 3.0 mm). It was placed near the center of. After putting this in a rubber bag, temporary crimping with a vacuum laminator and compression with an autoclave were performed under the conditions described in the paragraph <Handling> described later.
The glass and PET film are removed from the test pieces that have undergone the above steps, and three test pieces having a length of 150 mm x a width of 25 mm (area of the bonded area: length 75 mm x width 25 mm, area of the non-bonded area: length 75 mm x width 25 mm) are 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 a strong adhesive tape (manufactured by Nitto Denko Corporation: Hyper Joint H9004). A base material using a desktop precision universal testing machine (manufactured by Shimadzu Corporation: AGS-X) under the conditions of a peeling angle of 180 °, a tensile speed of 100 mm / min, and an environmental temperature of 23 ° C in accordance with JIS K6854-2. The peel strength between the layer (I) and the adhesive layer (II) was measured, respectively. The adhesive strength (unit: N / 25 mm) was obtained from the average value of the measured values, and evaluated according to the following criteria.
A: Maximum peel strength is over 20N / 25mm and adhesive layer (II) is material destruction B: Maximum peel strength is over 12N / 25mm, 20N / 25mm or less C: Maximum peel strength is 10N / 25mm Super, 12N / 25mm or less D: Maximum peel strength is 10N / 25mm or less

<Handling>
Each resin interlayer film produced in the examples or comparative examples described later was cut out to a size of 300 mm × 300 mm. Each of the cut out resin interlayer films is humidified in a constant temperature and humidity chamber (20 ° C.-65% RH) for 24 hours, and then between two flat float glasses (length 300 mm × width 300 mm × thickness 3.0 mm). Placed in each. After putting this in a rubber bag, put it in a vacuum laminator (1522N manufactured by Nisshinbo Mechatronics Co., Ltd.), and in the resin interlayer film (A-7) using thermoplastic polyurethane resin, the hot plate temperature is 100 ° C. and the vacuuming time is 12 minutes. Float glass by degassing under the conditions of press pressure 50 kPa, press time 17 minutes, hot plate temperature 165 ° C, evacuation time 12 minutes, press pressure 50 kPa, press time 17 minutes for other resin interlayers. And the resin interlayer were temporarily bonded. Then, the temporary crimped product taken out from the rubber bag was compressed by an autoclave to obtain a flat laminated glass. The conditions for the autoclave 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 handleability at the time of manufacturing laminated glass was evaluated according to the following criteria.
A: Can be manufactured without problems B: There is a problem with manufacturing (deflection or wrinkles of the resin interlayer film, or poor shaping)

<Adhesion between inorganic glass and adhesive layer (II) (compressive shear test)>
The compression shear test described in JP-A-2006-13505 was carried out on each resin interlayer film produced in Examples or Comparative Examples described later, and the adhesive strength between the inorganic glass and the adhesive layer (II) was evaluated. Specifically, the evaluation was performed according to the following procedure.
The resin interlayer film was cut out to a size of 100 mm × 100 mm. After controlling the humidity of the cut out resin interlayer film in a constant temperature and humidity chamber (20 ° C.-65% RH) for 24 hours, it is placed between two flat float glasses (length 100 mm x width 100 mm x thickness 3.0 mm). , The tin surface of the glass was placed so as to be in contact with the resin interlayer film. After putting this in a rubber bag, it is put into a vacuum laminator (1522N manufactured by Nisshinbo Mechatronics Co., Ltd.). For the other resin interlayer film, the float glass and the resin interlayer film were temporarily bonded by degassing under the conditions of a hot plate temperature of 165 ° C., a vacuuming time of 12 minutes, a press pressure of 50 kPa, and a press time of 17 minutes. .. Then, the temporary crimped product taken out from the rubber bag was compressed using an autoclave under the conditions of a pressure of 12 bar and a temperature of 140 ° C. for a total time of 90 minutes or less to obtain a flat laminated glass.
The obtained laminated glass was cut to obtain three test samples having a length of 25 mm and a width of 25 mm. Each test sample was sandwiched in the test apparatus shown in FIG. 2 at an angle of 45 °. By applying a force in the vertical direction to the test equipment, the test sample is sheared, the maximum shear force required for the separation between the glass and the resin interlayer film is obtained, and the average value of the three test samples is calculated. Calculated. The compression shear force (MPa) was obtained by dividing the obtained average value by the sample area (25 mm × 25 mm) × √2. The smaller the value of the compressive shearing force, the smaller the adhesive force between the glass and the resin interlayer film.

<Evaluation of heat-resistant creep property of laminated glass>
Each resin interlayer film produced in Examples or Comparative Examples described later was cut out to a size of 135 mm in length × 50 mm in width. Next, as shown in FIG. 3, between the float glasses 41 and 42 having a length of 165 mm, a width of 50 mm, and a thickness of 3 mm, 135 mm of the length of 165 mm of these float glasses is formed on both sides of the substrate layer (I) 52. The laminated glass 40 was manufactured by sandwiching the resin interlayer film (A) 61 so as to adhere to the resin interlayer film (A) 61 made of a laminated body provided with the adhesive layer (II) 51. The manufacturing procedure of the laminated glass is the same as the manufacturing procedure described in the paragraph <Handability> above.
Subsequently, as shown in FIG. 4, an iron plate 71 having a weight of 250 g was bonded to the glass 41 side of the laminated glass 40 using an instant adhesive 81 to manufacture a laminated glass 90 to which the iron plates were bonded. The laminated glass 90 to which the iron plate was bonded was leaned against the stand 101 and left in a chamber at 100 ° C. for one week. After being left to stand, the distance at which the glass 41 slipped was measured, and the distance was evaluated based on the following criteria, and this evaluation was used as the evaluation of heat-resistant creep property.
A: The distance that the glass 41 has slipped off is 1 mm or less.
B: The distance that the glass 41 has slipped off exceeds 1 mm.

In the following synthetic example, the compound was dried and purified by a conventional method and degassed with nitrogen. In addition, the transfer and supply of the compound were carried out in a nitrogen atmosphere.

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

Then, 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 dropping, the polymer contained in the reaction solution was sampled and the weight average molecular weight was measured and found to be 58,000. As described above, the weight average molecular weight of the methyl methacrylate polymer to be the polymer block (a2) was 24,000, so that the acrylic acid ester polymer block (a1) made of the n-butyl acrylate copolymer The weight average molecular weight was determined to be 34,000.

Subsequently, 18.0 g of methyl methacrylate for the second time was added to the reaction solution, the temperature of the reaction solution was returned to room temperature, and the mixture was stirred for 8 hours to form a second methacrylic acid ester polymer block (a2). did. Then, 4 g of methanol was added to the reaction solution to terminate 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 filtered. The acrylic block copolymer (A1) collected by filtration was dried at 80 ° C. and 1 torr (about 133 Pa) for 12 hours and isolated. 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, it was determined that the weight average molecular weight of the second methyl methacrylate polymer block (a2) was 10,000. This acrylic block copolymer (A1) was pelletized by 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 polymer block (PnBA) -methyl methacrylate polymer block (PMMA). It was a copolymer. The PMMA content (content of the polymer block (a2)) with respect to all the constituent units constituting this triblock copolymer is 50.0% by mass, and the weight average molecular weight of the triblock copolymer is 68,000 (). It was 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)]
Acrylic block copolymer 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 was changed to 79.0 g. The pellet of (A2) was obtained.
The structure of the obtained acrylic block copolymer (A2) is a triblock of methyl methacrylate polymer block (PMMA) -n-butyl polymer block (PnBA) -methyl methacrylate polymer block (PMMA). It was a copolymer. The PMMA content (content of the polymer block (a2)) with respect to all the constituent units constituting this triblock copolymer is 30.5% by mass, and the weight average molecular weight of the triblock copolymer is 64,000 (). It was 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)]
Acrylic block copolymer in the same manner as in Synthesis Example 2 except that the first addition amount of methyl methacrylate was changed to 19.0 g and the second addition amount of methyl methacrylate was changed to 28.0 g. The pellet of (A3) was obtained.
The structure of the obtained acrylic block copolymer (A3) is a triblock of methyl methacrylate polymer block (PMMA) -n-butyl polymer block (PnBA) -methyl methacrylate polymer block (PMMA). It was a copolymer. The PMMA content (content of the polymer block (a2)) with respect to all the constituent units constituting this triblock copolymer is 38.5% by mass, and the weight average molecular weight of the triblock copolymer is 69,000 (). It was 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 for the fact that the amount of methyl methacrylate added in the first time was changed to 36.0 g, the amount of n-butyl acrylate added was changed to 170 g, and the amount of methyl methacrylate added in the second time was changed to 36.0 g. Obtained pellets of an acrylic block copolymer (A4) 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 polymer block (PnBA) -methyl methacrylate polymer block (PMMA). It was a copolymer. The PMMA content (content of the polymer block (a2)) with respect to all the constituent units constituting this triblock copolymer is 30.0% by mass, and the weight average molecular weight of the triblock copolymer is 131,000 (. It was 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 (acrylic block copolymer (A1)) obtained in Synthesis Example 1 pre-dried at 60 ° C. for 24 hours was used in a 25 mφ single-screw extruder "VGM25-28EX" (manufactured by G & M Engineering Company Limited). , Extruded from a single-layer T-die at a resin temperature of 220 ° C. and taken up with a roll having a surface temperature of 60 ° C. to obtain an adhesive layer (II-1) having a width of 300 mm and a thickness of 0.20 mm.

[Preparation of adhesive layer (II-2)]
The adhesive layer (adhesive layer) except that the resin obtained in Synthesis Example 2 (acrylic block copolymer (A2)) was used instead of the acrylic block copolymer (A1) and the resin temperature was changed to 170 ° C. 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 (adhesive layer) except that the resin obtained in Synthesis Example 3 (acrylic block copolymer (A3)) was used instead of the acrylic block copolymer (A1) and the resin temperature was changed to 180 ° C. An adhesive layer (II-3) 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-4)]
The adhesive layer (adhesive layer) except that the resin obtained in Synthesis Example 4 (acrylic block copolymer (A4)) was used instead of the acrylic block copolymer (A1) and the resin temperature was changed to 190 ° C. An adhesive layer (II-4) 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-5)]
The adhesive layer (adhesive layer) except that the resin obtained in Synthesis Example 3 (acrylic block copolymer (A3)) was used instead of the acrylic block copolymer (A1) and the resin temperature was changed to 170 ° C. An adhesive layer (II-5) having 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. (the viscosity average degree of polymerization of the raw material polyvinyl alcohol is 1700, the acetal constituent unit content is 74 mol%, the vinyl alcohol unit content is 19 mol%, and vinyl acetate. Adhesive layer (II-) except that 61.5 parts by mass (unit content 7 mol%) and 20 parts by mass of diisodecylphthalate as a plasticizer were put into a single shaft extruder and the resin temperature was changed to 190 ° C. 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 the production method of 1).

[Preparation of adhesive layer (II-7)]
A formwork (length 30 cm x width 30 cm x height 0.80 mm) in which Argotec ST6050 (manufactured by SWM), which is a non-yellowing thermoplastic polyurethane resin sheet, is installed between two stainless steel plates (length 35 cm x width 35 cm). ). 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. Then, the resin sheet was hot-pressed at a pressure of 90 kgf / cm ² (about 8.8 MPa) for 180 seconds. Immediately after that, the stainless steel plate and the mold were set in a cooling press at 23 ° C. Pressure was applied to the resin sheet while cooling the resin sheet with a cooling press. By cutting out the resin sheet in the mold, an adhesive layer (II-7) having a length of 30 cm, a width of 30 cm, and a thickness of 0.20 mm was obtained.

[Preparation of base material layer (I)]
Polycarbonate resin "SDPOLYCA 301-4" (manufactured by Sumika Polycarbonate Limited) pre-dried at 100 ° C. for 24 hours was 280 using a 25 mmφ single-screw extruder "VGM25-28EX" (manufactured by G & M Engineering Company Limited). It was extruded from a single-layer T-die at a resin temperature of ° C. and taken up with a roll having a surface temperature of 140 ° C. to obtain a base material layer (I) having a width of 300 mm and a thickness of 0.40 mm.

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

[Examples 2 to 4]
In the same manner as in Example 1 except that the adhesive layers (II-2) to (II-4) were used instead of the adhesive layer (II-1), the long roll body of the laminated body and the resin interlayer film ( A-2) to (A-4) and laminated glass (A-2) to (A-4) were produced, respectively. 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]
The resin intermediate is the same as in Example 1 except that only the adhesive layer (II-5) obtained in the above [Preparation of the adhesive layer (II-5)] is used instead of the long roll body of the laminated body. A film (A-5) and a laminated glass (A-5) were manufactured. The adhesiveness between the inorganic glass and the adhesive layer (II-5) was 4.4 MPa.

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

[Comparative Example 3]
A 30 cm × 30 cm laminate, a resin interlayer film (A-7), and a laminated glass (same as in Example 1) except that the adhesive layer (II-7) was used instead of the adhesive layer (II-1). A-7) was manufactured.

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

As shown in Table 1, the resin interlayer films in Examples 1 to 4 may be combined with the base material layer (I) due to the excellent transparency of the acrylic block copolymer (X). It had low haze and low yellowness. This indicates that the laminated glass has excellent transparency when the laminated glass is produced using the resin interlayer films of Examples 1 to 4.
Further, by laminating the specific base material layer (I) and the specific adhesive layer (II) at an appropriate thickness ratio, the flexural rigidity range of the laminated body was satisfied at both 25 ° C. and 50 ° C. Therefore, the laminated body can be satisfactorily wound around a generally used 6-inch (about 15.24 cm) diameter winding core, and the long roll body of the laminated body is less likely to bend during transportation. In addition, the work efficiency of the laminated glass can be improved, the winding habit does not remain in the laminated body after rewinding, and as shown in the handling test results, no wrinkles occur and the laminated glass can be easily prepared. I was able to manufacture it. This indicates that the handleability of the resin interlayer film at the time of manufacturing laminated glass is extremely excellent not only at room temperature (25 ° C.) but also at a high temperature of 50 ° C.
Further, the laminated glass of Examples 1 to 4 has excellent adhesiveness between the base material layer (I) and the adhesive layer (II), and is also excellent in heat-resistant creep property. Further, the laminated glass of Examples 1 to 3 also had excellent adhesiveness (compression shear peeling strength) between the inorganic glass and the adhesive layer (II). From this, it was also confirmed that the laminated glass of Examples 1 to 3 maintained a very excellent compression shear peeling strength for a long period of time.

On the other hand, in Comparative Example 1, although the haze and the yellowness were excellent, the bending rigidity was insufficient, so that the work efficiency of transporting the long roll body was poor, and wrinkles were generated even when laminated with glass.
In Comparative Examples 2 and 3, the handleability at the time of producing the laminated glass was good, but the haze and the yellowness were inferior. Further, in Comparative Example 3, the heat-resistant creep property was also inferior.

The laminated glass of the present invention has extremely excellent transparency (low haze and low yellowing degree), and is also very excellent in handleability at the time of manufacturing laminated glass. It also has excellent adhesiveness between the base material layer (I) and the adhesive layer (II), excellent adhesiveness between the inorganic glass and the adhesive layer (II), and excellent heat-resistant creep property. Therefore, the laminated glass of the present invention may be a laminated glass for vehicle use (for example, an automobile front glass, an automobile side glass, an automobile sun roof, an automobile rear glass, a head-up display glass, etc.) or a building use (for example, a facade, an outer wall). Or laminated glass for roofs, panels, doors, windows, walls, roofs, sun roofs, sound insulation walls, display windows, balconies, handrail walls and other building materials, meeting room partition glass members, solar panels, etc.), especially for construction. It can be suitably used as a laminated glass for various purposes.

11 Inorganic glass 21 Adhesive layer (II) containing an acrylic block copolymer (X)
22 Base material layer (I) containing a polycarbonate resin
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 an acrylic block copolymer (X)
52 Base material layer (I) containing a polycarbonate resin
61 Resin interlayer film (A)
71 Iron plate 81 Instant adhesive 90 Laminated glass with iron plates bonded 101 Stand

Claims (7)

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

Laminated glass having a bending rigidity of 6 N · mm or more and 60 N · mm or less at 25 ° C. of the laminated body represented by. The following formula (2):

The laminated glass according to claim 1, wherein the laminated glass represented by the above item has a bending rigidity of 4 N · mm or more and 60 N · mm or less at 50 ° C. The acrylic block copolymer (X) contained in one or both of the adhesive layers (II) in the laminated body has the following conditions (i) to (iii):
(I) The acrylic block copolymer (X) is a polymer block having a methacrylic acid ester unit as a main constituent unit at one end or both ends of a polymer block (a1) having an acrylic acid ester unit as a main constituent unit. Having a structure in which (a2) is bonded,
(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 requirement of 10 to 60% by mass. The acrylic block copolymer (X) contained in one or both of the adhesive layers (II) in the laminate is methacrylic at both ends of the polymer block (a1) having an acrylic acid ester unit as a main constituent unit. The laminated glass according to any one of claims 1 to 3, which has a structure in which a polymer block (a2) having an acid ester unit as a main constituent unit is bonded. The laminated glass according to any one of claims 1 to 4, wherein the resin interlayer film (A) contains two or more of the laminated bodies. The laminated glass according to any one of claims 1 to 5, wherein the haze of the laminated body measured according to JIS K7136: 2000 is 5% or less. The laminated glass according to any one of claims 1 to 6, wherein the laminated glass has a yellowness of 3 or less as measured in accordance with JIS Z8722: 2009.

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