JP6033754B2 - Multilayer interlayer film - Google Patents

Description

  The present invention relates to a laminate having excellent interlayer adhesion.

  Polyvinyl acetal typified by polyvinyl butyral is excellent in adhesiveness to various organic and inorganic substrates, compatibility with other compounds, and solubility in organic solvents. For various adhesives and ceramics Widely used as binders, various inks, paints, etc. and interlayer films for laminated glass.

  Conventionally, as an interlayer film for laminated glass, a laminated sound insulation interlayer for the purpose of improving the sound insulation performance of glass has been studied (see Patent Document 1 and Patent Document 2). Such a laminated sound insulation interlayer is formed by laminating an a layer that expresses adhesiveness and mechanical strength with glass and a b layer that expresses sound insulation performance, in order to express these characteristics in a well-balanced manner. The polyvinyl acetal contained in the layer a and the polyvinyl acetal contained in the layer b are different in average residual hydroxyl group amount.

  By the way, in recent years, from the viewpoint of ecology, there is an increasing demand for making the life cycle of various products as long as possible. The laminated sound insulating interlayer is also required to maintain basic mechanical properties and sound insulating performance as an interlayer film for laminated glass even after long-term use as an interlayer film for laminated glass. However, one of the factors that shorten the product life cycle of the laminated sound insulation interlayer is that the interlayer adhesion between the a layer and the b layer is still insufficient.

  In particular, the laminated sound insulation intermediate film obtained by laminating the a layer and the b layer containing polyvinyl acetals having different average residual hydroxyl group amounts is long in an environment where the temperature changes greatly in a short time (an environment where the temperature difference between the day and day is large). When used for a period, delamination of the interlayer film for laminated glass occurs, and the safety as laminated glass may be impaired or the appearance may be impaired. In particular, in laminated glass whose end portion is not treated with a water-resistant sealing material, the moisture content of the interlayer film for laminated glass tends to be high around the end portion, and such a problem occurs remarkably.

JP 2011-225449 A JP 2011-084468 A

  The present invention solves the above-mentioned problems, and when used as an interlayer film for laminated glass, it has excellent adhesion to glass, mechanical strength, and sound insulation performance. It aims at providing the laminated body which peeling does not produce easily. An object of this invention is to provide the sheet | seat which is excellent in transparency, when a recycled product is manufactured from a trim or an off-spec product as a raw material.

［式中、（ａ２）は内径４ｍｍ、長さ１ｃｍのオクタデシルシリル基で表面修飾された球状シリカゲルを固定相として充填したカラム（ＯＤＳカラム）を用いた高速液体クロマトグラフィー（ＨＰＬＣ）分析におけるポリビニルアセタール（Ａ）に由来するピークの検出終わりの時間（分）を表し、（ｂ１）は前記高速液体クロマトグラフィー分析におけるポリビニルアセタール（Ｂ）に由来するピークの検出初めの時間（分）を表す。］
を満たす、積層体を提供することで好適に達成される。 According to the present invention, the above-described object is to provide an A layer containing 30 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 27 to 40 mol%, and an average residual hydroxyl group content of 15; A B layer containing 50 to 70 parts by mass of a plasticizer with respect to 100 parts by mass of ˜24 mol% polyvinyl acetal (B),

[Wherein (a2) is polyvinyl acetal in high performance liquid chromatography (HPLC) analysis using a column (ODS column) packed with a spherical silica gel surface modified with octadecylsilyl group having an inner diameter of 4 mm and a length of 1 cm as a stationary phase. The time (min) at the end of detection of the peak derived from (A) is represented, and (b1) represents the time (min) at the beginning of detection of the peak derived from polyvinyl acetal (B) in the high performance liquid chromatography analysis. ]
It is suitably achieved by providing a laminate that satisfies the above.

  The difference between the average residual hydroxyl group amount of the polyvinyl acetal (A) and the average residual hydroxyl group amount of the polyvinyl acetal (B) is preferably 7 to 13 mol%.

  It is preferable that the peak area of the polyvinyl acetal (A) existing in the range of (b1) to (a2) is 2 to 100% of the total peak area of the polyvinyl acetal (A).

  It is preferable that the peak area of the polyvinyl acetal (B) existing in the range of (b1) to (a2) is 2 to 100% of the total peak area of the polyvinyl acetal (B).

  In the high performance liquid chromatography analysis of the polyvinyl acetal (B), it is preferable that at least two points at which the peak is maximized are detected.

  It is preferable that at least one of the points at which the peak of the polyvinyl acetal (B) is maximized is detected for (b1) to (a2).

  In the high performance liquid chromatography analysis of the polyvinyl acetal (A), it is preferable that at least two points at which the peak is maximized are detected.

  It is preferable that at least one of the points at which the peak of the polyvinyl acetal (A) is maximized is detected for (b1) to (a2).

  It is preferable that the plasticizer contained in the A layer contains 80 to 100% by mass of triethylene glycol di-2-ethylhexanoate.

  It is preferable that the plasticizer contained in the B layer contains 80 to 100% by mass of triethylene glycol di-2-ethylhexanoate.

  It is preferable that A layer contains 0.1-3 mass parts of triethylene glycol mono 2-ethylhexanoate with respect to 100 mass parts of polyvinyl acetal (A).

  It is preferable that B layer contains 0.1-3 mass parts of triethylene glycol mono 2-ethylhexanoate with respect to 100 mass parts of polyvinyl acetal (B).

  According to the present invention, the above object is suitably achieved by providing a laminated glass obtained by laminating the laminated body between two glasses.

  It is preferable that the edge part of a laminated glass is not sealed.

Of the two glasses, one is preferably inorganic glass and one is organic glass.

  It is preferable that the haze of the laminated glass after use for 30 days in an atmosphere having a maximum temperature of 1 day and a minimum temperature of 15 to 25 ° C. is 1% or less.

［式中、（ａ２）は内径４ｍｍ、長さ１ｃｍのＯＤＳカラムを用いた高速液体クロマトグラフィー分析におけるポリビニルアセタール（Ａ）のピークの検出終わりの時間（分）、（ｂ１）はポリビニルアセタール（Ｂ）のピークの検出初めの時間（分）を表す。］を満たす、シートを提供することで好適に達成される。 According to the present invention, the object is to provide a molded product containing 30 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 27 to 40 mol%, and an average residual hydroxyl group content. A sheet obtained by melt-kneading a molded product containing 50 to 70 parts by mass of a plasticizer with respect to 100 parts by mass of 15 to 24 mol% of polyvinyl acetal (B) and forming the resulting kneaded material into a film. Yes, the following formula (I):

[In the formula, (a2) is the time (min) at the end of detection of the peak of polyvinyl acetal (A) in high performance liquid chromatography analysis using an ODS column having an inner diameter of 4 mm and a length of 1 cm, and (b1) is polyvinyl acetal (B ) Represents the time (minutes) at the start of peak detection. It is suitably achieved by providing a sheet that satisfies the above.

  The laminate of the present invention is preferably used as a raw material for the molded article containing the polyvinyl acetal (A) and the plasticizer and the molded article containing the polyvinyl acetal (B) and the plasticizer.

  According to the present invention, when used as an interlayer film for laminated glass, the laminate is excellent in adhesiveness with glass, mechanical strength and sound insulation performance, and does not easily cause delamination even when used for a long period of time in an environment where temperature changes are significant. Can provide the body.

It is a figure which shows the ratio of the mobile phase B which occupies for the mobile phase in each time with respect to the elapsed time (horizontal axis) from the sample injection | pouring in a high performance liquid chromatography (HPLC). It is a figure which shows the example of the chart (chromatogram) obtained in the HPLC analysis concerning embodiment of this invention. It is a figure which shows the example of the chart (chromatogram) obtained in the HPLC analysis concerning embodiment of this invention. It is a figure which shows the example of the chart (chromatogram) obtained in the HPLC analysis concerning embodiment of this invention.

  First, the polyvinyl acetal (A) contained in A layer which comprises the laminated body of this invention and the polyvinyl acetal (B) contained in B layer are demonstrated. The average amount of residual hydroxyl groups of the polyvinyl acetal (A) is 27 to 40 mol%, preferably 27 to 35 mol%, and more preferably 27 to 33 mol%. When the average residual hydroxyl group amount of the polyvinyl acetal (A) is within the above range, the resulting laminate has excellent mechanical strength, excellent adhesion to glass, and the availability of polyvinyl acetal necessary for the production of the laminate. This is preferable because it is industrially easy. Moreover, the average residual hydroxyl group amount of polyvinyl acetal (B) is 15-24 mol%, Preferably it is 16-23 mol%, More preferably, it is 17-22 mol%. When the average residual hydroxyl group amount of the polyvinyl acetal (B) is within the above range, a laminate having excellent sound insulation can be obtained.

を満たすものである。 In addition, in the analysis of the HPLC of an ODS column having an inner diameter of 4 mm and a length of 1 cm, the laminate of the present invention has an initial detection time (minute) of the peak of polyvinyl acetal (A) as (a1) and an end-of-detection time ( When (min) is (a2), the time (min) at the beginning of detection of the peak of polyvinyl acetal (B) is (b1), and the time (min) at the end of detection is (b2), the following formula (I) :

It satisfies.

  (A2) − (b1) ≧ 1.5 is preferable, (a2) − (b1) ≧ 2 is more preferable, and (a2) − (b1) ≧ 3 is further preferable. When ((a2)-(a1)) is smaller than 1, the proportion of polyvinyl acetal having the same degree of polarity contained in the A layer and the B layer is reduced, and the interlayer adhesion between the A layer and the B layer is sufficient. Disappear.

  Here, in the present invention, in the high performance liquid chromatography (HPLC) analysis of an ODS column having an inner diameter of 4 mm and a length of 1 cm, the peak detection start time (a1) derived from the polyvinyl acetal (A) and the peak detection end The time (a2) will be described. In FIG. 2, peak 1 is a peak derived from polyvinyl acetal (A), and peak 2 is a peak derived from polyvinyl acetal (B). The peak detection initial time (a1) derived from the polyvinyl acetal (A) is, as shown in FIG. 2, the detection intensity is the maximum of the detection intensity of the peak 1 in the elution time of the polyvinyl acetal (A). This is the minimum elution time (minutes) that is 1/100 or more of (the detected intensity at the point 11 at which the peak 1 is maximum). The polyvinyl acetal (A) peak detection end time (a2) is the maximum of the polyvinyl acetal (A) elution time at which the detection intensity is 1/100 or more of the maximum detection intensity of peak 1. Elution time (min).

  Similarly, the initial detection time (b1) of the polyvinyl acetal (B) is the maximum detection intensity of the peak 2 (the point at which the peak 2 is maximum) in the elution time of the polyvinyl acetal (B). This is the minimum elution time (minutes) that is 1/100 or more of the detected intensity (21). The detection end time (b2) of the peak of polyvinyl acetal (B) is the maximum of the elution time of polyvinyl acetal (B) at which the detection intensity is 1/100 or more of the maximum value of the detection intensity of peak 2. Elution time (min).

  Examples of the HPLC apparatus used for specifying polyvinyl acetal in the present invention include a high-pressure gradient HPLC system “Prominence” (manufactured by Shimadzu Corporation), and examples of the ODS column include “Shim-pack”. G-ODS (4) (inner diameter: 4 mm × length: 1 cm) ”(manufactured by Shimadzu Corporation) can be used, and any HPLC apparatus and ODS column having the same function can be used. . Examples of the detector include an evaporative light scattering detector “ELSD-LTII” (manufactured by Shimadzu Corporation), and an apparatus having the same function can be used.

  The HPLC analysis of each of the polyvinyl acetal (A) and the polyvinyl acetal (B) of the present invention is performed according to the following procedure. A mixed solvent having a volume ratio of ethanol / water of 4/1 as the mobile phase A and ethanol as the mobile phase B are used. Before the sample injection, the interior of the HPLC system is filled with mobile phase A. In this state, the sample is injected. Then, the ratio of mobile phase B in the mobile phase is increased at a constant rate (5 vol% / min) over 20 minutes immediately after sample injection. From 20 minutes after sample injection (at this point, the mobile phase is completely replaced by mobile phase B), mobile phase B is allowed to flow until all of the injected sample has eluted. FIG. 1 shows the elapsed time (horizontal axis) from sample injection in HPLC analysis and the ratio of mobile phase B to the mobile phase at each time.

  From the viewpoint of excellent interlayer adhesion between the A layer and the B layer even in an environment where the temperature change is significant, the peak area of the polyvinyl acetal (A) existing in the range of (b1) to (a2) is polyvinyl acetal (A). The percentage of the total peak area is preferably 2 to 100%, preferably 10 to 100%, more preferably 15 to 100%, and still more preferably 22 to 100%. 50 to 100% is particularly preferable. In addition, the peak area of the polyvinyl acetal (A) existing in the range of (b1) to (a2) is the area indicated by the hatched portion in FIG. 3, and the total peak area of the polyvinyl acetal (A) is It is the peak area of the polyvinyl acetal (A) in the range of (a1) to (a2).

  From the viewpoint of interlayer adhesion between the A layer and the B layer, the ratio of the peak area of the polyvinyl acetal (B) existing in the range of (b1) to (a2) to the total peak area of the polyvinyl acetal (B) is: It is preferably 2 to 100%, preferably 10 to 100%, more preferably 15 to 100%, and still more preferably 25 to 100%. In addition, the peak area of the polyvinyl acetal (B) existing in the range of (b1) to (a2) is an area indicated by a hatched portion in FIG.

  In HPLC analysis using an ODS column with an inner diameter of 4 mm and a length of 1 cm of polyvinyl acetal (A), at least one of the points where the peak becomes maximum is detected at elution times (b1) to (a2). preferable. By using the polyvinyl acetal (A) having a peak at such elution time, the interlayer adhesion between the A layer and the B layer becomes higher.

  Furthermore, from the viewpoint of interlayer adhesion between the A layer and the B layer, at least in the high performance liquid chromatography analysis using an ODS column of polyvinyl acetal (A) having an inner diameter of 4 mm and a length of 1 cm, the peak is at least maximized. Preferably two are detected.

  In the HPLC analysis using an ODS column having an inner diameter of 4 mm and a length of 1 cm for polyvinyl acetal (B), at least one of the points where the peak becomes maximum is detected at elution times (b1) to (a2). preferable. By using the polyvinyl acetal (B) having such a peak at the elution time, the interlayer adhesion between the A layer and the B layer becomes higher.

  In addition, from the viewpoint of interlaminar adhesion between the A layer and the B layer, at least two points where the peak is maximum are detected in the HPLC analysis using an ODS column of polyvinyl acetal (B) having an inner diameter of 4 mm and a length of 1 cm. It is preferred that

  The method for obtaining the polyvinyl acetal (A) and the polyvinyl acetal (B) used in the present invention is not particularly limited as long as they satisfy the provisions of the present invention. The method is illustrated below.

  The polyvinyl acetal (A) and the polyvinyl acetal (B) used in the present invention are obtained by a method of acetalizing polyvinyl alcohol. For example, after an aqueous polyvinyl alcohol solution having a concentration of 3 to 20% by mass is maintained in a temperature range of 80 to 100 ° C., the temperature is gradually cooled over 10 to 60 minutes. When the temperature falls to 0 to 30 ° C., an aldehyde and an acid catalyst such as hydrochloric acid or nitric acid are added, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant. During this reaction, polyvinyl alcohol having a certain degree of acetalization is precipitated (the reaction temperature at this time is defined as the precipitation reaction temperature). Thereafter, the temperature of the reaction solution is raised to a temperature of 30 to 80 ° C. over 30 to 200 minutes, and the reaction is carried out while maintaining the temperature for 10 to 200 minutes (the reaction temperature at this time is referred to as the driving reaction temperature). Next, a neutralizing agent such as an alkali is added to the reaction solution as necessary to neutralize the acid catalyst, washing with water, and drying to obtain a polyvinyl acetal.

  Examples of the polyvinyl acetal (A) used in the present invention include a method obtained by mixing two or more polyvinyl acetals having different average residual hydroxyl group amounts. In this case, for example, polyvinyl acetal having an average residual hydroxyl group amount of 25 to 40 mol%, preferably 27 to 34 mol%, more preferably 28 to 33 mol%, and an average residual hydroxyl group amount of 15 to 30 mol%, preferably 20 to 30 mol%, more preferably 25 to 30 mol% of polyvinyl acetal mixed with an average residual hydroxyl group amount of 1 mol% or more, preferably 2 mol% or more, more preferably 4 mol% or more. The polyvinyl acetal thus obtained can be mixed and used at an appropriate ratio so that the average residual hydroxyl group is 27 to 40 mol%. The mixing ratio of polyvinyl acetal having an average residual hydroxyl group content of 25 to 40 mol% and polyvinyl acetal having an average residual hydroxyl group content of 15 to 30 mol% is preferably 99/1 to 1/99, and 99/1 to 70. / 30 is more preferable, and 99/1 to 50/50 is further preferable. In the method of mixing two or more types of polyvinyl acetals having different average residual hydroxyl groups, the peak of the polyvinyl acetal (A) in the HPLC analysis of the polyvinyl acetal (A) is particularly at least 2 as the polyvinyl acetal (A) of the present invention. It is a suitable method for obtaining what is detected.

  Further, as a method of acetalizing the polyvinyl alcohol, a method such as a precipitation reaction temperature of 20 to 30 ° C. or a driving reaction temperature of 75 to 80 ° C .; a condition that the particle diameter of the resulting polyvinyl acetal is increased Or 30% to 90% of the total aldehyde used in the reaction is added before the polyvinyl acetal having a certain level of acetalization is precipitated, and 10% of the total aldehyde is precipitated. When a method such as adding ˜70% is used, the average residual hydroxyl group amount satisfies a specific value, and the distribution of the residual hydroxyl group amount is wide, that is, the one containing polyvinyl acetal having a polarity close to that of the polyvinyl acetal (B). Can be obtained. By using such a polyvinyl acetal as the polyvinyl acetal (A), a laminate satisfying the requirements of the present invention can be obtained.

  Moreover, as a polyvinyl acetal (B), the method of mixing the 2 or more types of polyvinyl acetal from which average amount of residual hydroxyl groups differs is mentioned, for example. In this case, for example, a polyvinyl acetal having an average residual hydroxyl group content of 25 to 35 mol%, preferably 25 to 33 mol%, more preferably 25 to 31 mol%, and an average residual hydroxyl group content of 14 to 30 mol%, preferably 16 to 27 mol%, more preferably 18 to 25 mol% of polyvinyl acetal, each having an average residual hydroxyl group content of 1 mol% or more, preferably 2 mol% or more, more preferably 4 mol% or more mixed. It can be used by mixing at an appropriate ratio so that the average residual hydroxyl group of the polyvinyl acetal is 15 to 24 mol%. The mixing ratio of polyvinyl acetal having an average residual hydroxyl group content of 25 to 35 mol% and polyvinyl acetal having an average residual hydroxyl group content of 14 to 30 mol% is preferably 99/1 to 1/99, and 70/30 to 1 / 99 is more preferable, and 50/50 to 1/99 is even more preferable. In the method of mixing two or more kinds of polyvinyl acetals having different average residual hydroxyl groups, the peak of the polyvinyl acetal (B) in the HPLC analysis of the polyvinyl acetal (B) is at least 2 in particular as the polyvinyl acetal (B) of the present invention. It is a suitable method for obtaining what is detected.

  Furthermore, the particle diameter of the polyvinyl acetal obtained is increased by a method of acetalizing the polyvinyl alcohol by a method such as a precipitation reaction temperature of 20-30 ° C. or a driving reaction temperature of 75-80 ° C. The method for carrying out the acetalization reaction under various conditions, or 30 to 90% of the total aldehyde used in the reaction is added before the polyvinyl acetal having reached a certain level of acetalization, and after the precipitation all the aldehyde In which the average residual hydroxyl group content satisfies a specific value and the distribution of the residual hydroxyl group content is broad, that is, a material containing a polyvinyl acetal having a polarity close to that of the polyvinyl acetal (A). Can be obtained. For this reason, it is excellent in interlayer adhesiveness with A layer. By using such a polyvinyl acetal as the polyvinyl acetal (B), a laminate satisfying the requirements of the present invention can be obtained. According to such a method, when HPLC analysis is performed on an ODS column having an average residual hydroxyl group content of 25 to 35 mol% and an inner diameter of 4 mm and a length of 1 cm, at least two points where the peak is maximized are detected. , Polyvinyl acetal (B) can be obtained.

  The aldehyde used in the acetalization reaction of the present invention is not particularly limited, but it is preferable to acetalize with a conventionally known aldehyde having 1 to 8 carbon atoms, among which aldehydes having 4 to 6 carbon atoms are preferable, and in particular, n-butyraldehyde. Is preferably used. In the present invention, polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.

  The difference between the average amount of residual hydroxyl groups of the polyvinyl acetal (A) used in the present invention and the average amount of residual hydroxyl groups of the polyvinyl acetal (B) is not particularly limited, but it is 7 to 13 moles from the viewpoint of expressing optimum sound insulation performance. %, More preferably 7.5 to 12.7 mol%, and still more preferably 8 to 12.5 mol%.

  Next, the plasticizer contained in the A layer and the B layer of the laminate of the present invention will be described. As the plasticizer used in the present invention, conventionally known plasticizers can be used, and in particular, dihydric alcohols such as triethylene glycol di-2-ethylhexanoate and oligoethylene glycol di-2-ethylhexanoate. Diester compound of carboxylic acid and monovalent carboxylic acid, or diester compound of dihydric carboxylic acid and monohydric alcohol such as dihexyl adipate, dioctyl adipate, di (2-butoxyethyl) adipate, etc. The plasticizer obtained is preferable in terms of compatibility with the polyvinyl acetal (A) and the polyvinyl acetal (B) and the plasticizing effect on the polyvinyl acetal (A) and the polyvinyl acetal (B).

  In particular, the plasticizer contained in the A layer and the B layer of the laminate of the present invention contains triethylene glycol di-2-ethylhexanoate, and the content of triethylene glycol di-2-ethylhexanoate Is preferably a plasticizer that is 80 to 100% by mass of the total amount of the plasticizer contained in the A layer. The content of triethylene glycol di-2-ethylhexanoate is more preferably 85 to 100% by mass, and still more preferably 90 to 100% by mass, based on the total amount of plasticizer contained in the A layer. Triethylene glycol di-2-ethylhexanoate has a high boiling point, is particularly compatible with polyvinyl acetal, and is particularly excellent in plasticizing effect to polyvinyl acetal. Also, the mechanical strength of the sheet obtained by mixing with polyvinyl acetal and the glass Excellent adhesion. Therefore, the plasticizer containing triethylene glycol di-2-ethylhexanoate within the above range is excellent in compatibility with polyvinyl acetal and plasticizing effect to polyvinyl acetal, and the dynamics of the sheet obtained by mixing with polyvinyl acetal. It is preferable at the point which is excellent in intensity | strength and the adhesiveness to glass.

  As content of the plasticizer in A layer, it is preferable that it is 30-50 mass parts with respect to 100 mass parts of polyvinyl acetal (A), It is more preferable that it is 31-47 mass parts, 32-45 mass parts It is more preferable that When the content of the plasticizer in the A layer is within the above range, the laminate is excellent in mechanical strength, excellent in workability when making a laminated glass using the laminate, and excellent in adhesion to glass. It is in.

  As content of the plasticizer in B layer, it is preferable that it is 50-70 mass parts with respect to 100 mass parts of polyvinyl acetal (B), It is more preferable that it is 51-68 mass parts, 52-66 mass parts It is more preferable that When the content of the plasticizer in the B layer is within the above range, the resulting laminate tends to be excellent in sound insulation and mechanical strength.

  Furthermore, in the A layer of the present invention, polyalkylene glycol monocarboxylic acid such as triethylene glycol mono 2-ethylhexanoate, oligoethylene glycol mono 2-ethyl hexanoate, etc. with respect to 100 parts by mass of polyvinyl acetal (A). The acid ester is preferably contained in an amount of 0.1 to 3 parts by mass, more preferably 0.15 to 1 part by mass, and further preferably 0.2 to 0.8 parts by mass. Although the kind of polyalkylene glycol monocarboxylic acid ester is not particularly limited, those having a structure similar to the plasticizer contained in the A layer are preferable from the viewpoint of compatibility with the plasticizer. In particular, when the layer A contains triethylene glycol di-2-ethylhexanoate as a plasticizer, the polyalkylene glycol monocarboxylic acid ester has a structure similar to that of triethylene glycol di-2-ethylhexanoate. It preferably contains ethylene glycol mono 2-ethylhexanoate.

  In the B layer of the present invention, polyalkylene glycol monocarboxylic acid such as triethylene glycol mono-2-ethylhexanoate or oligoethylene glycol mono2-ethylhexanoate is used with respect to 100 parts by mass of polyvinyl acetal (B). The acid ester is preferably contained in an amount of 0.1 to 3 parts by mass, more preferably 0.15 to 1.0 part by mass, and further preferably 0.2 to 0.8 parts by mass. Although the kind of polyalkylene glycol monocarboxylic acid ester is not particularly limited, those having a structure similar to that of the plasticizer contained in the B layer are preferable from the viewpoint of compatibility with the plasticizer. In particular, when the layer B contains triethylene glycol di-2-ethylhexanoate as a plasticizer, the polyalkylene glycol monocarboxylic acid ester has a structure similar to that of triethylene glycol di-2-ethylhexanoate. It preferably contains ethylene glycol mono 2-ethylhexanoate.

  The polyalkylene glycol monocarboxylic acid ester contained in the A layer and / or the B layer constituting the laminate of the present invention has an effect of compatibilizing polyvinyl acetals having slightly different residual hydroxyl groups in the vicinity of the interface between the A layer and the B layer, respectively. There is. Therefore, in the laminate including the polyalkylene glycol monocarboxylic acid ester in the A layer and / or the B layer, the interlayer adhesion between the A layer and the B layer is further improved. In addition, when the polyalkylene glycol monocarboxylic acid ester contained in the A layer is less than 0.1 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A), the polyalkylene glycol monocarboxylic acid ester contained in the B layer is When the amount is less than 0.1 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B), the effect of compatibilizing polyvinyl acetals having different residual hydroxyl amounts may not be sufficiently exhibited. On the other hand, when the content of the polyalkylene glycol monocarboxylic acid ester in the A layer exceeds 3 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A), or the content of the polyalkylene glycol monocarboxylic acid ester in the B layer is When it exceeds 3 mass parts with respect to 100 mass parts of polyvinyl acetal (B), the moisture resistance of the laminated body obtained and the adhesiveness to glass may become inadequate.

  As described above, the polyalkylene glycol monocarboxylic acid ester has an effect as a compatibilizing agent for compatibilizing polyvinyl acetals having different residual hydroxyl amounts. Therefore, the laminate of the present invention containing a predetermined amount of polyalkylene glycol monocarboxylic acid ester is excellent in recyclability. That is, when the trim generated when producing the laminated glass using the laminate is again melt-kneaded, compared to the case where the trim of the laminate not containing the polyalkylene glycol monocarboxylic acid ester is melt-kneaded. A film having excellent transparency can be obtained. When such recycling is performed, it is not necessary to add a reagent for improving transparency from the outside. Therefore, it is also preferable from the viewpoint of not requiring equipment and equipment for adding the reagent.

  The A layer and the B layer constituting the laminate of the present invention may contain an antioxidant, an ultraviolet absorber, an adhesion improver, and other additives as long as not departing from the gist of the present invention.

  When the antioxidant is added to the A layer or the B layer, the kind thereof is not particularly limited, and examples thereof include conventionally known phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. . Among these, phenolic antioxidants are preferable, and alkyl-substituted phenolic antioxidants are particularly preferable. These antioxidants can be used alone or in combination of two or more. Although the addition amount of antioxidant is not specifically limited, 0.0001-5 mass% with respect to the mass of A layer or B layer, Preferably it is good in it being the range of 0.001-1 mass%. If the added amount of the antioxidant is less than 0.0001% by mass relative to the mass of the A layer or B layer, a sufficient effect may not be obtained, and if it is more than 5% by mass, a remarkable effect can be expected. Absent.

  When the ultraviolet absorber is added to the A layer or the B layer, the kind thereof is not particularly limited. For example, conventionally known benzotriazole ultraviolet absorbers, oxalic anilide ultraviolet absorbers, benzoate ultraviolet absorbers, etc. Can be used. These ultraviolet absorbers can be used alone or in combination of two or more. Although the addition amount of a ultraviolet absorber is not specifically limited, 0.0001-5 mass% with respect to the mass of A layer or B layer, Preferably it is good in it being the range of 0.001-1 mass%. If the addition amount of the ultraviolet absorber is less than 0.0001% by mass with respect to the mass of the A layer or the B layer, a sufficient ultraviolet absorption effect may not be obtained. The effect cannot be expected.

  Moreover, when using the laminated body of this invention for the use which needs to adjust adhesiveness with glass appropriately, such as an interlayer film for laminated glasses, it is adhesiveness adjustment to A layer and B layer which comprise a laminated body. An agent may be added. As the adhesion adjusting agent, conventionally known ones can be used, for example, acetic acid, propionic acid, butanoic acid, hexanoic acid, sodium salt of organic acid such as 2-ethylbutanoic acid or 2-ethylhexanoic acid, A potassium salt or a magnesium salt is used. Two or more kinds of these adhesion modifiers may be added. The addition amount of the adhesion adjusting agent is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 0.1% by mass with respect to the mass of each of the A layer and the B layer. -0.03 mass% is still more preferable.

  The laminate of the present invention can be produced by a conventionally known method using polyvinyl acetal (A), polyvinyl acetal (B), plasticizer (A) and plasticizer (B). Specific examples of the production method of the laminate include a method in which the A layer and the B layer are individually formed by an extrusion film forming method, a cast film forming method, a press film forming method, etc. The method of laminating | stacking A layer and B layer simultaneously with film forming by the extrusion method etc. is mentioned.

  Although the thickness of A layer and B layer in the laminated body of this invention is not specifically limited, It is preferable that the thickness of A layer is 0.05-0.8 mm, and it is 0.15-0.6 mm. More preferably, it is 0.2-0.5 mm. If the thickness of the A layer is less than 0.05 mm, the mechanical strength of the laminate of the present invention may be insufficient, and if it is greater than 0.8 mm, the flexibility of the laminate of the present invention is insufficient. For example, when used as a laminated glass interlayer film, sufficient impact resistance may not be exhibited. Further, the thickness of the B layer is preferably 0.01 to 0.8 mm, more preferably 0.05 to 0.4 mm, and further preferably 0.07 to 0.3 mm. When the thickness of the B layer is less than 0.01 mm, preferable sound insulation performance may not be exhibited, and when it is greater than 0.8 mm, the mechanical strength may be insufficient.

  In addition, when a recycled product is manufactured using a trim or off-spec product generated when producing the laminate of the present invention as a raw material, a recycled product having better transparency than the conventional product can be obtained.

  The laminated body of the present invention can be used as laminated glass by laminating between two glasses. The glass used in that case is not particularly limited, but in addition to inorganic glass such as float plate glass, polished plate glass, mold plate glass, mesh plate glass, heat ray absorbing plate glass, conventionally known organic glass, etc. can be used, these are colorless or It may be colored and either transparent or non-transparent. These glasses may be used alone or in combination of two or more. When two or more types are used in combination, especially when laminated glass that uses inorganic glass such as float glass and organic glass such as acrylic and polycarbonate is used in an environment with temperature changes, there is a difference in the speed at which heat is transmitted from both the front and back surfaces. For this reason, stress due to the difference in coefficient of thermal expansion of each layer is generated at the interface between the layers of the laminate included in the laminated glass of the present invention, and as a result, delamination tends to occur. Since the body is excellent in interlayer adhesion, delamination hardly occurs even in such a laminated glass, which is preferable.

  The thickness of the glass used with the laminated glass of this invention is not limited, For example, glass of conventionally well-known thickness, such as 0.5 mm-20 mm, can be used.

  Since the laminate of the present invention is excellent in interlayer adhesion between the A layer and the B layer, it is preferable that delamination does not occur even when it is used in an environment where temperature change is significant. The problem of delamination tends to occur remarkably when the interlayer film for laminated glass absorbs water. Usually, an interlayer film for laminated glass is often used with its moisture content adjusted to about 0.5% by mass. However, the moisture content of the edge is not treated with a water-resistant sealant. May be higher than 1.0%. In the laminate of the present invention, the polyvinyl acetal contained in each layer is compatible with each other at the interface between the A layer and the B layer, and a mechanical bond is formed. Accordingly, the moisture content of the interlayer film for laminated glass is high, and even when hydrogen bonds between polyvinyl acetal molecules are broken to some extent, high adhesion can be maintained. The laminated glass used as can be suitably used for a long period of time even if it is not end-sealed.

  When the laminate of the present invention is used as an interlayer film for laminated glass, the shape of the outermost surface (surface to be bonded to glass) of the laminate is not particularly limited, but the handleability (bubble removal) when laminating with glass is not limited. In consideration, it is preferable to form a concavo-convex structure on the outermost surface of the laminate by a conventionally known method such as melt fracture or embossing.

  The laminated glass of the present invention can be produced by a conventionally known method, and examples thereof 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. . In addition, after the temporary pressure bonding by these methods, a method of putting the obtained temporary pressure bonded body into the autoclave can be additionally performed.

In the case of using a vacuum laminator apparatus, an example of the production conditions is as follows: lamination is performed at a temperature of 100 to 200 ° C., particularly 130 to 160 ° C. under a reduced pressure of 1 × 10 ^{−6 to} 3 × 10 ⁻² MPa. A method using a vacuum bag or a vacuum ring is described in, for example, European Patent No. 1235683, and is laminated at 130 to 145 ° C. under a pressure of about 2 × 10 ⁻² MPa, for example.

  In the case of using a nip roll, an example of the operating conditions includes a method in which the first pressure bonding is performed at a temperature equal to or lower than the flow start temperature of the plasticized polyvinyl acetal resin, and then the pressure bonding is further performed under conditions close to the flow start temperature. . Specifically, for example, after heating to 30 to 70 ° C. with an infrared heater or the like, degassing with a roll, and further heating to 50 to 120 ° C., followed by pressure bonding with a roll and bonding or temporary bonding may be mentioned. In addition, the operating conditions of the autoclave process additionally performed after the temporary pressure bonding are appropriately selected depending on the thickness and configuration of the module and the laminated glass. For example, under a pressure of 1.0 to 1.5 MPa, 130 to 145 It is carried out at a temperature of 0 C for 0.5-3 hours.

  The laminated glass including the laminate of the present invention is particularly excellent in interlayer adhesion. Therefore, in particular, the laminated glass is suitably used for applications in which the difference between the daily maximum temperature and the minimum temperature is 15 to 25 ° C and the minimum temperature is -20 to -10 ° C. The haze after use for 30 days in an atmosphere where the difference between the maximum temperature and the minimum temperature of the day is 15 to 25 ° C. and the minimum temperature is −20 to −10 ° C. is 1% or less. Preferably, it is 0.8% or less.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Preparation of PVB-1)
In a 10 L (liter) glass container equipped with a reflux condenser, thermometer, and squid type stirring blade, 8100 g of ion-exchanged water and 660 g of polyvinyl alcohol (PVA-1: viscosity average degree of polymerization 1700, saponification degree 99 mol%). Preparation (PVA concentration 7.5%) and the content was heated to 95 ° C. to completely dissolve the polyvinyl alcohol. Next, after gradually cooling to 5 ° C. over 120 minutes with stirring at 120 rpm, 384 g of butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 150 minutes (the precipitation of polyvinyl acetal was It was after the end of butyraldehyde addition). Thereafter, the temperature was raised to 50 ° C. over 60 minutes, held at 50 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water, an excess amount of aqueous sodium hydroxide solution was added to neutralize the remaining acid, and further washed with excess water and dried to obtain polyvinyl butyral (PVB-1). . The properties of the obtained PVB-1 were measured according to JIS K6728. The average degree of acetalization was 69 mol%, the average residual vinyl acetate group content was 1 mol%, and the average residual hydroxyl group content was 30 mol%. It was. The results are shown in Table 1.

(Preparation of PVB-2)
In the preparation of PVB-1, polyvinyl butyral (PVB-2) was obtained in the same manner except that the amount of butyraldehyde used was changed to 395 g. The precipitation of polyvinyl acetal occurred after the addition of butyraldehyde was completed. When the characteristics of PVB-2 were measured according to JIS K6728, the average degree of acetalization was 71 mol%, the average residual vinyl acetate group content was 1 mol%, and the average residual hydroxyl group content was 28 mol%. The results are shown in Table 1.

(Preparation of PVB-3)
A 10 L glass container equipped with a reflux condenser, a thermometer, and a squid type stirring blade is charged with 8100 g of ion exchange water and 723 g of polyvinyl alcohol (PVA-2: viscosity average polymerization degree 1700, saponification degree 90 mol%) (PVA). The concentration was 8.2%), and the contents were heated to 95 ° C. to completely dissolve the polyvinyl alcohol. Next, after gradually cooling to 5 ° C. with stirring at 120 rpm over about 30 minutes, 395 g of butyraldehyde and 540 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 150 minutes. Polyvinyl acetal precipitation occurred after the end of butyraldehyde addition. Thereafter, the temperature was raised to 50 ° C. over 60 minutes, held at 50 ° C. for 120 minutes, and then cooled to room temperature. The precipitated resin was washed with ion-exchanged water, an excess amount of aqueous sodium hydroxide solution was added to neutralize the remaining acid, and further washed with excess water and dried to obtain polyvinyl butyral (PVB-3). . The properties of the obtained PVB-3 were measured according to JIS K6728. The average degree of acetalization was 71 mol%, the average residual vinyl acetate group content was 9 mol%, and the average residual hydroxyl group content was 20 mol%. It was. The results are shown in Table 1.

(Preparation of PVB-4)
A 10 L glass container equipped with a reflux condenser, a thermometer, and a squid type stirring blade was charged with 8100 g of ion-exchanged water and 705 g of polyvinyl alcohol (PVA-3: viscosity average polymerization degree 1700, saponification degree 93 mol%) (PVA). The concentration was raised to 95 ° C., and the polyvinyl alcohol was completely dissolved. Next, after gradually cooling to 8 ° C. over about 30 minutes with stirring at 120 rpm, 415 g of butyraldehyde and 660 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 150 minutes. Then, it heated up to 68 degreeC over 60 minutes, and hold | maintained at 68 degreeC for 220 minutes, Then, it cooled to room temperature. After washing the precipitated resin with ion-exchanged water, an excess amount of sodium hydroxide aqueous solution was added to neutralize the remaining acid, and further washed with excess water and dried to obtain polyvinyl butyral (PVB-4). . When the properties of the obtained PVB-4 were measured according to JIS K6728, the average degree of acetalization was 74 mol%, the average residual vinyl acetate group content was 7 mol%, and the average residual hydroxyl group content was 19 mol%. It was. The results are shown in Table 1.

(Preparation of PVB-5)
A 10 L (liter) glass container equipped with a reflux condenser, a thermometer, and a squid type stirring blade was charged with 8100 g of ion-exchanged water and 723 g of PVA-2 (viscosity average polymerization degree 1700, saponification degree 90 mol%) (PVA). The concentration was 8.2%), and the contents were heated to 95 ° C. to completely dissolve the polyvinyl alcohol. Next, after gradually cooling to 17 ° C. over about 30 minutes with stirring at 120 rpm, 250 g of butyraldehyde and 500 mL of 30% nitric acid were added, and a butyralization reaction was performed for 100 minutes. During this reaction, polyvinyl acetal precipitated. Next, after adding 145 g of butyraldehyde and reacting at 17 ° C. for 50 minutes, the temperature was raised to 67 ° C. over 60 minutes, kept at 67 ° C. for 120 minutes, and then cooled to room temperature. After washing the precipitated resin with ion-exchanged water, an excess amount of sodium hydroxide aqueous solution is added to neutralize the remaining acid, and further washed with excess water and dried to obtain polyvinyl butyral (PVB-5). It was. The properties of the obtained PVB-5 were measured according to JIS K6728. The average degree of acetalization was 71 mol%, the average residual vinyl acetate group content was 9 mol%, and the average residual hydroxyl group content was 20 mol%. It was. The results are shown in Table 1.

(Preparation of PVB-6)
A 10 L glass container equipped with a reflux condenser, a thermometer, and a squid type stirring blade was charged with 8100 g of ion exchange water and 705 g of PVA-3 (viscosity average polymerization degree 1700, saponification degree 93 mol%) (PVA concentration 8. 0%), the contents were heated to 95 ° C. to completely dissolve the polyvinyl alcohol. Next, after gradually cooling to 18 ° C. over about 30 minutes with stirring at 120 rpm, 300 g of butyraldehyde and 550 mL of 30% nitric acid were added, and a butyralization reaction was performed for 100 minutes. During this reaction, polyvinyl acetal precipitated. Next, 115 g of butyraldehyde was added and reacted at 18 ° C. for 50 minutes. Then, the temperature was raised to 68 ° C. over 60 minutes, held at 68 ° C. for 220 minutes, and then cooled to room temperature. After washing the precipitated resin with ion-exchanged water, an excess amount of aqueous sodium hydroxide solution is added to neutralize the remaining acid, and further washed with excess water and dried to obtain polyvinyl butyral (PVB-6). It was. The properties of the obtained PVB-6 were measured according to JIS K6728. The average degree of acetalization was 74 mol%, the average residual vinyl acetate group content was 6 mol%, and the average residual hydroxyl group content was 20 mol%. It was. The results are shown in Table 1.

(Preparation of PVB-7)
A 10 L glass container equipped with a reflux condenser, a thermometer, and a squid type stirring blade is charged with 8100 g of ion exchange water and 741 g of polyvinyl alcohol (PVA-4: viscosity average polymerization degree 1700, saponification degree 87 mol%) (PVA). The concentration was increased to 8.4%), and the content was heated to 95 ° C. to completely dissolve the polyvinyl alcohol. Next, after gradually cooling to 17 ° C. over about 30 minutes with stirring at 120 rpm, 300 g of butyraldehyde and 600 mL of 20% hydrochloric acid were added, and a butyralization reaction was performed for 80 minutes. During this reaction, polyvinyl acetal precipitated. Next, 84 g of butyraldehyde was added and reacted at 17 ° C. for 50 minutes, then the temperature was raised to 66 ° C. over 60 minutes, kept at 66 ° C. for 180 minutes, and then cooled to room temperature. After washing the precipitated resin with ion-exchanged water, an excess amount of aqueous sodium hydroxide solution is added to neutralize the remaining acid, and further washed with excess water and dried to obtain polyvinyl butyral (PVB-7). It was. When the properties of the obtained PVB-7 were measured according to JIS K6728, the average degree of acetalization was 67 mol%, the average amount of residual vinyl acetate groups was 12 mol%, and the average amount of residual hydroxyl groups was 21 mol%. The results are shown in Table 1.

(Preparation of PVB-8)
20 parts by mass of PVB-1 and 80 parts by mass of PVB-3 were mixed to obtain polyvinyl acetal (PVB-8). The properties of the obtained PVB-8 were measured according to JIS K6728. The average degree of acetalization was 71 mol%, the average residual vinyl acetate group content was 7 mol%, and the average residual hydroxyl group content was 22 mol%. It was. The results are shown in Table 1.

(Preparation of PVB-9)
20 parts by mass of PVB-2 and 80 parts by mass of PVB-4 were mixed to obtain polyvinyl acetal (PVB-9). The properties of the obtained PVB-9 were measured according to JIS K6728. The average degree of acetalization was 74 mol%, the average residual vinyl acetate group content was 6 mol%, and the average residual hydroxyl group content was 20 mol%. It was. The results are shown in Table 1.

(Preparation of PVB-10)
80 parts by mass of PVB-1 and 20 parts by mass of PVB-3 were mixed to obtain polyvinyl acetal (PVB-10). The properties of the obtained PVB-10 were measured according to JIS K6728. The average degree of acetalization was 69 mol%, the average residual vinyl acetate group content was 3 mol%, and the average residual hydroxyl group content was 28 mol%. It was. The results are shown in Table 1.

(Analysis of PVB-1 to PVB-10 by HPLC)
(1) Preparation of analysis sample For each of PVB-1 to PVB-10 in a pressure test tube, 100 mg of polyvinyl acetal and 20 mL of ethanol (99.5%) are weighed and completely sealed, and then the pressure test tube is shaken. It was immersed in a constant temperature water bath. Then, the mixture was shaken at 70 ° C. for 4 hours to dissolve the polyvinyl acetal in ethanol. At 3.5 hours, all the polyvinyl acetals were completely dissolved in ethanol. After allowing to cool at room temperature, the mixture was filtered through a water-immersed PTFE membrane filter having a pore diameter of 0.45 μm and a diameter of 13 mm to obtain an HPLC test solution.

(2) HPLC measurement “Prominence” manufactured by Shimadzu Corporation as the HPLC system and “Shim-pack G-ODS (4)” manufactured by Shimadzu Corporation as the HPLC column (ODS column having an inner diameter of 4 mm and a length of 1 cm) are used. As a detector, “ELSD-LT II” manufactured by Shimadzu Corporation was used. The analysis was performed according to the following procedure. As the mobile phase A, a mixed solvent having an ethanol / water (volume ratio) of 4/1 was used, and as the mobile phase B, ethanol was used. Initially, the HPLC system is filled with mobile phase A. In this state, the sample is injected. Then, the ratio of the mobile phase B in the mobile phase was increased at a constant rate (5 vol% / min) over 20 minutes immediately after sample injection. After 20 minutes (the mobile phase is completely replaced by mobile phase B at this point), mobile phase B was allowed to flow until all of the injected sample had eluted. At that time, the sample injection amount was 30 μL, and the flow rate of the mobile phase was 0.4 mL / min. The column temperature was 45 ° C., and nitrogen gas was used as the nebulizer gas of the detector (gas supply pressure = 350 kPa, spray temperature 35 ° C. The analysis of the obtained data was performed by “Lab Solutions LC (ver. 5.42 SP3) "was used and the analysis was performed under the following conditions.
Width: 30 seconds immediately after sample injection, 200 seconds from 5 minutes to the end Slope: 50 μm
Drift: 0 μV / min DBL: 0 minutes Minimum area: 10,000 counts The baseline was determined by analyzing a blank test solution prepared in the same manner as in the preparation of the analytical sample except that polyvinyl acetal was dissolved. The results are shown in Table 1.

Example 1
100 parts by mass of PVB-1, 39 parts by mass of 3GO (triethylene glycol di-2-ethylhexanoate), 0.3 mass of triethylene glycol mono-2-ethylhexanoate (hereinafter referred to as carboxylic acid ester-1) After being melt-kneaded with a lab plast mill at 150 ° C. for 3 minutes, a sheet A having a thickness of 0.3 mm was obtained by a press film forming method. Further, 80 parts by mass of PVB-3, 20 parts by mass of PVB-1, 60 parts by mass of 3GO, 0.6 parts by mass of carboxylic acid ester-1 at 150 ° C. for 3 minutes using a lab plast mill, A sheet B having a thickness of 0.15 mm was obtained by a press film forming method. Sheet-A, sheet-B, and sheet-A were stacked in this order, and bonded by hot pressing to obtain laminate-1.

(Evaluation of adhesion to glass)
Laminate-1 cut to a size of 10 cm x 20 cm was sandwiched between two 10 cm x 20 cm x 2 mm thick float glass, temporarily bonded with a nip roll, and then treated with an autoclave at 140 ° C, 1.2 MPa for 60 minutes. Glass was used. When the Pummel test of the obtained laminated glass was implemented, the Pummel value was 9.

(Evaluation of loss factor of laminated glass)
Laminated body-1 was sandwiched between 3 mm thick float glass, temporarily bonded with a nip roll, and then treated with an autoclave at 140 ° C., 1.2 MPa for 60 minutes to obtain a laminated glass. The obtained laminated glass is vibrated with a vibrator (EMIC, small vibration generator 512-A), and the frequency response function at that time is detected with an FFT analyzer (Ono Sokki, DS-2100). The loss coefficient at 2000 Hz was calculated using servo analysis software (DS-0242, manufactured by Ono Sokki Co., Ltd.). The measurement was performed in an atmosphere at 20 ° C. The larger the loss factor, the better the sound insulation performance of the laminated glass.

(Cycle test 1)
Laminate-1 was cut to a size of 30 cm x 30 cm, sandwiched between two pieces of 30 cm x 30 cm x 2 mm glass, temporarily bonded with a nip roll, and then treated with an autoclave at 140 ° C, 1.2 MPa for 60 minutes. And laminated glass. The obtained laminated glass was held at 40 ° C. and 90% RH for 10 hours, then cooled from 40 ° C. to −40 ° C. over 2 hours (humidity unadjusted), and held at −40 ° C. for 10 hours (humidity not yet adjusted). Adjustment), and the process of heating from -40 ° C. to 40 ° C. over 2 hours (humidity unadjusted) was defined as one cycle, and the cycle was repeated 50 cycles. The state of delamination (end part and center part) of the A layer and the B layer in the laminated glass after repeating 50 cycles was confirmed.

(Cycle test 2)
Laminate-1 was cut to a size of 30 cm x 30 cm, sandwiched between two pieces of 30 cm x 30 cm x 2 mm glass, temporarily bonded with a nip roll, and then treated with an autoclave at 140 ° C, 1.2 MPa for 60 minutes. And laminated glass. The obtained laminated glass was held at 40 ° C. and 90% RH for 2 hours, then cooled from 40 ° C. to −40 ° C. over 1 hour (humidity unadjusted), and held at −40 ° C. for 2 hours (humidity unadjusted) ) Furthermore, the process of heating from -40 ° C. to 40 ° C. over 1 hour (humidity unadjusted) was defined as one cycle, and this cycle was repeated 50 cycles. The state of delamination (end part and center part) of the A layer and the B layer in the laminated glass after repeating 50 cycles was confirmed.

(Boiling cooling cycle test of laminate)
Laminated body-1 was cut into 2 cm × 2 cm (10 sheets), poured into water heated to 80 ° C. and treated for 30 minutes, and then laminated body-1 taken out from the heated water was quickly cooled with ice water (0 ° C. ) And treated for 5 minutes. The cycle was repeated 10 times, and the number of samples in which peeling occurred was measured.

(Simulated recycling test)
Laminate-1 was melt-kneaded at 60 ° C. and 150 ° C. for 5 minutes using a lab plast mill, and the resulting kneaded material was formed into a film by a press film formation method to obtain a 0.8 mm thick sheet. Obtained. The sheet was sandwiched between 3 mm thick float glass, temporarily attached with a nip roll, and then treated with an autoclave at 140 ° C., 1.2 MPa for 60 minutes to obtain a laminated glass. When the haze of the laminated glass was evaluated, it was 10.2%.

(Example 2) to (Example 21) and (Comparative Example 1) to (Comparative Example 6)
According to the configurations and compositions shown in Tables 2 and 3, Laminate-2 to Laminate-21, and Comparative Example Laminate-1 to Comparative Example Laminate-6 were prepared, and the same method as Example 1 was used. Evaluation was performed. The numerical values in the columns of plasticizer and carboxylic acid ester-1 in Table 2 and Table 3 represent the content of each compound relative to 100 parts by mass of polyvinyl acetal (A) or polyvinyl acetal (B). The results of HPLC analysis are shown in Table 4, and other evaluation results are shown in Table 5.

  When used as an interlayer film for laminated glass, the laminate of the present invention has excellent adhesion to glass, mechanical strength, and sound insulation performance, and does not cause delamination even when used for a long period of time in an environment with significant temperature changes. Therefore, it is suitable as an interlayer film for laminated glass. In addition, when a trim or off-spec product generated when the laminate of the present invention is produced is used as a raw material, a recycled product having better transparency than the conventional one can be obtained.

1 Peak of HPLC analysis of polyvinyl acetal (A) 11 Maximum point of HPLC analysis peak of polyvinyl acetal (A) 2 Peak of HPLC analysis of polyvinyl acetal (B) 21 Maximum point of HPLC analysis peak of polyvinyl acetal (B)

Claims (18)

A layer containing 30 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 27 to 40 mol%, and a polyvinyl acetal (B ) A B layer containing 50 to 70 parts by mass of a plasticizer with respect to 100 parts by mass;

[Wherein (a2) is polyvinyl acetal in high performance liquid chromatography (HPLC) analysis using a column (ODS column) packed with a spherical silica gel surface modified with octadecylsilyl group having an inner diameter of 4 mm and a length of 1 cm as a stationary phase. The time (min) at the end of detection of the peak derived from (A) is represented, and (b1) represents the time (min) at the beginning of detection of the peak derived from polyvinyl acetal (B) in the high performance liquid chromatography analysis. ]
Satisfying the laminate. The laminate according to claim 1, wherein the difference between the average residual hydroxyl group content of the polyvinyl acetal (A) and the average residual hydroxyl group content of the polyvinyl acetal (B) is 7 to 13 mol%. The laminate according to claim 1 or 2, wherein the peak area of the polyvinyl acetal (A) existing in the range of (b1) to (a2) is 2 to 100% of the total peak area of the polyvinyl acetal (A). The peak area of the polyvinyl acetal (B) existing in the range of (b1) to (a2) is 2 to 100% of the total peak area of the polyvinyl acetal (B). Laminated body. The laminate according to any one of claims 1 to 4, wherein at least two points at which peaks become maximum are detected in the high performance liquid chromatography analysis of polyvinyl acetal (B). The laminate according to claim 5, wherein at least one of the points at which the peak of the polyvinyl acetal (B) is maximized is detected for (b1) to (a2). The laminated body according to any one of claims 1 to 6, wherein at least two points at which peaks become maximum are detected in the high performance liquid chromatography analysis of polyvinyl acetal (A). The laminate according to claim 7, wherein at least one of the points at which the peak of the polyvinyl acetal (A) is maximized is detected for (b1) to (a2). The laminated body in any one of Claims 1-8 in which the plasticizer contained in A layer contains 80-100 mass% of triethylene glycol di 2-ethylhexanoate. The laminated body in any one of Claims 1-9 in which the plasticizer contained in B layer contains 80-100 mass% of triethylene glycol di 2-ethylhexanoate. A layer contains the door triethylene glycol mono-2-ethylhexanoate er preparative A laminate according to any one of claims 1 to 10. The layered product according to any one of claims 1 to 11, wherein the B layer contains 0.1 to 3 parts by mass of triethylene glycol mono-2-ethylhexanoate with respect to 100 parts by mass of the polyvinyl acetal (B). Laminated glass obtained by laminating the laminate according to any one of claims 1 to 12 between two glasses. The laminated glass of Claim 13 whose edge part is not sealed. The laminated glass according to claim 13, wherein one of the two glasses is inorganic glass and one is organic glass. The laminated glass according to any one of claims 13 to 15, wherein the haze after use for 30 days in an atmosphere having a daily maximum temperature and a minimum temperature of 15 to 25 ° C is 1% or less. A molded article containing 30 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 27 to 40 mol%, and a polyvinyl acetal having an average residual hydroxyl group content of 15 to 24 mol% ( B) A sheet obtained by melt-kneading a molded product containing 50 to 70 parts by mass of a plasticizer with respect to 100 parts by mass, and forming the obtained kneaded product into a film, and the following formula (I):

[In the formula, (a2) is the time (min) at the end of detection of the peak of polyvinyl acetal (A) in high performance liquid chromatography analysis using an ODS column having an inner diameter of 4 mm and a length of 1 cm, and (b1) is polyvinyl acetal (B ) Represents the time (minutes) at the start of peak detection. ]
Meet the sheet. A layer containing 30 to 50 parts by mass of a plasticizer with respect to 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 27 to 40 mol%, and a polyvinyl acetal (B ) A layer in a laminate comprising a B layer containing 50 to 70 parts by mass of a plasticizer with respect to 100 parts by mass is used as a molded product containing a polyvinyl acetal (A) and a plasticizer. The sheet according to claim 17, which is used as a molded product containing B) and a plasticizer.

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