JP2011068529A - Intermediate film for laminated glass, multilayered intermediate film for laminated glass and laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an intermediate film for laminated glass where penetration resistance at a high temperature around 5°C is enhanced. <P>SOLUTION: The intermediate film 2 for the laminated glass includes a thermoplastic resin and a plasticizer. The plasticizer is at least one selected from the group consisting of the plasticizer, an epoxidized vegetable oil and a polyester plasticizer whose formulas are denoted as formula (1) in which R1, R2 and R3 each represents a 8-15C alkyl. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an interlayer film for laminated glass containing a thermoplastic resin and a plasticizer, and a multilayer interlayer film for laminated glass and laminated glass using the interlayer film for laminated glass.

  Laminated glass is excellent in safety because it has less scattering of glass fragments even if it is damaged by external impact. For this reason, laminated glass is widely used in automobiles, railway vehicles, aircraft, ships, buildings, and the like.

  Laminated glass is manufactured by sandwiching an interlayer film for laminated glass between a pair of glass plates. Laminated glass is required to have high penetration resistance.

  As a method for obtaining laminated glass having high penetration resistance, conventionally, in an intermediate film containing a polyvinyl acetal resin and a plasticizer, there are a method for increasing the hydroxyl group content of the polyvinyl acetal resin and a method for reducing the plasticizer content. Are known.

  Further, as an example of the interlayer film for laminated glass having high penetration resistance, the following Patent Document 1 discloses an interlayer film containing 100 parts by weight of polyvinyl butyral resin and 20 to 80 parts by weight of an ether ester plasticizer. Has been. Here, three or more ether ester plasticizers having different degrees of polymerization are contained, and the ether ester plasticizer is a diester of polyethylene glycol and 2-ethylhexyl acid having an average degree of polymerization of 5 to 10.

JP-A-11-106594

  Laminated glass is often used at a high temperature of about 35 ° C., for example, in summer.

  In conventional laminated glass, even though the penetration resistance at normal temperature (23 ° C.) is high, the penetration resistance at a high temperature around 35 ° C. may be greatly reduced.

  Furthermore, the interlayer film having a high hydroxyl group content and the interlayer film having a small plasticizer content in the polyvinyl acetal resin has low flexibility and has a problem in handling.

  An object of the present invention is to provide an interlayer film for laminated glass capable of enhancing penetration resistance at a high temperature around 35 ° C., and a multilayer interlayer film for laminated glass and a laminated glass using the interlayer film for laminated glass. is there.

  According to a wide aspect of the present invention, a thermoplastic resin and a plasticizer are contained, and the plasticizer is selected from the group consisting of a plasticizer represented by the following formula (1), an epoxidized vegetable oil, and a polyester plasticizer. An interlayer film for laminated glass is provided.

  In said formula (1), R1, R2, and R3 show a C8-C15 alkyl group, respectively.

  In a specific aspect of the interlayer film for laminated glass according to the present invention, the thermoplastic resin is a polyvinyl acetal resin.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the plasticizer is a plasticizer represented by the formula (1).

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the epoxidized vegetable oil is an epoxidized vegetable oil represented by the following formula (2).

  In the above formula (2), R11 to R13 each represent an alkylene group having 4 to 10 carbon atoms, at least one of R14 to R16 represents an organic group containing an epoxy group, and includes an epoxy group of R14 to 16 A group that is not an organic group represents an alkyl group having 1 to 10 carbon atoms.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the organic group containing the epoxy group in the formula (2) is a group represented by the following formula (11).

  In said formula (11), R21 shows a C1-C10 alkylene group, R22 shows a C1-C15 alkyl group, n1 shows the integer of 0-2. When n1 is 2, the plurality of R21s may be the same or different.

  In another specific aspect of the interlayer film for laminated glass according to the present invention, the polyester plasticizer includes a monohydric alcohol and a monobasic acid at both ends of the polycondensate of the polybasic acid and the polyhydric alcohol. It is a derivative of a polycondensate obtained by reacting at least one kind.

  In still another specific aspect of the interlayer film for laminated glass according to the present invention, the polyester plasticizer is a polyester plasticizer represented by the following formula (3).

  In the above formula (3), A represents a polybasic acid residue, G represents a polyhydric alcohol residue, R31 and R32 each represent a monohydric alcohol residue or a monobasic acid residue, n2 represents an integer of 1 or more.

  The multilayer interlayer film for laminated glass according to the present invention is a multilayer interlayer film for laminated glass in which a plurality of interlayer films are laminated, and at least one of the plurality of interlayer films is configured according to the present invention. An interlayer film for laminated glass.

  The laminated glass according to the present invention includes first and second laminated glass constituent members and an intermediate film sandwiched between the first and second laminated glass constituent members, and the intermediate film is the present invention. Or a laminated interlayer film for laminated glass in which a plurality of interlayer films including the interlayer film for laminated glass are laminated.

  Since the interlayer film for laminated glass according to the present invention contains a thermoplastic resin and the specific plasticizer, penetration resistance at a high temperature around 35 ° C. can be improved. By using the interlayer film for laminated glass according to the present invention, a laminated glass having high penetration resistance at a high temperature around 35 ° C. can be provided.

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

  Details of the present invention will be described below.

  The interlayer film for laminated glass according to the present invention contains a thermoplastic resin and a plasticizer.

(Thermoplastic resin)
A conventionally well-known thermoplastic resin can be used for the said thermoplastic resin contained in the intermediate film for laminated glasses which concerns on this invention, It does not specifically limit.

  Examples of the thermoplastic resin include polyvinyl acetal resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic copolymer resin, polyurethane resin, and polyvinyl alcohol resin. As for the said thermoplastic resin, only 1 type may be used and 2 or more types may be used together.

  The thermoplastic resin is preferably a polyvinyl acetal resin. When the polyvinyl acetal resin and the specific plasticizer are used in combination, the penetration resistance at a high temperature around 35 ° C. can be further enhanced. Furthermore, the combined use of the polyvinyl acetal resin and the specific plasticizer can further increase the adhesion of the interlayer film to the laminated glass component.

  The polyvinyl acetal resin is a resin obtained by acetalizing a polyvinyl alcohol resin with an aldehyde. As the polyvinyl acetal resin, a polyvinyl formal resin obtained by reacting a polyvinyl alcohol resin and formaldehyde, a narrowly defined polyvinyl acetal resin obtained by reacting a polyvinyl alcohol resin and acetaldehyde, and a polyvinyl alcohol resin and n-butyraldehyde And polyvinyl butyral resin obtained by reacting.

  The polyvinyl acetal resin can be produced, for example, by acetalizing polyvinyl alcohol. The polyvinyl alcohol can be produced, for example, by saponifying polyvinyl acetate.

  The polyvinyl acetal resin is not particularly limited. The polyvinyl acetal resin is preferably a polyvinyl butyral resin. By using the polyvinyl butyral resin, the adhesive force of the interlayer film to the laminated glass constituent member can be further increased.

  It is preferable that the content rate of the hydroxyl group of the said polyvinyl acetal resin exists in the range of 15-40 mol%. The more preferable lower limit of the hydroxyl group content is 18 mol%, and the more preferable upper limit is 35 mol%. If the hydroxyl group content is too low, the moisture resistance of the interlayer film may be lowered. Moreover, when the content rate of the said hydroxyl group is too high, there exists a tendency for the penetration resistance of a laminated glass to become low. Furthermore, the flexibility of the intermediate film is reduced, and problems are likely to occur in the handling of the intermediate film.

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

  The degree of acetylation of the polyvinyl acetal resin is preferably in the range of 0.1 to 30 mol%. The more preferable lower limit of the acetylation degree is 0.3 mol%, the more preferable upper limit is 20 mol%, and the more preferable upper limit is 17 mol%. If the acetylation degree is too low, the plasticizer tends to migrate to the surface of the interlayer film. If the degree of acetylation is too high, the moisture resistance of the interlayer film may be lowered.

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

  The degree of acetalization of the polyvinyl acetal resin is preferably in the range of 60 to 75 mol%. A more preferable lower limit of the degree of acetalization is 63 mol%, and a more preferable upper limit is 70 mol%. If the degree of acetalization is too low, the plasticizer tends to migrate to the surface of the interlayer film. When the said acetalization degree is too high, there exists a tendency for the penetration resistance of a laminated glass to become low.

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

  The degree of polymerization of the polyvinyl alcohol is preferably in the range of 1,000 to 4,500. The more preferable lower limit of the polymerization degree is 1,300, and the more preferable upper limit is 3,700. When the said polymerization degree is too low, there exists a tendency for the penetration resistance of a laminated glass to become low. If the degree of polymerization is too high, the flexibility of the intermediate film is lowered, and problems are likely to occur in the handling of the intermediate film.

(Plasticizer)
The plasticizer contained in the interlayer film for laminated glass according to the present invention is at least one selected from the group consisting of a plasticizer represented by the following formula (1), an epoxidized vegetable oil, and a polyester plasticizer.

  In said formula (1), R1, R2, and R3 show a C8-C15 alkyl group, respectively. R1, R2 and R3 may be the same or different. The alkyl groups of R1, R2, and R3 may be an alkyl group having a linear structure or an alkyl group having a branched structure.

  When one or two plasticizers are used, the plasticizer may be at least one of the plasticizer represented by the above formula (1) and the epoxidized vegetable oil. ) And at least one of the polyester plasticizers, or at least one of the epoxidized vegetable oil and the polyester plasticizer.

  When one kind of the plasticizer is used, the plasticizer may be a plasticizer represented by the above formula (1), the epoxidized vegetable oil, or the polyester plasticizer. Good.

  In any case of the plasticizer represented by the formula (1), the epoxidized vegetable oil, and the polyester plasticizer, the plasticizer has a molecular weight in the range of 500 to 3,000. Is preferred. There exists a tendency for the penetration resistance in the high temperature of 35 degreeC vicinity of a laminated glass to become low, so that the molecular weight of the said plasticizer is small. As the molecular weight of the plasticizer increases, the penetration resistance at a high temperature around 35 ° C. tends to increase. The reason for this is considered to be that as the molecular weight of the plasticizer increases, the interaction between the plasticizer and the thermoplastic resin increases. Further, when the plasticizer has a molecular weight of 3,000 or less, the flexibility of the intermediate film is increased, and the handleability of the intermediate film can be improved. Furthermore, the miscibility of the said plasticizer and a thermoplastic resin can be improved as the molecular weight of the said plasticizer is 3,000 or less.

  A more preferable upper limit of the molecular weight of the plasticizer represented by the above formula (1) is 1,200. When the molecular weight of the plasticizer represented by the above formula (1) is 1,200 or less, the flexibility of the interlayer film is further increased, and the handleability of the interlayer film can be further enhanced.

  R1, R2 and R3 in the above formula (1) are not particularly limited as long as they are alkyl groups having 8 to 15 carbon atoms. R1, R2 and R3 are each an n-octyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-stearyl group, isostearyl group, n-tetradecyl group or iso A tetradecyl group is preferred. The upper limit with preferable carbon number of the alkyl group of said R1, R2 and R3 is 12.

  The epoxidized vegetable oil is produced using vegetable oil as a raw material. For example, the epoxidized vegetable oil can be obtained by epoxidizing the vegetable oil. The vegetable oil is a mixture containing various organic acids such as linoleic acid, oleic acid, α-linolenic acid and stearic acid. Therefore, the epoxidized vegetable oil obtained by epoxidizing the vegetable oil is often not a single compound, and is often a mixture containing a plurality of types of compounds. Specifically, a plurality of compounds corresponding to the epoxidized vegetable oil represented by the following formula (2) are often contained.

  In the above formula (2), R11 to R13 each represent an alkylene group having 4 to 10 carbon atoms, at least one of R14 to R16 represents an organic group containing an epoxy group, and includes an epoxy group of R14 to 16 A group that is not an organic group represents an alkyl group having 1 to 10 carbon atoms. Said R11-R13 may be the same and may differ. Said R14-R16 may be the same and may differ. R11 to R13 may be an alkylene group having a linear structure or an alkylene group having a branched structure. R11 to R13 are preferably alkylene groups having a linear structure. When R14 to R16 have an alkyl group having 1 to 10 carbon atoms, the alkyl group may have a linear structure or a branched structure.

  In addition, when R14 is an alkyl group having 1 to 10 carbon atoms, the —R11-R14 group is an alkyl group having 5 to 20 carbon atoms, and the R15 is an alkyl group having 1 to 10 carbon atoms. -R12-R15 group is an alkyl group having 5 to 20 carbon atoms, and when R16 is an alkyl group having 1 to 10 carbon atoms, -R13-R16 group is an alkyl group having 5 to 20 carbon atoms. It is a group.

  From the viewpoint of further improving the penetration resistance at a high temperature around 35 ° C., the epoxidized vegetable oil is preferably an epoxidized vegetable oil represented by the above formula (2).

  From the viewpoint of further improving penetration resistance at a high temperature around 35 ° C., the organic group containing the epoxy group in the formula (2) is preferably a group represented by the following formula (11).

  In said formula (11), R21 shows a C1-C10 alkylene group, R22 shows a C1-C15 alkyl group, n1 shows the integer of 0-2. When n1 is 2, the plurality of R21s may be the same or different.

  The alkylene group of R21 in the above formula (11) may be an alkylene group having a linear structure or an alkylene group having a branched structure. R21 is preferably an alkylene group having a linear structure.

  Specific examples of the group represented by the formula (11) include groups represented by the following formula (11A), formula (11B), and formula (11C).

  In said formula (11A), R22 shows a C1-C15 alkyl group.

  In said formula (11B), R21 shows a C1-C10 alkylene group, R22 shows a C1-C15 alkyl group.

  In said formula (11C), R21 shows a C1-C10 alkylene group, R22 shows a C1-C15 alkyl group. Several R21 may be the same and may differ.

  A more preferable upper limit of the molecular weight of the epoxidized vegetable oil is 2,000. When the molecular weight of the plasticizer represented by the above formula (1) is 2,000 or less, the flexibility of the interlayer film is further increased, and the handleability of the interlayer film can be further enhanced.

  Moreover, from the viewpoint of further improving the penetration resistance at a high temperature around 35 ° C., the epoxidized vegetable oil is preferably at least one of epoxidized soybean oil and epoxidized linseed oil.

  Examples of the polyester plasticizer include polycondensates of polybasic acids and polyhydric alcohols or derivatives of the polycondensates.

  From the viewpoint of further improving penetration resistance at a high temperature around 35 ° C., the polyester plasticizer is preferably a polycondensate of a polybasic acid and a polyhydric alcohol or a derivative of the polycondensate. A polycondensate derivative obtained by reacting at least one of a monohydric alcohol and a monobasic acid at both ends of the polycondensate of an acid and a polyhydric alcohol is more preferable.

  From the viewpoint of further improving the penetration resistance at a high temperature around 35 ° C., the polyester plasticizer is preferably a polyester plasticizer represented by the following formula (3).

  In the above formula (3), A represents a polybasic acid residue, G represents a polyhydric alcohol residue, R31 and R32 each represent a monohydric alcohol residue or a monobasic acid residue, n2 represents an integer of 1 or more. R31 and R32 may be the same or different.

  The above polybasic acids are o-phthalic acid, m-phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid Sebacic acid, fumaric acid, maleic acid, apple acid, tartaric acid, citramalic acid, and citric acid are preferred.

  The polyhydric alcohol is preferably a dihydric alcohol. The dihydric alcohol is preferably at least one of butylene glycol and neopentyl glycol.

  The butylene glycol is preferably at least one selected from the group consisting of 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, isobutylene glycol and 1,2-butylene glycol.

  The content of the plasticizer is preferably in the range of 30 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin. The minimum with more preferable content of the said plasticizer with respect to 100 weight part of said thermoplastic resins is 35 weight part, and a more preferable upper limit is 90 weight part. When the content of the plasticizer is within the above range, penetration resistance at a high temperature around 35 ° C. can be further enhanced. When there is too little content of the said plasticizer, the softness | flexibility of an intermediate film will become low and it will be easy to produce a problem in handling. When there is too much content of the said plasticizer, there exists a tendency for the penetration resistance of an intermediate film to become low. Moreover, in order to improve penetration resistance, the thickness of the intermediate film may need to be increased more than necessary. When the thickness of the intermediate film is increased, the intermediate film is likely to be heavy or a problem may occur in handling.

  The interlayer film for laminated glass according to the present invention contains a plasticizer other than the plasticizer represented by the above formula (1), the epoxidized vegetable oil and the polyester plasticizer as long as sufficient penetration resistance is maintained. You may contain.

(Other ingredients)
The interlayer film for laminated glass according to the present invention may contain additives such as an ultraviolet absorber, an antioxidant, a light stabilizer, an antistatic agent, a pigment, a dye, an adhesion modifier, and an infrared absorber. . The interlayer film for laminated glass according to the present invention preferably contains an ultraviolet absorber. The interlayer film for laminated glass according to the present invention preferably contains an infrared absorber.

  The said infrared absorber will not be specifically limited if it has the performance which shields infrared rays. The infrared absorber is composed of tin-doped indium oxide particles, antimony-doped tin oxide particles, zinc oxide particles doped with an element other than zinc element, lanthanum hexaboride particles, zinc antimonate particles, and an infrared absorber having a phthalocyanine structure. It is preferably at least one selected from the group consisting of

  The content of the infrared absorber is preferably in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When there is too little content of the said infrared absorber, an intermediate film may not fully shield infrared rays. When there is too much content of the said infrared absorber, the transparency of an intermediate film may become low.

(Interlayer film for laminated glass)
Since the interlayer film for laminated glass according to the present invention contains a thermoplastic resin and the specific plasticizer, the interlayer film for laminated glass contains a thermoplastic resin and does not contain the specific plasticizer. When the thickness is the same, the penetration resistance at a high temperature around 35 ° C. becomes high.

  The thickness of the interlayer film for laminated glass according to the present invention is correlated with the penetration resistance of the laminated glass. Usually, the thicker the interlayer film for laminated glass, the higher the penetration resistance of the laminated glass. From the viewpoint of further improving the penetration resistance at a high temperature around 35 ° C., the thickness of the interlayer film for laminated glass is preferably in the range of 0.1 to 3 mm. The more preferable lower limit of the thickness of the interlayer film for laminated glass is 0.2 mm, the more preferable lower limit is 0.25 mm, the more preferable upper limit is 1.5 mm, and the further preferable upper limit is 1 mm.

  The manufacturing method of the interlayer film for laminated glass according to the present invention may be a conventionally known method and is not particularly limited. For example, the manufacturing method etc. which knead | mix the said thermoplastic resin, the said plasticizer, and the other component mix | blended as needed, and shape | mold the intermediate film for laminated glasses are mentioned. Since it is suitable for continuous production, an extrusion method is preferred.

  The kneading method is not particularly limited. Examples of this method include a method using an extruder, a plastograph, a kneader, a Banbury mixer, a calendar roll, or the like. Especially, since it is suitable for continuous production, a method using an extruder is preferable, and a method using a twin screw extruder is more preferable.

(Multilayer interlayer film for laminated glass)
The multilayer interlayer film for laminated glass according to the present invention has a multilayer structure in which a plurality of interlayer films are laminated. At least one of the plurality of interlayer films is the interlayer film for laminated glass according to the present invention. All of the plurality of interlayer films may be the interlayer film for laminated glass according to the present invention.

  The thickness of the multilayer interlayer film for laminated glass is preferably in the range of 0.1 to 3 mm. The more preferable lower limit of the thickness of the multilayer interlayer film for laminated glass is 0.2 mm, the more preferable lower limit is 0.25 mm, the more preferable upper limit is 1.5 mm, and the further preferable upper limit is 1 mm.

  As a method of laminating a plurality of intermediate films, a method of stacking a plurality of intermediate films, heating and pressing them, and integrating them is preferably used. Simultaneously with the production of the laminated glass, a plurality of interlayer films may be laminated to form a multilayer interlayer film. Furthermore, the multilayer interlayer film may be integrally formed by a multilayer extrusion method.

(Laminated glass)
In FIG. 1, an example of the laminated glass using the intermediate film for laminated glasses which concerns on one Embodiment of this invention is shown with sectional drawing.

  A laminated glass 1 shown in FIG. 1 includes an intermediate film 2 and first and second laminated glass constituting members 3 and 4. The intermediate film 2 is used to obtain a laminated glass. The interlayer film 2 is an interlayer film for laminated glass. The intermediate film 2 is sandwiched between the first and second laminated glass constituting members 3 and 4. Therefore, the laminated glass 1 is constituted by laminating the first laminated glass constituting member 3, the intermediate film 2, and the second laminated glass constituting member 4 in this order.

  The intermediate film 2 contains a thermoplastic resin and the specific plasticizer.

  FIG. 2 is a sectional view showing another example of laminated glass using the interlayer film for laminated glass according to one embodiment of the present invention. The same components as those of the laminated glass 1 are denoted by the same reference numerals and description thereof is omitted.

  A laminated glass 11 shown in FIG. 2 includes a multilayer intermediate film 12 and first and second laminated glass constituting members 3 and 4. The multilayer intermediate film 12 is used to obtain a laminated glass. The multilayer intermediate film 12 is a multilayer interlayer film for laminated glass. The multilayer intermediate film 12 is sandwiched between the first and second laminated glass constituent members 3 and 4.

  The multilayer intermediate film 12 includes an intermediate film 2, a second intermediate film 13 stacked on one surface of the intermediate film 2, and a third intermediate film 14 stacked on the other surface of the intermediate film 2. . Therefore, the multilayer intermediate film 12 has a three-layer multilayer structure. Instead of the second and third intermediate films 13 and 14, the intermediate film 2 may be used. The second and third intermediate films 13 and 14 may contain a thermoplastic resin and the specific plasticizer. The multilayer interlayer film may have a two-layer structure in which two interlayer films are stacked, or may have a multilayer structure in which three or more interlayer films are stacked.

  Examples of the first and second laminated glass constituting members 3 and 4 include glass plates and PET (polyethylene terephthalate) films. In the laminated glasses 1 and 11, not only the laminated glass in which the intermediate film or the multilayer intermediate film is sandwiched between the two glass plates, but also the interlayer film or the multilayer intermediate film is sandwiched between the glass plate and the PET film or the like. Laminated glass is also included. Laminated glass 1 and 11 is a laminated body provided with a glass plate, and it is sufficient that at least one glass plate is used. Further, another laminated glass constituent member may be further laminated on the outer surface of at least one of the first and second laminated glass constituent members 3 and 4. The another laminated glass constituent member may be a glass plate.

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

  The thickness of the first and second laminated glass constituting members 3 and 4 is preferably in the range of 1 to 3 mm. Moreover, when the laminated glass structural members 3 and 4 are glass plates, it is preferable that the thickness of this glass plate exists in the range of 1-3 mm.

  The manufacturing method of the laminated glasses 1 and 11 is not specifically limited. For example, the intermediate film 2 or the multilayer intermediate film 12 is sandwiched between the first and second laminated glass constituting members 3 and 4, and passed through a pressing roll, or put in a rubber bag and sucked under reduced pressure, The air remaining between the first and second laminated glass constituting members 3 and 4 and the intermediate film 2 or the multilayer intermediate film 12 is degassed. Then, it pre-adheres at about 70-110 degreeC, and a laminated body is obtained. Next, the laminated body is put in an autoclave or pressed, and pressed at about 120 to 150 ° C. and a pressure of 1 to 1.5 MPa. Thus, the laminated glasses 1 and 11 can be obtained.

  Laminated glasses 1 and 11 can be used for automobiles, railway vehicles, aircraft, ships, buildings, and the like. Laminated glasses 1 and 11 can be used for a windshield, side glass, rear glass, roof glass, or the like of an automobile.

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

  The following plasticizers were prepared.

(Plasticizer represented by the above formula (1))
Tris (2-ethylhexyl) trimellitate (molecular weight 547)
Tris (normal octyl) trimellitate (molecular weight 547)
Tris (isodecyl) trimellitate (molecular weight 631)

  Plasticizer (A): an epoxidized vegetable oil represented by the above formula (2), wherein R11 and R12 in the above formula (2) are each an alkylene group having a linear structure of 7 carbon atoms, and R13 Is an alkylene group having a linear structure with 9 carbon atoms, R14 is a group represented by the following formula (a), R15 is an alkyl group having a linear structure with 8 carbon atoms, and R16 is the following formula It is a group represented by (b).

(Polyester plasticizer)
Poly (1,3-butanediol) adipate (weight average molecular weight 1500)
Poly (1,2-butanediol) adipate (weight average molecular weight 800)

(Other plasticizers)
Triethylene glycol di-2-ethylhexanoate (3GO)

Example 1
(1) Production of interlayer film for laminated glass 45 parts by weight of tris (2-ethylhexyl) trimellitate, 0.2 part by weight of 2,6-di-t-butyl-p-cresol (BHT) as an antioxidant, and ultraviolet rays A mixture with 0.2 part by weight of an absorbent (“TINUVIN 326” manufactured by Ciba Specialty Chemicals) was stirred at 80 ° C. for 2 hours to prepare a plasticizer solution.

  Next, 100 parts by weight of a polyvinyl butyral resin (average polymerization degree 1700, butyralization degree 68.5 mol%, acetylation degree 0.9 mol%, hydroxyl group content 30.6 mol%) and the plasticizer solution are The mixture was sufficiently mixed and extruded using an extruder so as to have a thickness of 0.76 mm to produce a single-layer intermediate film. At this time, in order to adjust the adhesive strength of the intermediate film, an aqueous magnesium acetate solution was added so that the Mg concentration in the intermediate film was 65 ppm.

(2) Production of laminated glass The obtained interlayer film was allowed to stand for 24 hours under constant temperature and humidity conditions of 23 ° C. and relative humidity of 28%. Thereafter, an interlayer film was sandwiched between two transparent float glasses (length 300 mm × width 300 mm × thickness 2.3 mm) to obtain a laminate. The obtained laminated body was temporarily pressure-bonded using a 230 ° C. heating roll. Then, using an autoclave, it pressure-bonded for 20 minutes on conditions of 135 degreeC and a pressure of 1.2 MPa, and produced the laminated glass.

(Examples 2 to 13 and Comparative Examples 1 to 3)
An interlayer film and a laminated glass were obtained in the same manner as in Example 1 except that the types and blending amounts of the plasticizer were as shown in Tables 1 and 2 below.

(Example 14)
The mixture used for the preparation of the plasticizer solution was further blended with 0.28 parts by weight of ITO particles (volume average particle diameter 35 nm) to obtain a plasticizer solution. Example 1 except that this plasticizer solution was used. Similarly, an interlayer film and a laminated glass were obtained.

(Examples 15 to 19)
An interlayer film and a laminated glass were obtained in the same manner as in Example 14 except that the type of plasticizer was as shown in Table 3 below.

(Example 20)
A laminated glass having a multilayer intermediate film in which two intermediate films A and B were laminated was produced.

(1) Preparation of Composition A 40 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) and 2,6-di-t-butyl-p-cresol (BHT) 0.2 as an antioxidant A mixture of 0.2 part by weight, 0.2 part by weight of an ultraviolet absorber (“TINUVIN 326” manufactured by Ciba Specialty Chemicals) and 0.28 part by weight of ITO particles (volume average particle diameter: 35 nm) is stirred at 80 ° C. for 2 hours. Then, a plasticizer solution was prepared.

  Next, 100 parts by weight of a polyvinyl butyral resin (average polymerization degree 1700, butyralization degree 68.5 mol%, acetylation degree 0.9 mol%, hydroxyl group content 30.6 mol%) and the plasticizer solution are Mix thoroughly. At this time, in order to adjust the adhesive strength of the intermediate film, a magnesium acetate aqueous solution was added so that the Mg concentration in the intermediate film was 65 ppm, thereby preparing a composition A.

(2) Preparation of Composition B 45 parts by weight of tris (2-ethylhexyl) trimellitate, 0.2 part by weight of 2,6-di-t-butyl-p-cresol (BHT) as an antioxidant, and UV absorber (“TINUVIN 326” manufactured by Ciba Specialty Chemicals Co., Ltd.) A mixture of 0.2 parts by weight and 0.28 parts by weight of ITO particles (volume average particle diameter 35 nm) was stirred at 80 ° C. for 2 hours, and a plasticizer solution was added. Produced.

  Next, 100 parts by weight of a polyvinyl butyral resin (average polymerization degree 1700, butyralization degree 68.5 mol%, acetylation degree 0.9 mol%, hydroxyl group content 30.6 mol%) and the plasticizer solution are The composition B was prepared by mixing well.

(3) Production of multilayer interlayer film for laminated glass By co-extrusion of composition A and composition B, interlayer film A (thickness 150 μm), interlayer film B (460 μm) and interlayer film A (thickness 150 μm) A three-layer interlayer film was prepared so as to be sequentially stacked. The intermediate film A was formed from the composition A, and the intermediate film B was formed from the composition B.

(4) Production of laminated glass The obtained multilayer interlayer film was allowed to stand for 24 hours under constant temperature and humidity conditions of 23 ° C. and relative humidity of 28%. Thereafter, a multilayer intermediate film was sandwiched between two transparent float glasses (length 300 mm × width 300 mm × thickness 2.3 mm) to obtain a laminate. The obtained laminated body was temporarily pressure-bonded using a 230 ° C. heating roll. Then, using an autoclave, it pressure-bonded for 20 minutes on conditions of 135 degreeC and a pressure of 1.2 MPa, and produced the laminated glass.

(Examples 21 to 25)
A multilayer interlayer film and a laminated glass were obtained in the same manner as in Example 20 except that the type of plasticizer of the interlayer film B was as shown in Table 4 below.

(Evaluation)
(1) Penetration resistance evaluation of laminated glass The obtained laminated glass (length 300 mm x width 300 mm) was adjusted so that the surface temperature was 35 ° C. Next, in accordance with JIS R3212, a rigid sphere having a mass of 2260 g and a diameter of 82 mm was dropped from the height of 4 m onto the center portion of the laminated glass for each of the six laminated glasses. For all six laminated glasses, the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. If the number of laminated glasses in which the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was 3 or less, it was rejected. In the case of four sheets, the penetration resistance of six new laminated glasses was evaluated. In the case of 5 sheets, one additional laminated glass was additionally tested, and the case where the hard sphere did not penetrate within 5 seconds after the collision of the hard sphere was regarded as acceptable. In the same manner, from a height of 5 m, a hard sphere having a mass of 2260 g and a diameter of 82 mm was dropped on the center of the laminated glass for each of the 6 laminated glasses, and the penetration resistance was evaluated.

(2) Miscibility of polyvinyl butyral resin and plasticizer On the surface of the obtained interlayer film or multilayer interlayer film, two lines were written and marked with a red oily magic in the vertical and horizontal directions respectively. The marked interlayer film or multilayer interlayer film was placed so that the main surface was located in a plane parallel to the vertical direction. This was left to stand for one month under constant temperature and humidity conditions of 23 ° C. and a relative humidity of 28%. In an intermediate film or a multilayered intermediate film after being left unacceptable, the oily magic bleed and sag are not observed on any of the four lines, and the case where it is observed on at least one of the four lines. It was rejected.

  The results are shown in Tables 1 to 4 below.

DESCRIPTION OF SYMBOLS 1 ... Laminated glass 2 ... Intermediate film 3 ... 1st laminated glass structural member 4 ... 2nd laminated glass structural member 11 ... Laminated glass 12 ... Multilayer intermediate film 13 ... 2nd intermediate film 14 ... 3rd intermediate film

Claims (9)

Containing a thermoplastic resin and a plasticizer,
An interlayer film for laminated glass, wherein the plasticizer is at least one selected from the group consisting of a plasticizer represented by the following formula (1), an epoxidized vegetable oil, and a polyester plasticizer.

In the formula (1), R1, R2 and R3 each represent an alkyl group having 8 to 15 carbon atoms.   The interlayer film for laminated glass according to claim 1, wherein the thermoplastic resin is a polyvinyl acetal resin.   The interlayer film for laminated glass according to claim 1 or 2, wherein the plasticizer is a plasticizer represented by the formula (1). The interlayer film for laminated glass according to any one of claims 1 to 3, wherein the epoxidized vegetable oil is an epoxidized vegetable oil represented by the following formula (2).

In the formula (2), R11 to R13 each represent an alkylene group having 4 to 10 carbon atoms, at least one of R14 to R16 represents an organic group containing an epoxy group, and includes an epoxy group of R14 to 16 A group that is not an organic group represents an alkyl group having 1 to 10 carbon atoms. The organic film containing the said epoxy group in the said Formula (2) is an intermediate film for laminated glasses of Claim 4 which is group represented by following formula (11).

In said formula (11), R21 shows a C1-C10 alkylene group, R22 shows a C1-C15 alkyl group, n1 shows the integer of 0-2. When n1 is 2, the plurality of R21s may be the same or different.   The polyester plasticizer is a derivative of a polycondensate obtained by reacting at least one of a monohydric alcohol and a monobasic acid at both ends of a polycondensate of a polybasic acid and a polyhydric alcohol. The interlayer film for laminated glass according to any one of -5. The interlayer film for laminated glass according to claim 6, wherein the polyester plasticizer is a polyester plasticizer represented by the following formula (3).

In the formula (3), A represents a polybasic acid residue, G represents a polyhydric alcohol residue, R31 and R32 represent a monohydric alcohol residue or a monobasic acid residue, respectively. n2 represents an integer of 1 or more. A multilayer interlayer film for laminated glass in which a plurality of interlayer films are laminated,
A multilayer interlayer film for laminated glass, wherein at least one interlayer film of the plurality of interlayer films is the interlayer film for laminated glass according to any one of claims 1 to 7. First and second laminated glass components;
An intermediate film sandwiched between the first and second laminated glass constituent members,
The interlayer film is a multilayer interlayer film for laminated glass in which a plurality of interlayer films including the interlayer film for laminated glass according to any one of claims 1 to 7 or the interlayer film for laminated glass are laminated. Glass.

Images