WO2014188543A1 - Film intermédiaire multicouche - Google Patents

Film intermédiaire multicouche Download PDF

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Publication number
WO2014188543A1
WO2014188543A1 PCT/JP2013/064260 JP2013064260W WO2014188543A1 WO 2014188543 A1 WO2014188543 A1 WO 2014188543A1 JP 2013064260 W JP2013064260 W JP 2013064260W WO 2014188543 A1 WO2014188543 A1 WO 2014188543A1
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Prior art keywords
polyvinyl acetal
mass
parts
mol
layer
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PCT/JP2013/064260
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English (en)
Japanese (ja)
Inventor
芳聡 浅沼
中野　陽子
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株式会社クラレ
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Priority to PCT/JP2013/064260 priority Critical patent/WO2014188543A1/fr
Priority to JP2013525029A priority patent/JP5465812B1/ja
Publication of WO2014188543A1 publication Critical patent/WO2014188543A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/22—Layered products comprising a layer of synthetic resin characterised by the use of special additives using plasticisers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10605—Type of plasticiser
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/70—Scrap or recycled material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • B32B2307/102—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties

Definitions

  • 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.
  • adhesives and ceramics Widely used as binders, various inks, paints, etc. and interlayer films 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.
  • 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.
  • 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.
  • 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).
  • delamination of the interlayer film for laminated glass occurs, and the safety as laminated glass may be impaired or the appearance may be impaired.
  • the moisture content of the interlayer film for laminated glass tends to be high around the end portion, and such a problem occurs remarkably.
  • 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.
  • the above 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
  • (a2) is a 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 content of polyvinyl acetal (A) and the average residual hydroxyl group content of polyvinyl acetal (B) is preferably 7 to 13 mol%.
  • the peak area of the polyvinyl acetal (A) existing in the range of (b1) to (a2) is preferably 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 preferably 2 to 100% of the total peak area of the polyvinyl acetal (B).
  • At least one of the points at which the peak of the polyvinyl acetal (B) becomes maximum is detected at (b1) to (a2).
  • At least one of the points at which the peak of the polyvinyl acetal (A) becomes maximum is detected at (b1) to (a2).
  • the plasticizer contained in the A layer preferably contains 80 to 100% by mass of triethylene glycol di-2-ethylhexanoate.
  • the plasticizer contained in the B layer preferably contains 80 to 100% by mass of triethylene glycol di-2-ethylhexanoate.
  • the layer A preferably 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 (A).
  • the B layer preferably 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).
  • the above object is suitably achieved by providing a laminated glass obtained by laminating the laminated body between two glasses.
  • the end of the laminated glass is not sealed.
  • one is preferably inorganic glass and one is organic glass.
  • the haze of the laminated glass after use for 30 days in an atmosphere where the difference between the highest temperature and the lowest temperature is 15-25 ° C. is 1% or less.
  • 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 of A sheet obtained by melt-kneading a molded article 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 product into a film.
  • (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 preferable to use as a raw material for the molded product containing the polyvinyl acetal (A) and the plasticizer and the molded product containing the polyvinyl acetal (B) and the plasticizer.
  • the laminate 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.
  • the average residual hydroxyl group content of the polyvinyl acetal (A) is 27 to 40 mol%, preferably 27 to 35 mol%, and more preferably 27 to 33 mol%.
  • 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.
  • the average residual hydroxyl group content of the polyvinyl acetal (B) is 15 to 24 mol%, preferably 16 to 23 mol%, more preferably 17 to 22 mol%.
  • 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.
  • 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.
  • ((a2)-(a1)) is smaller than 1, the proportion of polyvinyl acetal having the same polarity contained in the A layer and the B layer decreases, and the interlayer adhesion between the A layer and the B layer is sufficient. Disappear.
  • peak 1 is a peak derived from polyvinyl acetal (A)
  • 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).
  • 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).
  • 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).
  • the detector include an evaporative light scattering detector “ELSD-LTII” (manufactured by Shimadzu Corporation), and an apparatus having the same function can be used.
  • 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.
  • the mobile phase A a mixed solvent having a volume ratio of ethanol / water of 4/1 is used, and as the mobile phase B, ethanol is used.
  • 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.
  • the peak area of the polyvinyl acetal (A) existing in the range of (b1) to (a2) is the polyvinyl acetal (A)
  • the proportion of the total peak area is preferably 2 to 100%, preferably 10 to 100%, more preferably 15 to 100%, and further preferably 22 to 100%. 50 to 100% is particularly preferable.
  • 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 This is the peak area of the polyvinyl acetal (A) in the range of (a1) to (a2).
  • 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 further preferably 25 to 100%.
  • the peak area of the polyvinyl acetal (B) existing in the range of (b1) to (a2) is the area indicated by the hatched portion in FIG.
  • the peak is at least maximized.
  • the peak is at least maximized.
  • 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 carried out for 30 to 300 minutes while keeping the temperature constant.
  • an aldehyde and an acid catalyst such as hydrochloric acid or nitric acid
  • reaction temperature at this time is defined as the precipitation reaction temperature.
  • 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).
  • 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 kinds of polyvinyl acetals having different average residual hydroxyl group amounts.
  • polyvinyl acetal having an average residual hydroxyl group content of 25 to 40 mol%, preferably 27 to 34 mol%, more preferably 28 to 33 mol%, and an average residual hydroxyl group content of 15 to 30 mol%, preferably 20 to 30 mol%, more preferably 25 to 30 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.
  • the polyvinyl acetal thus prepared 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, preferably 99/1 to 70. / 30 is more preferable, and 99/1 to 50/50 is further preferable.
  • 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.
  • a method for 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 degree of acetalization is precipitated, and 10% of the total aldehyde is precipitated.
  • the average residual hydroxyl group content satisfies a specific value, and the distribution of the residual hydroxyl group is broad, that is, the one containing polyvinyl acetal having a polarity close to that of the polyvinyl acetal (B).
  • a polyvinyl acetal as the polyvinyl acetal (A)
  • a laminate satisfying the requirements of the present invention can be obtained.
  • polyvinyl acetal (B) for example, a method of mixing two or more kinds of polyvinyl acetals having different average residual hydroxyl group amounts can be mentioned.
  • 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.
  • the polyvinyl acetal thus prepared can be used by mixing at an appropriate ratio so that the average residual hydroxyl group 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, preferably 70/30 to 1 / 99 is more preferable, and 50/50 to 1/99 is even more preferable.
  • 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.
  • the particle diameter of the obtained polyvinyl acetal is increased by a method such as a precipitation reaction temperature of 20 to 30 ° C. or a driving reaction temperature of 75 to 80 ° C.
  • the method for carrying out the acetalization reaction under various conditions, or 30 to 90% of the total aldehyde used for the reaction is added before the polyvinyl acetal having reached a certain level of acetalization, and after the precipitation all the aldehyde
  • the average residual hydroxyl group content satisfies a specific value and the distribution of the residual hydroxyl group content is wide, that is, contains a polyvinyl acetal having a polarity close to that of the polyvinyl acetal (A).
  • A polyvinyl acetal having a polarity close to that of the polyvinyl acetal
  • A polyvinyl acetal
  • the aldehyde used in the acetalization reaction of the present invention is not particularly limited, but acetalization with a conventionally known aldehyde having 1 to 8 carbon atoms is preferable, and aldehyde having 4 to 6 carbon atoms is preferable, and n-butyraldehyde is particularly preferable. Is preferably used.
  • polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.
  • the difference between the average residual hydroxyl group amount of the polyvinyl acetal (A) used in the present invention and the average residual hydroxyl group amount of the polyvinyl acetal (B) is not particularly limited, but is 7 to 13 mol 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%.
  • plasticizer contained in the A layer and the B layer of the laminate of the present invention will be described.
  • 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).
  • 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 80-100% 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 on polyvinyl acetal.
  • the mechanical strength of a 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 on 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
  • the content of the plasticizer in the layer A is preferably 30 to 50 parts by mass, more preferably 31 to 47 parts by mass, and more preferably 32 to 45 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A). 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.
  • the content of the plasticizer in the B layer is preferably 50 to 70 parts by mass, more preferably 51 to 68 parts by mass, and more preferably 52 to 66 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B). 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.
  • polyalkylene glycol monocarboxylic acid such as triethylene glycol mono-2-ethylhexanoate, oligoethylene glycol mono2-ethylhexanoate, 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.
  • 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.
  • the polyalkylene glycol monocarboxylic acid ester has a structure similar to that of triethylene glycol di-2-ethylhexanoate.
  • it contains ethylene glycol mono 2-ethylhexanoate.
  • 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.
  • 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.
  • the polyalkylene glycol monocarboxylic acid ester has a structure similar to that of triethylene glycol di-2-ethylhexanoate.
  • it 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.
  • 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.
  • 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.
  • the polyalkylene glycol monocarboxylic acid ester has an effect as a compatibilizing agent for compatibilizing polyvinyl acetals having different residual hydroxyl groups. 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 unless they are contrary to the gist of the present invention.
  • the kind thereof is not particularly limited, and examples thereof include conventionally known phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. .
  • 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.
  • the addition amount of the antioxidant is not particularly limited, but is 0.0001 to 5% by mass, preferably 0.001 to 1% by mass with respect to the mass of the A layer or the B layer. 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.
  • the kind thereof is not particularly limited.
  • 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.
  • the addition amount of the ultraviolet absorber is not particularly limited, but is 0.0001 to 5% by mass, preferably 0.001 to 1% by mass with respect to the mass of the A layer or the B layer. 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.
  • the laminated body of this invention 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.
  • the adhesion adjusting agent conventionally known ones can be used. For example, sodium salt of organic acid such as acetic acid, propionic acid, butanoic acid, hexanoic acid, 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 adhesiveness adjusting agent is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 0.1% by mass, more preferably 0.001 to the mass of each of the A layer and the B layer. More preferably, it is 0.03 mass%.
  • 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
  • the thicknesses of the A layer and B layer in the laminate of the present invention are not particularly limited, but the thickness of the A layer is preferably 0.05 to 0.8 mm, and preferably 0.15 to 0.6 mm. More preferably, it is 0.2 to 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.
  • the laminate of the present invention can be used as a 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.
  • the thickness of the glass used in the laminated glass of the present invention is not limited, and a glass having a conventionally known thickness such as 0.5 mm to 20 mm can be used.
  • the laminate of the present invention is excellent in interlaminar adhesion between the A layer and the B layer, and therefore, it is preferable that delamination does not occur even when 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.
  • an interlayer film for laminated glass is often used with its moisture content adjusted to about 0.5% by mass.
  • the moisture content of the edge is not treated with a water-resistant sealant. May be higher than 1.0%.
  • 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.
  • 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.
  • 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.
  • 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. .
  • a method of putting the obtained temporary pressure bonded body into the autoclave can be additionally performed.
  • 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.
  • 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. .
  • 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 to 3 hours.
  • the laminated glass containing 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.
  • 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.
  • PVB-2 Polyvinyl butyral (PVB-2) was obtained in the same manner except that the amount of butyraldehyde used was changed to 395 g in the preparation of PVB-1. The precipitation of polyvinyl acetal occurred after the addition of butyraldehyde was completed.
  • the properties 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.
  • PVB-4 polyvinyl butyral
  • PVB-7 polyvinyl butyral
  • 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.
  • PVB-10 polyvinyl acetal
  • 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 ⁇ L, and the flow rate of the mobile phase was 0.4 mL / min.
  • 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.
  • Example 1 100 parts by weight of PVB-1, 39 parts by weight of 3GO (triethylene glycol di-2-ethylhexanoate), 0.3 parts by weight of triethylene glycol mono-2-ethylhexanoate (hereinafter referred to as carboxylic acid ester-1) was melt-kneaded in a lab plast mill at 150 ° C. for 3 minutes, and then 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 were melt-kneaded in a lab plast mill at 150 ° C. for 3 minutes, 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 adhered by hot pressing to obtain a laminate-1.
  • 3GO triethylene glycol di-2-
  • 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 processed with an autoclave at 140 ° C, 1.2 MPa for 60 minutes and combined. Glass was used. When the Pummel test of the obtained laminated glass was implemented, the Pummel value was 9.
  • Laminate-1 was sandwiched between float glass with a thickness of 3 mm, temporarily bonded with a nip roll, and then treated with an autoclave at 140 ° C. and 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).
  • EMIC small vibration generator 512-A
  • 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.
  • Laminate-1 was cut to a size of 30 cm ⁇ 30 cm, sandwiched between two pieces of 30 cm ⁇ 30 cm ⁇ 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 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.
  • Laminate-1 was cut to a size of 30 cm ⁇ 30 cm, sandwiched between two pieces of 30 cm ⁇ 30 cm ⁇ 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) In addition, 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.
  • Laminate-1 was melt-kneaded at 60 ° C. and 150 ° C. for 5 minutes using a Laboplast mill, and the resulting kneaded material was formed into a film by a press film formation method. 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 (Example 2) to (Example 21) and (Comparative Example 1) to (Comparative Example 6)
  • Laminate-2 to Laminate-21, and Comparative Example Laminate-1 to Comparative Example Laminate-6 were prepared, and the same method as in 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 with respect 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.
  • the laminate of the present invention 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un stratifié qui présente d'excellentes propriétés d'isolation phonique, une excellente résistance mécanique et une excellente adhésion avec le verre lorsqu'il est utilisé en tant que film intermédiaire pour du verre feuilleté, et qui est peu susceptible de produire un détachement de couche intermédiaire même lorsqu'il est utilisé à long terme dans un environnement présentant une importante différence de température diurne entre le chaud et le froid et une température d'air froid qui est très basse. Le stratifié comprend : une couche A contenant 30 à 50 parties en masse d'un plastifiant par rapport à 100 parties en masse d'un acétal polyvinylique (A) possédant une quantité moyenne de groupes hydroxyle résiduels dans la plage de 27 à 40 % molaires ; et une couche B contenant 50 à 70 parties en masse d'un plastifiant par rapport à 100 parties en masse d'un acétal polyvinylique (B) possédant une quantité moyenne de groupes hydroxyle résiduels dans la plage de 15 à 24 % molaires. De plus, lorsque l'on analyse l'acétal polyvinylique (A) dans une colonne ODS possédant une longueur de 1 cm et un diamètre interne de 4 mm, l'acétal polyvinylique (A) est détecté à un temps de dissolution de a1 à a2 minutes, et lorsque l'on analyse l'acétal polyvinylique (B) dans une colonne ODS possédant une longueur de 1 cm et un diamètre interne de 4 mm, l'acétal polyvinylique (B) est détecté à un temps de dissolution de b1 à b2 minutes. De plus, (a2-b1)≥1.
PCT/JP2013/064260 2013-05-22 2013-05-22 Film intermédiaire multicouche WO2014188543A1 (fr)

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Cited By (3)

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US20160046783A1 (en) * 2013-03-22 2016-02-18 Kuraray Co., Ltd. Composition having excellent transparency
US20160053102A1 (en) * 2013-03-22 2016-02-25 Kuraray Co., Ltd. Polyvinyl acetal composition
EP3460000A4 (fr) * 2016-05-18 2020-02-26 Kuraray Co., Ltd. Composition de résine, film et couche intermédiaire pour verre feuilleté

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JP6033754B2 (ja) * 2013-10-21 2016-11-30 株式会社クラレ 多層中間膜
JP6113640B2 (ja) * 2013-12-17 2017-04-12 株式会社クラレ 積層体
KR102314702B1 (ko) * 2014-09-12 2021-10-20 세키스이가가쿠 고교가부시키가이샤 합판유리용 중간막 및 합판유리

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WO2011078314A1 (fr) * 2009-12-25 2011-06-30 積水化学工業株式会社 Film intermédiaire pour verre laminé, et verre laminé
JP2013006727A (ja) * 2011-06-23 2013-01-10 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
JP2013006726A (ja) * 2011-06-23 2013-01-10 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス

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JPH11323055A (ja) * 1998-05-18 1999-11-26 Sekisui Chem Co Ltd 可塑剤
JPH11323056A (ja) * 1998-05-18 1999-11-26 Sekisui Chem Co Ltd 合わせガラス用中間膜および合わせガラス

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WO2011078314A1 (fr) * 2009-12-25 2011-06-30 積水化学工業株式会社 Film intermédiaire pour verre laminé, et verre laminé
JP2013006727A (ja) * 2011-06-23 2013-01-10 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス
JP2013006726A (ja) * 2011-06-23 2013-01-10 Sekisui Chem Co Ltd 合わせガラス用中間膜及び合わせガラス

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160046783A1 (en) * 2013-03-22 2016-02-18 Kuraray Co., Ltd. Composition having excellent transparency
US20160053102A1 (en) * 2013-03-22 2016-02-25 Kuraray Co., Ltd. Polyvinyl acetal composition
US10323143B2 (en) * 2013-03-22 2019-06-18 Kuraray Co., Ltd. Polyvinyl acetal composition
EP3460000A4 (fr) * 2016-05-18 2020-02-26 Kuraray Co., Ltd. Composition de résine, film et couche intermédiaire pour verre feuilleté

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