JP2011046559A - Interlayer for laminated glass and laminated glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an interlayer for laminated glass which, when used for constituting laminated glass enhances the impenetrability and the sound insulation of the laminated glass obtained and reduces the lowering of the impenetrability over time. <P>SOLUTION: The interlayer for laminated glass includes a thermoplastic resin, a first plasticizer having a structure expressed by formula (1): HO-(R<SP>1</SP>O)<SB>m</SB>-R<SP>2</SP>-(R<SP>3</SP>O)<SB>n</SB>-H, and a second plasticizer being a diester compound. The content of the first plasticizer is 28-50 pts.wt. and that of the second plasticizer is 10-35 to 100 pts.wt. of the thermoplastic resin. The total content of the first plasticizer and the second plasticizer is 40-65 pts.wt. In the formula (1), R<SP>1</SP>represents a 1-18C alkylene group; R<SP>2</SP>represents a 4-10 alkylene group having a branched structure; R<SP>3</SP>represents a 1-18C alkylene group; the total of<SB>m</SB>and<SB>n</SB>are numbers in the range of 2-10. <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 more specifically, an interlayer film for laminated glass capable of obtaining a laminated glass excellent in penetration resistance and sound insulation, and the The present invention relates to a laminated glass using an 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, the said laminated glass is widely used for a motor vehicle, a rail vehicle, an aircraft, a ship, a building, etc. The laminated glass is manufactured by sandwiching an interlayer film for laminated glass between a pair of glass plates.

  As an example of the interlayer film for laminated glass, Patent Document 1 listed below includes 100 parts by weight of polyvinyl acetal resin, triethylene glycol mono-2-ethylhexanoate, and triethylene glycol di-2-ethylhexanoate. An interlayer film for laminated glass containing 20 to 60 parts by weight of the above mixture is disclosed.

  Further, in Patent Document 2 below, 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one metal salt of 0.001 to 1 of an alkali metal salt and an alkaline earth metal salt A sound insulation layer containing 0.0 part by weight and 30 parts by weight or more of a plasticizer is disclosed. This sound insulation layer may be a single layer and used as an interlayer film for laminated glass.

  Furthermore, Patent Document 2 below also describes an interlayer film for laminated glass in which the sound insulating layer and another layer are laminated. The other layer laminated on the sound insulation layer is composed of 100 parts by weight of a polyvinyl acetal resin having an acetalization degree of 60 to 85 mol%, and at least one metal salt of an alkali metal salt and an alkaline earth metal salt 0.001 to 0.001. 1.0 part by weight and a plasticizer of 30 parts by weight or less are included.

JP 2001-097745 A JP 2007-070200 A

  When the laminated glass is configured using the interlayer film for laminated glass described in Patent Document 1, the sound insulating property in the frequency region near 2000 Hz of the laminated glass is not sufficient, and therefore, the deterioration of the sound insulating property due to the coincidence effect is avoided. It may not be possible. In particular, the laminated glass may not have sufficient sound insulation around 20 ° C.

  Here, the coincidence effect means that when a sound wave is incident on the glass plate, the transverse wave propagates on the glass surface due to the rigidity and inertia of the glass plate, and the transverse wave and the incident sound resonate. This is a phenomenon that occurs.

  In recent years, in order to improve the sound insulating properties of laminated glass, it has been studied to include an excessive amount of a plasticizer in an interlayer film for laminated glass. By including an excessive amount of plasticizer in the interlayer film for laminated glass, the sound insulation of the laminated glass can be improved. However, when an excessive amount of plasticizer is used, the plasticizer may bleed out on the surface of the interlayer film for laminated glass.

  Even when the laminated glass is constituted by using the sound insulating layer described in Patent Document 2 as a single layer as an interlayer film for laminated glass, the laminated glass may not have sufficient sound insulating properties at around 20 ° C.

  Moreover, when a laminated glass is comprised using the intermediate film for laminated glasses by which the sound-insulating layer of the said patent document 2 and another layer were laminated | stacked, the sound-insulating property in 20 degreeC vicinity of a laminated glass is improved to some extent. be able to. However, since the interlayer film for laminated glass has the above laminated structure, optical distortion may occur in the interlayer film for laminated glass. Furthermore, there is a problem that the production of the interlayer film for laminated glass becomes complicated and the cost becomes high.

  An object of the present invention is to improve the penetration resistance and sound insulation of the obtained laminated glass when used for constituting a laminated glass, and to suppress a decrease in penetration resistance over time. An interlayer film for laminated glass and a laminated glass using the interlayer film for laminated glass are provided.

  According to the present invention, it contains a thermoplastic resin, a first plasticizer having a structure represented by the following formula (1), and a second plasticizer that is a diester compound, and is 100 weights of the thermoplastic resin. Content of the first plasticizer is 28 to 50 parts by weight, the content of the second plasticizer is 10 to 35 parts by weight, and the total of the first and second plasticizers An interlayer film for laminated glass having a content of 40 to 65 parts by weight is provided.

  In the above formula (1), R1 represents an alkylene group having 1 to 18 carbon atoms, R2 represents an alkylene group having a branched structure having 4 to 10 carbon atoms, R3 represents an alkylene group having 1 to 18 carbon atoms, m and n are numbers in the range of 2 to 10 in total.

  On the specific situation with the intermediate film for laminated glasses which concerns on this invention, the 2nd plasticizer which is the said diester compound has a structure represented by following formula (21).

In the above formula (21), R11 and R12 represents an organic group having 5 to 10 carbon atoms, R13 _is, -CH 2 -CH ₂ - _{group, -CH 2 -CH (CH 3)} - group or a -CH ₂ - Represents a CH ₂ —CH ₂ — group, and p represents an integer in the range of 3 to 10.

  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. It is the intermediate film for laminated glasses comprised according to this.

  The interlayer film for laminated glass according to the present invention contains a thermoplastic resin, and further specifies a first plasticizer having a structure represented by the above formula (1) and a second plasticizer that is a diester compound. Therefore, when used to construct a laminated glass, the penetration resistance and sound insulation of the obtained laminated glass can be improved. Furthermore, it is possible to suppress a decrease in penetration resistance of the laminated glass over time.

  In addition, by sandwiching the interlayer film for laminated glass according to the present invention between the first and second laminated glass constituent members, the penetration resistance and the sound insulation are high, and further the deterioration of the penetration resistance with time is suppressed. Laminated glass can be provided.

FIG. 1 is a cross-sectional view showing a laminated glass using an 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, a first plasticizer having a structure represented by the following formula (1), and a second plasticizer that is a diester compound.

  In the above formula (1), R1 represents an alkylene group having 1 to 18 carbon atoms, R2 represents an alkylene group having a branched structure having 4 to 10 carbon atoms, R3 represents an alkylene group having 1 to 18 carbon atoms, m and n are numbers in the range of 2 to 10 in total.

(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. By the combined use of the polyvinyl acetal resin and the specific plasticizer, the adhesive strength of the interlayer film to the laminated glass constituent member can be further increased.

  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 manufacturing method of the said polyvinyl acetal resin is not specifically limited. For example, a polyvinyl alcohol resin is dissolved in warm water or hot water, and the obtained aqueous solution is maintained at a predetermined temperature of about 0 to 95 ° C. An aldehyde and an acid catalyst are added to the aqueous solution, and the acetalization reaction proceeds while stirring. Next, the reaction is completed by raising the reaction temperature and aging. Thereafter, various steps of neutralization, washing with water and drying are performed. In this way, a powdery polyvinyl acetal resin can be obtained.

  It is preferable that the hydroxyl group content (hydroxyl group amount) of the polyvinyl acetal resin is in the range of 15 to 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 preferable lower limit of the degree of acetylation (acetyl group amount) of the polyvinyl acetal resin is 0.1 mol%, the more preferable lower limit is 0.3 mol%, the still more preferable lower limit is 0.5 mol%, and the preferable upper limit is 30 mol%. A more preferable upper limit is 25 mol%, and a further preferable upper limit is 20 mol%. If the degree of acetylation is too low, the compatibility between the polyvinyl acetal resin and the plasticizer may be reduced. In addition, the glass transition temperature of the polyvinyl acetal resin may not be sufficiently lowered. For this reason, the sound insulation performance in a low temperature region tends to be low. 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 preferable lower limit of the degree of acetalization of the polyvinyl acetal resin is 60 mol%, the more preferable lower limit is 63 mol%, the preferable upper limit is 85 mol%, the more preferable upper limit is 75 mol%, and the further preferable upper limit is 70 mol%. When the degree of acetalization is too low, the compatibility between the polyvinyl acetal resin and the plasticizer may be low, and the glass transition temperature of the interlayer film for laminated glass may not be sufficiently lowered. For this reason, the sound insulation performance in a low temperature region tends to be low. When the said acetalization degree is too high, reaction time required in order to manufacture polyvinyl acetal resin may become long.

  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 acetalization is obtained by measuring the amount of acetyl group and the amount of vinyl alcohol by a method based on JIS K6728 “Testing method for polyvinyl butyral” or by a method using nuclear magnetic resonance (NMR). The molar fraction can be calculated from the result, and then calculated by subtracting the amount of acetyl group and the amount of vinyl alcohol from 100 mol%.

  When the polyvinyl acetal resin is a polyvinyl butyral resin, the degree of acetalization (degree of butyralization) and the amount of acetyl group are determined in accordance with JIS K 6728 “Testing method for polyvinyl butyral” or infrared absorption spectrum (IR). And can be calculated from results measured by a method using nuclear magnetic resonance (NMR).

(First and second plasticizers)
The plasticizer contained in the interlayer film for laminated glass according to the present invention contains a first plasticizer having a structure represented by the following formula (1) and a second plasticizer that is a diester compound. .

  In the above formula (1), R1 represents an alkylene group having 1 to 18 carbon atoms, R2 represents an alkylene group having a branched structure having 4 to 10 carbon atoms, R3 represents an alkylene group having 1 to 18 carbon atoms, m and n are numbers in the range of 2 to 10 in total.

  R1 in the above formula (1) represents an alkylene group having 1 to 18 carbon atoms. When the carbon number of R1 exceeds 18, the thermoplastic resin and the first plasticizer may not be compatible. Said R1 will not be specifically limited if it is a C1-C18 alkylene group. Examples of R1 include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, Examples include a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group. The alkylene group may be an alkylene group having a straight chain structure or an alkylene group having a branched structure.

  Since a laminated glass more excellent in sound insulation can be obtained, the R1 is an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. An alkylene group having 2 to 5 carbon atoms such as an ethylene group, a propylene group, a butylene group, and a pentylene group is more preferable.

  R2 in the above formula (1) represents an alkylene group having a branched structure having 4 to 10 carbon atoms. When the carbon number of R2 exceeds 10, the thermoplastic resin and the first plasticizer may not be compatible. R2 is not particularly limited as long as it is an alkylene group having a branched structure having 4 to 10 carbon atoms. Examples of R2 include 2-methylpropylene group, 2-ethylpropylene group, 2-propylpropylene group, 2,2-dimethylpropylene group, 2,2-diethylpropylene group, 2,2-dipropylpropylene group, 2-methylbutylene group, 2-ethylbutylene group, 2-propylbutylene group, 2,3-dimethylbutylene group, 2,3-diethylbutylene group, 2,3-dipropylbutylene group and 2-butyl-2-ethyl A propylene group etc. are mentioned.

  Since a laminated glass with higher sound insulation can be obtained, the R2 is 2,2-dimethylpropylene group, 2,2-diethylpropylene group, 2,2-dipropylpropylene group, 2,3-dimethylbutylene. An alkylene group having a branched structure of 5 to 10 carbon atoms such as a group, 2,3-diethylbutylene group, 2,3-dipropylbutylene group and 2-butyl-2-ethylpropylene group is preferable.

  Further, since whitening is less likely to occur in the periphery of the laminated glass exposed to high temperature and high humidity, R2 is 2,2-diethylpropylene group, 2,2-dipropylpropylene group, 2,3- More preferably, it is an alkylene group having a branched structure of 6 to 10 carbon atoms such as a dimethylbutylene group, a 2,3-diethylbutylene group, a 2,3-dipropylbutylene group, and a 2-butyl-2-ethylpropylene group. 2-butyl-2-ethylpropylene group is more preferable.

  The 2-butyl-2-ethylpropylene group is represented by the following formula (11).

  R2 in the above formula (1) is an alkylene group having a branched structure having 4 to 10 carbon atoms, and the alkylene group has a side chain branched from the main chain, and the side chain has a carbon number. Two or more alkyl groups are preferred. In this case, when the laminated glass is exposed to high temperature and high humidity, whitening hardly occurs in the peripheral portion of the laminated glass. The alkylene group only needs to have at least one alkyl group having 2 or more carbon atoms as the branched side chain, and may have a plurality of the alkyl groups. The alkylene group preferably has a plurality of alkyl groups having 2 or more carbon atoms as the branched side chain. The alkyl group having 2 or more carbon atoms preferably has a linear structure.

  The alkylene group having the branched structure preferably has an alkyl group having 3 or more carbon atoms, more preferably an alkyl group having 4 or more carbon atoms, as a side chain branched from the main chain. In this case, whitening is less likely to occur in the peripheral portion of the laminated glass exposed to high temperature and high humidity.

  R3 in the above formula (1) represents an alkylene group having 1 to 18 carbon atoms. When the number of carbon atoms in R3 exceeds 18, the thermoplastic resin and the first plasticizer may not be compatible. R3 is not particularly limited as long as it is an alkylene group having 1 to 18 carbon atoms. Examples of R3 include a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, Examples include a pentadecylene group, a hexadecylene group, a heptadecylene group, and an octadecylene group. The alkylene group may be an alkylene group having a straight chain structure or an alkylene group having a branched structure.

  Since a laminated glass more excellent in sound insulation can be obtained, the R3 is an alkylene group having 1 to 6 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group and a hexylene group. An alkylene group having 2 to 5 carbon atoms such as an ethylene group, a propylene group, a butylene group, and a pentylene group is more preferable.

  In the above formula (1), R1 is an alkylene group having 2 to 5 carbon atoms, R2 is an alkylene group having a branched structure having 5 to 10 carbon atoms, and R3 is an alkylene group having 2 to 5 carbon atoms. It is preferable. In this case, the sound insulation property around 20 ° C. of the laminated glass can be further enhanced.

  Specific examples of the plasticizer represented by the above formula (1) include neopentyl glycol ethoxylate, neopentyl glycol propoxylate, and 2-butyl-2-ethyl-1,3-β-hydroxyethoxy-propane. Can be mentioned.

  Since a laminated glass having higher sound insulation can be obtained, the first plasticizer includes neopentyl glycol ethoxylate, neopentyl glycol propoxylate, and 2-butyl-2-ethyl-1,3-β-hydroxy. It is preferably at least one selected from the group consisting of ethoxy-propane. Since the laminated glass having higher sound insulation can be obtained, the first plasticizer is neopentyl glycol ethoxylate and 2-butyl-2-ethyl-1,3-β-hydroxyethoxy-propane. More preferably, it is at least one. Furthermore, 2-butyl-2-ethyl-1,3-β-hydroxyethoxy-propane is more preferable because whitening is less likely to occur in the peripheral portion of the laminated glass.

  The neopentyl glycol ethoxylate has a structure represented by the following formula (2).

  In said formula (2), s and t are numbers in the range of 2-10 in total (s + t).

  The 2-butyl-2-ethyl-1,3-β-hydroxyethoxy-propane is an alkylene group in which R2 in the above formula (1) has a branched structure having 9 carbon atoms. Moreover, this alkylene group has a carbon number 2 ethyl group and a carbon number 4 n-butyl group as a side chain branched from the main chain.

  The 2-butyl-2-ethyl-1,3-β-hydroxyethoxy-propane has a structure represented by the following formula (3).

  In said formula (3), s and t are numbers in the range of 2-10 in total (s + t).

  In addition, m, n, s, and t show an average added mole number. The sum of m and n (m + n) and the sum of s and t (s + t) are preferably numbers in the range of 3-9, and more preferably numbers in the range of 4-8.

  In the above formula (1), R2 is an alkylene group having a branched structure, and a plasticizer having an alkyl group having 2 or more carbon atoms as a side chain from which the alkylene group is branched was used as the first plasticizer. In this case, particularly when 2-butyl-2-ethyl-1,3-β-hydroxyethoxy-propane is used as the first plasticizer, the peripheral portion of the laminated glass exposed to high temperature and high humidity is used. Whitening can be further suppressed.

  The second plasticizer contained in the interlayer film for laminated glass according to the present invention is a diester compound. The said diester compound can use the conventionally well-known diester compound used for the intermediate film for laminated glasses, for example, It does not specifically limit. As for the said diester compound, only 1 type may be used and 2 or more types may be used together.

  The 2nd plasticizer which is the said diester compound has a structure represented by following formula (21).

In the above formula (21), R11 and R12 represents an organic group having 5 to 10 carbon atoms, R13 _is, -CH 2 -CH ₂ - _{group, -CH 2 -CH (CH 3)} - group or a -CH ₂ - Represents a CH ₂ —CH ₂ — group, and p represents an integer in the range of 3 to 10.

  Specific examples of the second plasticizer include triethylene glycol di-2-ethylbutyrate (3GH), triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di n-heptanoate (3G7). ), Triethylene glycol dicaprylate, triethylene glycol di-n-octoate, tetraethylene glycol di-2-ethylbutyrate, tetraethylene glycol di-n-heptanoate, tetraethylene glycol di-2-ethylhexanoate, pentaethylene Glycol di-2-ethylhexanoate, octaethylene glycol di-2-ethylhexanoate, nonaethylene glycol di-2-ethylhexanoate, decaethylene glycol di-2-ethylhexanoate, tetraethylene group Koruji -n- heptanoate and tetraethylene glycol di -n- octanoate, and the like. From the viewpoint of further improving the penetration resistance of the laminated glass, the second plasticizer is preferably triethylene glycol di (2-ethylhexanoate).

  The content of the first plasticizer is in the range of 28 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin. If the content of the first plasticizer is less than 28 parts by weight, the sound insulating properties of the laminated glass may deteriorate. When content of the said plasticizer exceeds 50 weight part, the penetration resistance of a laminated glass may fall. A preferable lower limit of the content of the first plasticizer with respect to 100 parts by weight of the thermoplastic resin is 32 parts by weight, a more preferable lower limit is 35 parts by weight, a preferable upper limit is 48 parts by weight, and a more preferable upper limit is 45 parts by weight.

  The content of the second plasticizer is in the range of 10 to 35 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When the content of the second plasticizer is within the above range, the penetration resistance and sound insulation of the laminated glass can be increased, and further, the decrease in penetration resistance over time can be suppressed. The preferable lower limit of the content of the second plasticizer with respect to 100 parts by weight of the thermoplastic resin is 15 parts by weight, the more preferable lower limit is 17 parts by weight, the preferable upper limit is 33 parts by weight, and the more preferable upper limit is 30 parts by weight.

  The total content of the first plasticizer and the second plasticizer is in the range of 40 to 65 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When the total content of the first and second plasticizers is within the above range, the penetration resistance and sound insulation of the laminated glass can be further improved, and further, the deterioration of penetration resistance with time is suppressed. be able to. A preferred lower limit of the total content of the first and second plasticizers relative to 100 parts by weight of the thermoplastic resin is 42 parts by weight, a more preferred lower limit is 45 parts by weight, a preferred upper limit is 60 parts by weight, and a more preferred upper limit is 55 parts. Parts by weight.

  Conventionally, when an interlayer film for laminated glass is formed, if the content of a plasticizer that is generally used is increased, the sound insulation of the laminated glass tends to increase. However, the plasticizer bleed out easily occurs on the surface of the interlayer film for laminated glass.

  In the interlayer film for laminated glass according to the present invention, the content of the first plasticizer, the content of the second plasticizer, and the content of the first and second plasticizers are within the above ranges. The penetration resistance and sound insulation of the laminated glass can be greatly enhanced. In addition, bleed-out hardly occurs on the surface of the interlayer film for laminated glass, and deterioration of penetration resistance with time can be suppressed.

(Other ingredients)
The interlayer film for laminated glass according to the present invention includes an ultraviolet absorber, an antioxidant, a light stabilizer, a flame retardant, an antistatic agent, a pigment, a dye, an adhesive force adjusting agent, a moisture resistant agent, and a fluorescent whitening as necessary. An additive such as an agent and an infrared absorber may be contained. The interlayer film for laminated glass according to the present invention preferably contains an antioxidant. The interlayer film for laminated glass according to the present invention preferably contains an ultraviolet absorber.

(Interlayer film for laminated glass)
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 is, the higher the penetration resistance of the laminated glass tends to be.

  From the viewpoint of further improving the penetration resistance of the interlayer film for laminated glass, 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 0.25 mm, and the more preferable upper limit is 1.5 mm. When the thickness of the interlayer film for laminated glass is too thin, the penetration resistance of the laminated glass tends to be lowered. If the thickness of the interlayer film for laminated glass is too thick, the transparency of the interlayer film for laminated glass may be lowered.

  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.

(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 further contains the first and second plasticizers at the specific content.

  Examples of the first and second laminated glass constituting members 3 and 4 include glass plates and PET (polyethylene terephthalate) films. In the laminated glass 1, not only a laminated glass in which an intermediate film or a multilayer intermediate film is sandwiched between two glass plates, but also an intermediate film or a multilayer intermediate film is sandwiched between a glass plate and a PET film or the like. Laminated glass is also included. Laminated glass 1 is a glass plate-containing laminate, and at least one glass plate is preferably used.

  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. When the laminated glass constituent members 3 and 4 are PET films, the thickness of the PET film is preferably in the range of 0.03 to 0.5 mm.

  The manufacturing method of the laminated glass 1 is not specifically limited. For example, the intermediate film 2 is sandwiched between the first and second laminated glass constituent 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 laminated glass constituent members 3 and 4 and the intermediate film 2 is deaerated. 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 glass 1 can be obtained.

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

  Regarding the sound transmission loss of the laminated glass obtained by sandwiching the interlayer film for laminated glass of the present invention between two clear glasses having a thickness of 2.0 mm, it is minimal in the vicinity of a frequency of 2,000 Hz in an environment of 20 ° C. The sound transmission loss is preferably 30 dB or more.

  An apparatus for measuring the loss factor is not particularly limited. As this device, for example, a mechanical impedance measuring device (“XG-81” manufactured by Lion Co., Ltd.) and the like can be mentioned.

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

  The following first and second plasticizers were prepared.

(First plasticizer)
1) 2-butyl-2-ethyl-1,3-β-hydroxyethoxy-propane (“DMH-40” manufactured by Nippon Emulsifier Co., Ltd.) (in the above formula (1), R1 = ethylene group, R2 = 2-butyl- 2-ethylpropylene group, R3 = ethylene group, m + n (average number of moles added) = 4.5)
2) Neopentyl glycol ethoxylate (“NGE-04” manufactured by Yokkaichi Gosei Co., Ltd.) (in the formula (1), R1 = ethylene group, R2 = 2,2-dimethylpropylene group, R3 = ethylene group, m + n (average added mole) Number) = 4.5)

(Second plasticizer)
1) Triethylene glycol di-2-ethylhexanoate (3GO)
2) Tetraethylene glycol di-2-ethylhexanoate (4GO)

Example 1
(1) Preparation of interlayer film for laminated glass 40 parts by weight of 2-butyl-2-ethyl-1,3-β-hydroxyethoxy-propane and 10 parts by weight of triethylene glycol di-2-ethylhexanoate (3GO) And 0.2 part by weight of an antioxidant (2,6-di-t-butyl-p-cresol (BHT)) and an ultraviolet absorber (“TINUVIN 326” manufactured by Ciba Specialty Chemicals) 0.2 parts by weight was added and dissolved to prepare a plasticizer solution.

  Next, 100 parts by weight of polyvinyl butyral resin (degree of butyralization 68.5 mol%, degree of acetylation 0.9 mol%, hydroxyl group content 30.6 mol%) and the obtained plasticizer solution 50.4 wt. Were mixed together and extruded using an extruder to produce an interlayer film for laminated glass having a thickness of 0.78 mm.

  Similarly, an interlayer film for laminated glass having a thickness of 1 mm was produced.

(2) Production of laminated glass Each obtained laminated glass interlayer film was sandwiched between two transparent float glasses (length 300 mm x width 300 mm x thickness 2.5 mm) to obtain a laminate. The obtained laminate was temporarily pressure-bonded using a heating roll having a maximum temperature of 230 ° C. Then, the laminated body temporarily crimped | bonded for 20 minutes on the conditions of 135 degreeC and the pressure of 1.2 MPa using the autoclave by the heating roll method, and produced the laminated glass.

(Examples 2 to 17 and Comparative Examples 1 to 6)
An interlayer film for laminated glass and laminated glass were obtained in the same manner as in Example 1 except that the type and blending amount of the plasticizer were as shown in Tables 1 and 2 below.

(Bleedout evaluation)
On the surface of the obtained interlayer film for laminated glass, two lines each having a length of 10 cm were written and marked with a red oily magic in the vertical direction and the horizontal direction. The marked interlayer film for laminated glass was placed so that the main surface was located in a plane parallel to the vertical direction. This was left to stand for 1 month under constant temperature and humidity conditions of 23 ° C. and relative humidity of 28%. In the interlayer film for laminated glass after standing, if the oily magic bleed and sag are not observed on any of the four lines, pass “○” and observe on at least one of the four lines. The case where it was rejected was regarded as a failure “x”.

(Evaluation of sound insulation)
The obtained laminated glass (thickness of the interlayer film for laminated glass: 0.78 mm) was cut into a size of 25 mm long × 300 mm wide to produce a laminated glass for sound insulation evaluation. This laminated glass for sound insulation evaluation is vibrated by a vibration generator for damping test (“Vibrator G21-005D” manufactured by KENKEN Co., Ltd.), and the vibration characteristics obtained from the vibration are measured by a mechanical impedance measuring device (RION Co., Ltd.). The vibration spectrum was analyzed with an FFT spectrum analyzer (“FFT analyzer HP3582A” manufactured by Yokogawa Hured Packard). From the ratio of the loss factor thus obtained and the resonance frequency of the laminated glass, a graph showing the relationship between the sound frequency (Hz) and the sound transmission loss (dB) at 20 ° C. is created. The minimum sound transmission loss (TL value) in the vicinity of 000 Hz was determined. The higher the TL value, the higher the sound insulation. The results are shown in Tables 1 and 2 below, where “◯” indicates a case where the TL value is 30 dB or more and “X” indicates a case where the TL value is less than 30 dB.

(Evaluation of penetration resistance of laminated glass)
The obtained laminated glass (length 300 mm × width 300 mm, thickness 1 mm of the interlayer film for laminated glass) was adjusted so that the surface temperature was 30 ° C. Next, in accordance with JIS R3212, a hard sphere having a mass of 2260 g ± 20 g and a diameter of 82 mm was dropped from a predetermined height onto the central portion of the laminated glass. The maximum height at which the hard sphere did not penetrate was measured to evaluate the penetration resistance of the initial laminated glass.

  The obtained laminated glass was stored for 4 weeks under constant temperature and humidity conditions of 50 ° C. and a relative humidity of 30%. The laminated glass after storage for 4 weeks was similarly evaluated for penetration resistance of the laminated glass after aging.

  The results are shown in Tables 1 and 2 below, assuming that the maximum height at which the hard sphere did not penetrate was 4 m or more at the initial stage and after the lapse of time, and “x” when the maximum height was less than 4 m. .

  The results are shown in Tables 1 and 2 below.

DESCRIPTION OF SYMBOLS 1 ... Laminated glass 2 ... Intermediate film 3 ... 1st laminated glass structural member 4 ... 2nd laminated glass structural member

Claims (3)

Containing a thermoplastic resin, a first plasticizer having a structure represented by the following formula (1), and a second plasticizer which is a diester compound;
The content of the first plasticizer is 28 to 50 parts by weight, the content of the second plasticizer is 10 to 35 parts by weight, and the first and second parts with respect to 100 parts by weight of the thermoplastic resin. The interlayer film for laminated glass, wherein the total content of the plasticizer is 40 to 65 parts by weight.

In the above formula (1), R1 represents an alkylene group having 1 to 18 carbon atoms, R2 represents an alkylene group having a branched structure having 4 to 10 carbon atoms, R3 represents an alkylene group having 1 to 18 carbon atoms, m and n are numbers in the range of 2 to 10 in total. The interlayer film for laminated glass according to claim 1, wherein the second plasticizer that is the diester compound has a structure represented by the following formula (21).

In the above formula (21), R11 and R12 represents an organic group having 5 to 10 carbon atoms, R13 _is, -CH 2 -CH ₂ - _{group, -CH 2 -CH (CH 3)} - group or a -CH ₂ - Represents a CH ₂ —CH ₂ — group, and p represents an integer in the range of 3 to 10. First and second laminated glass components;
An intermediate film sandwiched between the first and second laminated glass constituent members,
Laminated glass, wherein the interlayer film is the interlayer film for laminated glass according to claim 1 or 2.

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