WO2014188545A1 - 積層体 - Google Patents
積層体 Download PDFInfo
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- WO2014188545A1 WO2014188545A1 PCT/JP2013/064262 JP2013064262W WO2014188545A1 WO 2014188545 A1 WO2014188545 A1 WO 2014188545A1 JP 2013064262 W JP2013064262 W JP 2013064262W WO 2014188545 A1 WO2014188545 A1 WO 2014188545A1
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- WIPO (PCT)
- Prior art keywords
- plasticizer
- laminate
- layer
- content
- polyvinyl acetal
- Prior art date
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Classifications
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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
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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
- 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
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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
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
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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
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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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
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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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
- B32B27/30—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
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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
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
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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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
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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
- B32B2250/00—Layers arrangement
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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
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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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
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/10—Properties of the layers or laminate having particular acoustical properties
- B32B2307/102—Insulating
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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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
- B32B2551/00—Optical elements
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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
- B32B2605/00—Vehicles
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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
- B32B2605/00—Vehicles
- B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
Definitions
- the present invention relates to a laminate containing polyvinyl acetal.
- a sheet containing polyvinyl acetal and a plasticizer is widely used as an interlayer film for laminated glass because of its excellent adhesion and transparency to glass, mechanical strength and flexibility.
- the plasticizer may bleed out, and when stored in a warehouse, etc., when the outside air temperature increases to 25 ° C to 40 ° C, such as in summer. Under such a high temperature, the intermediate film is likely to be deformed or the interlayer films are likely to be blocked. Usually, it is stored in a warehouse, etc., adjusted to low temperature and low humidity so that plasticizer bleed, deformation and blocking do not occur by air conditioning equipment.
- the inside of the warehouse becomes hot and humid due to, for example, a failure of the air conditioning equipment, and the moisture content of the interlayer film for laminated glass may be extremely high. If the interlayer film for laminated glass having a high water content is left as it is, water and plasticizer may be phase-separated in the interlayer film, or the plasticizer may bleed on the surface of the interlayer film. The transparency and mechanical properties of the interlayer film may deteriorate.
- an interlayer film for multilayer laminated glass has been studied as an interlayer film for laminated glass having sound insulation properties.
- the interlayer film for sound insulating laminated glass includes a layer having a low plasticizer content for the purpose of expressing mechanical strength or exhibiting adhesiveness to glass, and a layer having a high plasticizer content for expressing sound insulating properties.
- an interlayer film for sound-insulating multilayer laminated glass is used (see Patent Documents 1 and 2).
- the interlayer film for multilayer laminated glass When the interlayer film for multilayer laminated glass is also stored for a long time in a state of high moisture content, the moisture content becomes remarkably high, and water and plasticizer are phase-separated in the interlayer film, and the plasticizer bleeds on the surface of the interlayer film. Therefore, it is necessary to dry the interlayer film for multilayer laminated glass having a high moisture content in a low temperature and low humidity atmosphere.
- an interlayer film for multilayer laminated glass having a high water content is rapidly dried in an atmosphere of low temperature and low humidity, the interlayer film becomes opaque due to phase separation of water and plasticizer from polyvinyl acetal in the interlayer film.
- water or a plasticizer may bleed between the interlayers of the intermediate film to cause delamination or decrease in transparency.
- the interlayer film for laminated glass generally contains a plasticizer, and the plasticizer is extracted by water adhering to the exposed portion of the interlayer film at the end of the laminated glass. May peel off or air bubbles may be generated to impair the appearance of the laminated glass.
- the plasticizer may volatilize from the edge of the laminated glass when a laminated glass is produced through a decompression step or when used for a long time.
- the present invention solves the above problems, and the plasticizer contained in the laminate is difficult to be extracted and volatilized by water, and a laminate having a high moisture content can be rapidly dried in an atmosphere of low temperature and low humidity. It is an object of the present invention to provide a laminate in which water and plasticizer are less likely to phase separate from polyvinyl acetal in the laminate and water or plasticizer is less likely to bleed between layers.
- the above object includes a layer containing polyvinyl acetal (A), a plasticizer (Ap) and a dispersant (Ad), a polyvinyl acetal (B) and a plasticizer (Bp).
- B layer which may contain (Bd), the mass ratio of the content of the dispersant (Ad) to the content of the plasticizer (Ap) in the A layer is the ratio of the plasticizer (Bp) in the B layer.
- a monovalent carboxylic acid having a mass ratio of the content of the dispersant (Bd) to the content and a plasticizer (Ap) of 1 molecule of m-valent alcohol (m represents a natural number of 2 to 4) and 8 to 16 carbon atoms.
- an ester compound having a chemical structure obtained by an esterification reaction with an m molecule wherein the dispersant (Ad) has a chemical structure obtained by hydrolyzing at least one ester bond of the plasticizer (Ap); m-1) to 1 hydroxyl group and 1 to (m-1)
- An ester compound having a chemical structure wherein the dispersant (Bd) has a chemical structure obtained by hydrolyzing at least one ester bond of the plasticizer (Bp) and has (n-1) to one hydroxyl group And a laminate having 1 to (n-1) ester bonds.
- the m-valent alcohol is preferably a condensate of ethylene glycol having a condensation degree of 3 to 20.
- the n-valent alcohol is preferably a condensate of ethylene glycol having a condensation degree of 3 to 20.
- the average residual hydroxyl group content of polyvinyl acetal (A) is preferably 20 to 40 mol%.
- the average residual hydroxyl group content of polyvinyl acetal (B) is preferably 10 to 35 mol%, and the average residual vinyl ester group amount is preferably 0.01 to 25 mol%.
- the content of the plasticizer (Ap) with respect to 100 parts by mass of the polyvinyl acetal (A) in the A layer is less than the content of the plasticizer (Bp) with respect to 100 parts by mass of the polyvinyl acetal (B) in the B layer.
- the content of the plasticizer (Ap) in the A layer is preferably 20 to 60 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A).
- the content of the plasticizer (Bp) in the B layer is preferably 30 to 80 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B).
- the monovalent carboxylic acid it is preferable that at least two organic groups other than a carbonyl group are bonded to carbon adjacent to the carboxyl group.
- It is a laminate composed of three or more layers, and at least one of the two outer layers of the laminate is preferably an A layer.
- the above object is suitably achieved by providing a laminated glass including the laminate.
- the plasticizer contained in the laminate is difficult to be extracted and volatilized by water, and even if the laminate having a high moisture content is rapidly dried in a low-temperature and low-temperature atmosphere, It is possible to provide a laminate in which the plasticizer is less likely to phase separate from the polyvinyl acetal and is less likely to bleed between water and the plasticizer.
- the average residual hydroxyl group amount of the polyvinyl acetal (A) used in the present invention is not particularly limited, but is usually preferably 20 to 40 mol%, more preferably 23 to 38 mol%, further preferably 25 to 36 mol%, more preferably 26 to 29 mol% is particularly preferred. If the average residual hydroxyl group content is less than 20 mol%, the mechanical strength of the resulting laminate and the adhesion to glass may be reduced, and if it exceeds 40 mol%, it is compatible with the plasticizer (Ap). May be significantly reduced.
- the average degree of acetalization of the polyvinyl acetal (A) is not limited, but is usually preferably 50 to 78 mol%, more preferably 60 to 74 mol%, and further preferably 65 to 73 mol%. If the average degree of acetalization is less than 50 mol%, the compatibility with the plasticizer (Ap) may be significantly reduced, and if it exceeds 78 mol%, the mechanical strength of the resulting laminate may be reduced. is there.
- the average residual vinyl ester group amount of the polyvinyl acetal (A) is not particularly limited, but is usually preferably 0.01 to 15 mol%, more preferably 0.01 to 10 mol%, still more preferably 0.01 to 5 mol%. .
- the average residual vinyl ester group amount is less than 0.01 mol%, it is difficult to produce industrially inexpensively.
- the average vinyl ester group amount exceeds 15 mol% when the resulting laminate is used for a long period of time, vinyl ester groups are not formed. The laminated body is likely to be colored due to hydrolysis.
- the average residual hydroxyl group amount of the polyvinyl acetal (B) used in the present invention is not particularly limited, but is usually preferably 10 to 35 mol%, more preferably 13 to 33 mol%, and further preferably 15 to 30 mol%. If the average residual hydroxyl group content is less than 10 mol%, the mechanical strength and the adhesion to glass may be significantly reduced, and if it exceeds 35 mol%, the compatibility with the plasticizer (Bp) may be reduced. .
- the average degree of acetalization of the polyvinyl acetal (B) is not limited, but is usually preferably 60 to 84 mol%, more preferably 65 to 82 mol%, and further preferably 70 to 80 mol%. If the average degree of acetalization is less than 60 mol%, the compatibility with the plasticizer (Bp) may be lowered, and if it exceeds 84 mol%, the mechanical strength of the resulting laminate may be lowered.
- the average residual vinyl ester group amount of the polyvinyl acetal (B) is not particularly limited, but is usually preferably 0.01 to 25 mol%, more preferably 3 to 16 mol%, still more preferably 3 to 15 mol%, and 4 to 13 Mole% is particularly preferred. Those having an average residual vinyl ester group amount of less than 0.01 mol% are difficult to produce industrially at low cost, and the compatibility with the plasticizer (Bp) may be lowered. On the other hand, when the content exceeds 25 mol%, the laminate is likely to be colored due to hydrolysis of the vinyl ester group when the resulting laminate is used for a long period of time.
- the average residual hydroxyl group content of the polyvinyl acetal (A) is preferably larger than the average residual hydroxyl group content of the polyvinyl acetal (B), more preferably 3 to 20 mol%, and particularly preferably 5 to 15 mol%.
- water and plasticizers are difficult to phase separate from polyvinyl acetal in the laminate even if the laminate having a high water content is rapidly dried in a low temperature and low temperature atmosphere. Further, it is preferable that bleeding between layers of water or a plasticizer does not easily occur, and it is preferable from the viewpoint of sound insulation performance when the laminate is used as an interlayer film for sound insulation laminated glass.
- the polyvinyl acetal (A) and the polyvinyl acetal (B) used in the present invention are produced using polyvinyl alcohol as a raw material.
- Polyvinyl alcohol can be obtained by a conventionally known method. That is, it can be obtained by polymerizing a vinyl ester compound and saponifying the obtained polymer.
- a method for polymerizing the vinyl ester compound conventionally known methods such as a solution polymerization method, a bulk polymerization method, a suspension polymerization method, and an emulsion polymerization method can be applied.
- As a polymerization initiator used in these polymerization methods an azo initiator, a peroxide initiator, a redox initiator, or the like can be used as appropriate.
- the saponification reaction is carried out by subjecting the vinyl ester group of the polymer to alcoholysis or hydrolysis using a conventionally known alkali catalyst or acid catalyst.
- a conventionally known alkali catalyst or acid catalyst e.g., methanol as a solvent and caustic soda (NaOH) as a catalyst is simple and most preferable.
- vinyl ester compound examples include conventionally known carboxylic acid vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, vinyl benzoate, and vinyl acetate is preferred.
- a modified polyvinyl alcohol obtained by saponifying a copolymer obtained by copolymerizing a vinyl ester compound and a monomer copolymerizable with the vinyl ester compound is used.
- the monomer copolymerizable with the vinyl ester compound is usually used in a proportion of less than 10 mol% with respect to the vinyl ester compound.
- the viscosity average degree of polymerization of polyvinyl alcohol used as a raw material for the polyvinyl acetal used in the present invention is not particularly limited and can be appropriately selected depending on the application, but is usually preferably 150 to 3000, more preferably 200 to 2500, and more preferably 1000 to 2000. Is more preferable.
- the viscosity average degree of polymerization of polyvinyl alcohol is lower than 150, the mechanical strength of the obtained laminate tends to be insufficient, and when it is higher than 3000, the handleability of the obtained laminate may be deteriorated.
- the polyvinyl acetal used in the present invention can be produced by a conventionally known method.
- it can be produced by a precipitation method under the following reaction conditions.
- an aqueous polyvinyl alcohol solution having a concentration of 3 to 40% by mass is maintained in a temperature range of 80 to 100 ° C. and then gradually cooled over 10 to 60 minutes.
- an aldehyde and an acid catalyst are added, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant.
- polyvinyl acetal having a certain degree of acetalization is deposited.
- the reaction solution is heated to a temperature of 30 to 80 ° C. over 30 to 300 minutes, and the temperature is maintained for 10 to 500 minutes.
- the acid catalyst is neutralized, washed with water, and dried to obtain polyvinyl acetal.
- the acid catalyst used in the acetalization reaction is not particularly limited, and any of organic acids such as acetic acid and paratoluenesulfonic acid or inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid can be used, and hydrochloric acid, sulfuric acid and nitric acid are particularly preferable. .
- the aldehyde used in the acetalization reaction is not particularly limited, but it is preferable to acetalize with an aldehyde having 1 to 8 carbon atoms. Of these, aldehydes having 4 to 6 carbon atoms are preferably used, and n-butyraldehyde is particularly preferably used. In the present invention, polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.
- the plasticizer (Ap) contained in layer A constituting the laminate of the present invention has a chemical structure obtained by an esterification reaction of one molecule of m-valent alcohol and one molecule of monovalent carboxylic acid having 8 to 16 carbon atoms. It is an ester compound.
- m represents a natural number of 2-4.
- the plasticizer (Ap) may have a chemical structure obtained by an esterification reaction between one molecule of m-valent alcohol and one molecule of monovalent carboxylic acid having 8 to 16 carbon atoms. Those obtained by a method other than the esterification reaction with m-monovalent carboxylic acid having 8 to 16 carbon atoms may be used.
- m-valent alcohols examples include ethylene glycol, ethylene glycol condensates, propylene glycol, propylene glycol condensates, dihydric alcohols such as 3-methyl-1,5-pentanediol and 1,4-cyclohexanedimethanol; glycerin And trihydric alcohols such as erythritol and pentaerythritol.
- the obtained plasticizer (Ap) is excellent in compatibility with the polyvinyl acetal (A) and plasticizing effect, has a high boiling point, and is bivalent from the viewpoint that even when the laminate is in contact with water, it is difficult to extract with water.
- Alcohols are preferable, ethylene glycol condensates such as triethylene glycol and tetraethylene glycol are more preferable, ethylene glycol having a condensation degree of 3 to 20 is more preferable, and ethylene glycol condensates having a condensation degree of 3 to 10 are preferable. Particularly preferred is a condensate of ethylene glycol having a degree of condensation of 3 or 4.
- Examples of the monovalent carboxylic acid having 8 to 16 carbon atoms include octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexadecanoic acid, 2-methylheptanoic acid, 2-ethylheptanoic acid, 2,2 -Dimethylhexanoic acid and the like.
- monovalent carboxylic acids having 8 to 12 carbon atoms, particularly 8 to 10 carbon atoms are excellent in compatibility with the plasticizer (Ap) of the resulting plasticizer (Ap) and plasticizing effect, and have a high boiling point.
- the monovalent carboxylic acid in which at least two organic groups other than the carboxyl group are bonded to the carbon adjacent to the carboxyl group is preferable from the viewpoint of enhancing the hydrolysis resistance of the plasticizer (Ap).
- monovalent carboxylic acids include 2-ethylhexanoic acid, 2-methylheptanoic acid, 2-ethylheptanoic acid, 2,2-dimethylhexanoic acid, and the like.
- ester compounds having a chemical structure obtained by esterification of one molecule of m-valent alcohol and one molecule of monovalent carboxylic acid having 8 to 16 carbon atoms include triethylene glycol di-2-ethylhexanoate and tetraethylene glycol. Di-2-ethylhexanoate, triethylene glycol dinonanoate, triethylene glycol didecanoate, triethylene glycol didodecanoate, decaethylene glycol di-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, etc. Is mentioned.
- triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, triethylene glycol dinonanoate, and glycerin tri-2-ethylhexanoate are compatible with polyvinyl acetal (A). And it is excellent from the viewpoint that it is excellent in plasticizing effect, has a high boiling point, and is difficult to be extracted with water even when the laminate is in contact with water. These may be used alone or in combination of two or more.
- the content of the plasticizer (Ap) in the layer A constituting the laminate of the present invention is not particularly limited, but is preferably 20 to 60 parts by weight, and preferably 25 to 55 parts by weight with respect to 100 parts by weight of the polyvinyl acetal (A). Is more preferable, and 30 to 50 parts by mass is even more preferable.
- the content of the plasticizer (Ap) is less than 20 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A)
- the resulting laminate tends to have insufficient flexibility and impact as an interlayer film for laminated glass. Absorption may be a problem.
- the amount is more than 60 parts by mass, the mechanical strength of the obtained laminate tends to be insufficient.
- the plasticizer (Bp) contained in the B layer constituting the laminate of the present invention has a chemical structure obtained by an esterification reaction of one molecule of n-valent alcohol and n molecule of monovalent carboxylic acid having 8 to 16 carbon atoms. It is an ester compound.
- n represents a natural number of 2-4.
- the plasticizer (Bp) only needs to have a chemical structure obtained by esterification reaction between one molecule of n-valent alcohol and one molecule of monovalent carboxylic acid having 8 to 16 carbon atoms. Those obtained by a method other than the esterification reaction with n-monovalent monocarboxylic acid having 8 to 16 carbon atoms may be used.
- n-valent alcohol examples include the same compounds as those exemplified as the m-valent alcohol, and preferred compounds are also the same.
- ester compounds having a chemical structure obtained by esterification of one molecule of an n-valent alcohol and one molecule of a monovalent carboxylic acid having 8 to 16 carbon atoms include triethylene glycol di-2-ethylhexanoate and tetraethylene glycol. Di-2-ethylhexanoate, triethylene glycol dinonanoate, triethylene glycol didecanoate, triethylene glycol didodecanoate, decaethylene glycol di-2-ethylhexanoate, glycerin tri-2-ethylhexanoate, etc. Is mentioned.
- triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, triethylene glycol dinonanoate, and glycerin tri-2-ethylhexanoate are compatible with polyvinyl acetal (B). And it is excellent from the viewpoint that it is excellent in plasticizing effect, has a high boiling point, and is difficult to be extracted with water even when the laminate is in contact with water. These may be used alone or in combination of two or more.
- the content of the plasticizer (Bp) in the B layer constituting the laminate of the present invention is not particularly limited, but is usually preferably 30 to 80 parts by mass, and 33 to 75 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B). Is more preferable, and 40 to 70 parts by mass is even more preferable.
- the content of the plasticizer (Bp) is less than 30 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B)
- a desired sound insulation is exhibited when the obtained laminate is used for an interlayer film for sound insulation laminated glass. There are cases where it is not possible.
- the amount is more than 80 parts by mass, the resulting laminated body tends to have insufficient mechanical strength.
- the relationship between the content of the plasticizer (Ap) in the A layer and the content of the plasticizer (Bp) in the B layer is not strictly limited, but the polyvinyl acetal (A) 100 in the A layer is not limited. It is preferable that content of the plasticizer (Ap) with respect to a mass part is less than content of the plasticizer (Bp) with respect to 100 mass parts of polyvinyl acetal (B) in B layer.
- the plasticizer (Ap) content relative to 100 parts by mass of the polyvinyl acetal (A) is a plasticizer relative to 100 parts by mass of the polyvinyl acetal (B) (
- the content of Bp) is preferably 5 to 60 parts by mass, and more preferably 10 to 40 parts by mass.
- the dispersant (Ad) has a chemical structure obtained by hydrolyzing at least one ester bond of the plasticizer (Ap), and has (m ⁇ 1) to 1 hydroxyl group and 1 to (m ⁇ 1) units. It is a compound having an ester bond.
- the dispersant (Ad) may have a chemical structure obtained by hydrolyzing at least one ester bond of the plasticizer (Ap), and may be obtained by a method other than hydrolyzing the plasticizer (Ap). You may use what was made.
- dispersant (Ad) examples include triethylene glycol mono-2-ethylhexanoate (chemical structure obtained by hydrolyzing one ester bond of triethylene glycol di-2-ethylhexanoate), tetraethylene glycol mono-2-ethyl, and the like.
- Hexanoate (chemical structure that hydrolyzed one ester bond of tetraethylene glycol di-2-ethylhexanoate), triethylene glycol monodecanoate (hydrolyzed one ester bond of triethylene glycol didecanoate) Chemical structure), triethylene glycol monododecanoate (chemical structure obtained by hydrolyzing one ester bond of tetraethylene glycol didodecanoate), decaethylene glycol mono-2-ethylhexanoate (decaethylene glycol di-2-ethylhexanoate) Chemical structure hydrolyzed one ester bond of noate), triethylene glycol monononanoate (chemical structure hydrolyzed one ester bond of triethylene glycol dinonanoate), glycerin di-2-ethylhexanoate (glycerin) Chemical structure obtained by hydrolyzing one ester bond of tri-2-ethylhexanoate), glycerin mono 2-ethylhexano
- triethylene glycol mono-2-ethylhexanoate, tetraethylene glycol mono-2-ethylhexanoate, and triethylene glycol monononanoate are liquid at room temperature and excellent in handleability, and polyvinyl acetal (A) and plasticizer It is suitable because it is particularly excellent in compatibility with (Ap).
- the content of the dispersant (Ad) in the layer A constituting the laminate of the present invention is not particularly limited, but is usually preferably 0.01 to 6 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A), and 0.06 Is more preferably 4 parts by mass, and further preferably 0.09 to 2.4 parts by mass.
- the content of the dispersant (Ad) is less than 0.01 parts by mass, when a laminate having a high water content is rapidly dried in an atmosphere of low temperature and low humidity, water or a plasticizer is contained in the polyvinyl acetal. Phase separation may cause the laminate to become opaque, or water or a plasticizer may bleed between the layers of the laminate to cause delamination or a decrease in transparency.
- the dispersant (Bd) has a chemical structure obtained by hydrolyzing at least one ester bond of the plasticizer (Bp), and has (n-1) to 1 hydroxyl group and 1 to (n-1) units. It is a compound having an ester bond.
- the dispersant (Bd) may have a chemical structure obtained by hydrolyzing at least one ester bond of the plasticizer (Bp), and may be obtained by a method other than hydrolyzing the plasticizer (Bp). You may use what was made.
- dispersant (Bd) examples include triethylene glycol mono-2-ethylhexanoate, tetraethylene glycol mono-2-ethylhexanoate, triethylene glycol monodecanoate, triethylene glycol monododecanoate, and decaethylene glycol.
- examples thereof include mono-2-ethylhexanoate, triethylene glycol monononanoate, glycerin di-2-ethylhexanoate, and glycerin mono-2-ethylhexanoate.
- triethylene glycol mono-2-ethylhexanoate, tetraethylene glycol mono-2-ethylhexanoate, and triethylene glycol monononanoate are particularly liquid and easy to handle at room temperature, and polyvinyl acetal (B) and plastic This is preferred because it is particularly excellent in compatibility with the agent (Bp).
- the content of the dispersant (B) in the B layer constituting the laminate of the present invention is not particularly limited, but is usually preferably 0 to 4 parts by mass, and preferably 0.01 to 3 parts per 100 parts by mass of the polyvinyl acetal (B). Part by mass is more preferable, and 0.03 to 2.2 parts by mass is even more preferable.
- that content of a dispersing agent (Bd) is 0 mass part means that a dispersing agent (Bd) is not included in B layer.
- the content of the dispersing agent (Bd) exceeds 4 parts by mass, the dispersing agent (Bd) volatilizes or when the B layer comes into contact with water, the dispersing agent (Bd) is extracted with water. Physical properties may change.
- the mass ratio of the content of the dispersant (Ad) to the content of the plasticizer (Ap) in the A layer (hereinafter referred to as mass ratio A) is the content of the plasticizer (Bp) in the B layer. It is necessary to be larger than the mass ratio of the content of the dispersant (Bd) to the amount (hereinafter referred to as mass ratio B).
- mass ratio B is 0, or the mass ratio A is 1.05 times or more of the mass ratio B. More preferably, the mass ratio A is 1.1 times or more of the mass ratio B, more preferably 1.25 times or more, and particularly preferably 1.5 times or more.
- the plasticizer (Ap) and the plasticizer (Bp) may be the same or different, but are preferably the same from the viewpoint of reducing costs in the production of the A layer and the B layer.
- the laminate of the present invention may further contain an antioxidant, an ultraviolet absorber, an adhesion improver, and other additives.
- the type of antioxidant that the laminate of the present invention may contain.
- conventionally known phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like can be used. Of these, phenolic antioxidants are preferred.
- Antioxidants may be used alone or in combination of two or more.
- the amount thereof is not particularly limited, but is usually preferably 0.0001 to 5% by mass and more preferably 0.001 to 1% by mass with respect to the mass of the laminate. When the amount is less than 0.0001% by mass, a sufficient effect as an antioxidant may not be obtained, and when the amount is more than 5% by mass, a remarkable effect cannot be expected.
- the type of ultraviolet absorber that the laminate of the present invention may contain there is no particular limitation on the type of ultraviolet absorber that the laminate of the present invention may contain.
- conventionally known benzotriazole ultraviolet absorbers, oxalic anilide ultraviolet absorbers, benzoate ultraviolet absorbers, and the like can be used.
- the ultraviolet absorbers may be used alone or in combination of two or more.
- the amount is not particularly limited, but is usually preferably 0.0001 to 5% by mass, and more preferably 0.001 to 1% by mass with respect to the mass of the laminate. When the amount is less than 0.0001% by mass, a sufficient effect as an ultraviolet absorber may not be obtained, and when the amount is more than 5% by mass, a remarkable effect cannot be expected.
- the laminate of the present invention is particularly preferably used as an interlayer film for laminated glass.
- an adhesion adjusting agent is added to the layer that adheres to the glass.
- the adhesion adjusting agent include sodium salt, potassium salt, magnesium salt and the like of organic acids such as acetic acid, propionic acid, butanoic acid, hexanoic acid, 2-ethylbutanoic acid and 2-ethylhexanoic acid. More than one kind may be added.
- a magnesium salt such as magnesium acetate, magnesium acetate tetrahydrate, magnesium butanoate, magnesium 2-ethylbutanoate, magnesium 2-ethylhexanoate is added to the A layer. It is preferable.
- the addition amount of the adhesion modifier is 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A) from the viewpoints of penetration resistance of the laminated glass and prevention of glass fragment scattering when the laminated glass is broken. Is preferably 0.005 to 0.08 parts by mass, more preferably 0.01 to 0.06 parts by mass, and particularly preferably 0.03 to 0.055 parts by mass.
- Magnesium salt absorbs less water than potassium salt and sodium salt, so when magnesium salt is added to layer A as an adhesive strength modifier, a laminate with a high moisture content is rapidly applied in a low temperature and low humidity atmosphere. Even when dried, water and plasticizer are difficult to phase separate from polyvinyl acetal in the laminate, and water and plasticizer are difficult to bleed between layers of the laminate.
- the method for producing the laminate of the present invention is not particularly limited, and conventionally known methods can be applied.
- the components constituting the A layer and the components constituting the B layer are melt-kneaded with an extruder and then co-extruded with a multilayer film forming machine; the A layer individually prepared by hot pressing or casting after the melt-kneading And a method of laminating and laminating the B layers and adhering them by hot pressing or the like, if necessary.
- the moisture content of the laminate of the present invention is not particularly limited. However, if the moisture content is too high, the plasticizer may bleed from the laminate, so 0.01 to 0.9% by mass is usually preferable. Is more preferably 0.8 to 0.8% by mass, and further preferably 0.2 to 0.7% by mass.
- the thickness of the A layer and the B layer in the laminate of the present invention is not particularly limited.
- the thickness of the A layer is usually preferably 0.05 to 1.2 mm, more preferably 0.07 to 1 mm, and further preferably 0.1 to 0.7 mm. If it is thinner than 0.05 mm, the mechanical strength of the laminate of the present invention tends to decrease, and if it is thicker than 1.2 mm, the flexibility of the laminate of the present invention tends to be insufficient, as an interlayer film for laminated glass. In use, the safety of the resulting laminated glass may be reduced.
- the thickness of the B layer is usually preferably 0.01 to 1 mm, more preferably 0.02 to 0.8 mm, and further preferably 0.05 to 0.5 mm. If it is thinner than 0.01 mm, the sound insulation performance of the laminated glass having the laminate of the present invention as an intermediate film may be deteriorated, and even if it is thicker than 1 mm, the mechanical strength of the laminate of the present invention does not tend to improve any more. It is in.
- the ratio of the thickness of the A layer to the thickness of the B layer is not particularly limited, but is preferably 0.05 to 4, more preferably 0.07 to 2, more preferably 0.1 to 2, from the viewpoint of the mechanical strength and the sound insulation. 0.8 is more preferable.
- the laminate of the present invention it is preferable that at least one of the outermost layers of the laminate is an A layer.
- Examples of such laminates are A layer / B layer / A layer, A layer / B layer / A layer / B layer / A layer and the like.
- Examples include a laminate in which one layer such as A layer / B layer / A layer / B layer is an A layer.
- both outermost layers are A layers because the adhesiveness between the laminate and the glass can be adjusted appropriately.
- the thickness of the laminate is not particularly limited, but is usually preferably 0.2 to 2 mm, more preferably 0.25 to 1.8 mm, and More preferably, the thickness is 3 to 1.5 mm.
- the thickness of the laminate is thinner than 0.2 mm, the mechanical strength tends to be insufficient, and when it is thicker than 2 mm, the flexibility tends to be insufficient.
- the glass material when using the laminate of the present invention as an interlayer film for laminated glass is not particularly limited, inorganic glass such as float plate glass, heat tempered glass, chemically tempered glass; organic glass such as polymethyl methacrylate, polycarbonate, etc. Conventionally known glass can be used. These may be colorless or colored, transparent or non-transparent, and two or more of them may be used in combination. Although there is no limitation in particular in the thickness of glass, Usually, 20 mm or less is preferable and 10 mm or less is more preferable.
- the shape of the outermost surface of the laminated body is not particularly limited, but considering the handleability when producing a laminated glass (for example, bubble removal in the laminate), 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 method of producing laminated glass using the laminate of the present invention as an interlayer film for laminated glass is not particularly limited.
- a method of undergoing a decompression step using a vacuum laminator device or a vacuum bag Conventionally known methods such as a processing method can be mentioned.
- An example of manufacturing conditions when using a vacuum laminator apparatus is as follows: glass at a temperature of 100 to 200 ° C., preferably 130 to 160 ° C. under a reduced pressure of 1 ⁇ 10 ⁇ 6 to 3 ⁇ 10 ⁇ 2 MPa. An interlayer film for laminated glass is laminated.
- a method using a vacuum bag is described, for example, in EP 1356683. For example, lamination is performed at 130 to 145 ° C. under a pressure of about 2 ⁇ 10 ⁇ 2 MPa.
- an example of the operating condition of the nip roll is to heat the glass and the laminate to 30 to 70 ° C. with an infrared heater, etc., then degas by sandwiching with a roll, and further to 50 to After heating to 120 ° C., the film is temporarily bonded by pressing with a roll.
- the step of treating with an autoclave is performed at a temperature of 130 to 145 ° C. for 30 minutes to 200 minutes, for example, under a pressure of 1.0 to 1.5 MPa.
- PVB-1 polyvinyl butyral
- PVB-3 (Preparation of PVB-3)
- PVA-1 was changed to PVA-2 (viscosity average polymerization degree 1700, saponification degree 92 mol%) 200 g
- butyraldehyde used was changed to 120 g
- a butyralization reaction was carried out at 5 ° C.
- PVB-3 was obtained in the same manner except that the temperature was raised to 68 ° C. over 70 minutes and the reaction was carried out at 68 ° C. for 110 minutes.
- the obtained PVB-3 was measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 74 mol%, the average residual vinyl ester group amount was 7 mol%, and the average residual hydroxyl group amount was 19 mol%. there were.
- PVB-4 (Preparation of PVB-4)
- PVA-2 was changed to 200 g of PVA-3 (viscosity average polymerization degree 1700, saponification degree 89 mol%), but butyraldehyde was used in an amount of 117 g, and a butyralization reaction was carried out at 5 ° C.
- PVB-4 was obtained in the same manner except that the temperature was raised to 65 ° C. over 70 minutes and the reaction was carried out at 65 ° C. for 140 minutes.
- the obtained PVB-4 was measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 75 mol%, the average amount of residual vinyl ester groups was 9 mol%, and the average amount of residual hydroxyl groups was 16 mol%. there were.
- Example 1 (Production of laminate) 100 parts by weight of PVB-1, 39 parts by weight of triethylene glycol di-2-ethylhexanoate as plasticizer (Ap), 0.3 parts by weight of triethylene glycol mono-2-ethylhexanoate as dispersant (Ad) Eat and 0.048 parts by mass of magnesium acetate tetrahydrate were kneaded in a Laboplast mill at 160 ° C. for 8 minutes. The obtained kneaded material was pressed for 30 minutes in a mold having a thickness of 0.38 mm under the conditions of 160 ° C. and 50 kg / cm 2 to obtain a sheet A having a thickness of 0.38 mm.
- Sheet A and sheet B are stacked in the order of sheet A / sheet B / sheet A and pressed in a 0.9 mm thick formwork at 135 ° C. and 10 kg / cm 2 , and layer A (0.38 mm) / Laminated body-1 consisting of B layer (0.14 mm) / A layer (0.38 mm) was obtained.
- the laminate-1 obtained as described above was conditioned in an oven at 35 ° C. and 80% RH for 12 hours in a thermo-hygrostat.
- the humidity-controlled laminate-1 was further conditioned under the following conditions (a), (b), and (c), and was evaluated according to the following criteria to be "18 hours".
- Condition (a) Treated at 23 ° C. and 28% RH for 18 hours.
- Condition (b) treated at 29 ° C. and 55% RH for 18 hours, then treated at 23 ° C. and 28% RH for 18 hours.
- Laminated glass-1 was treated with hot water at 60 ° C. for 12 hours and then treated in an atmosphere of 23 ° C. and 28% RH for 108 hours (this treatment is defined as one cycle). After repeating this process 10 times, from each end of the laminated glass, visually check for defects (exfoliation of the glass and the interlayer film for laminated glass, peeling of the interlayer of the interlayer film) due to extraction of components contained in the laminate. According to the above, it was evaluated as “none” when evaluated in three stages of “none”, “somewhat present”, and “present”.
- Examples 2 to 31, Comparative Examples 1 to 13 A laminated body and a laminated glass were produced in the same manner as in Example 1 except that the compositions of the A layer and the B layer were changed as shown in Table 2 and Table 4, and were similarly evaluated. The results are shown in Table 3 and Table 5.
- the laminate of the present invention has a high water content at high temperature and high humidity, and then water in the laminate even when rapidly dried in an atmosphere of low temperature and low humidity.
- the plasticizer is difficult to phase separate from the polyvinyl acetal and does not cause water or plasticizer bleeding between the layers of the laminate.
- the mass ratio of the content of the dispersant (Ad) to the content of the plasticizer (Ap) in the A layer is the plasticizer (Bp) in the B layer.
- the moisture content of the laminate in which the outermost layers are both A layers is preferably high, it is caused by being larger than the mass ratio of the content of the dispersant (Bd) to the content of It is considered that the moisture content of the B layer also decreases before phase separation or bleed occurs as a result of moisture transferring from the B layer to the A layer as the water volatilizes.
- the laminated body of the present invention is such that the plasticizer contained in the laminated body is difficult to be extracted and volatilized by water, and even if the laminated body having a high water content is rapidly dried in an atmosphere of low temperature and low humidity, And the plasticizer is difficult to phase separate from the polyvinyl acetal, and bleeding between layers of water and the plasticizer is difficult to occur.
Landscapes
- Joining Of Glass To Other Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
還流冷却器、温度計、イカリ型攪拌翼を備えた3L(リットル)のガラス製容器に、イオン交換水2000g、ポリビニルアルコール(PVA-1)(粘度平均重合度1700、けん化度99モル%)200gを仕込み(PVA濃度9.1%)、内容物を95℃に昇温して完全に溶解させた。次に、120rpmで攪拌下、7℃まで約30分かけて徐々に冷却した後、ブチルアルデヒド113gと35%の塩酸70gを添加し、ブチラール化反応を30分間行った。その後、60分かけて60℃まで昇温し、60℃にて120分間保持した後、直ちに冷水浴で冷却した。ポリビニルアセタール樹脂をイオン交換水で洗浄した後、水酸化ナトリウム水溶液で残存する酸触媒を中和し、さらにイオン交換水で洗浄し、脱水し、乾燥してポリビニルブチラール(PVB-1)を得た。得られたPVB-1をJIS K6728にしたがって測定したところ、表1に示すとおり、平均アセタール化度は68モル%、平均残存ビニルエステル基量は1モル%、平均残存水酸基量は31モル%であった。
PVB-1の調製において、ブチルアルデヒド使用量を118gに変更した以外は同様にして反応を行い、PVB-2を得た。得られたPVB-2をJIS K6728にしたがって測定したところ、表1に示すとおり、平均アセタール化度は71モル%、平均残存ビニルエステル基量は1モル%、平均残存水酸基量は28モル%であった。
PVB-1の調製において、PVA-1をPVA-2(粘度平均重合度1700、けん化度92モル%)200gに、また、ブチルアルデヒド使用量を120gに変更し、さらに5℃でブチラール化反応を実施した後、68℃まで70分かけて昇温し、68℃で110分反応を行った以外は同様にして、PVB-3を得た。得られたPVB-3をJIS K6728にしたがって測定したところ、表1に示すとおり、平均アセタール化度は74モル%、平均残存ビニルエステル基量は7モル%、平均残存水酸基量は19モル%であった。
PVB-3の調製において、PVA-2をPVA-3(粘度平均重合度1700、けん化度89モル%)200gに、また、ブチルアルデヒド使用量を117gに変更し、さらに5℃でブチラール化反応を実施した後、65℃まで70分かけて昇温し、65℃で140分反応を行った以外は同様にして、PVB-4を得た。得られたPVB-4をJIS K6728にしたがって測定したところ、表1に示すとおり、平均アセタール化度は75モル%、平均残存ビニルエステル基量は9モル%、平均残存水酸基量は16モル%であった。
(積層体の作製)
100質量部のPVB-1、可塑剤(Ap)として39質量部のトリエチレングリコールジ2-エチルヘキサノエート、分散剤(Ad)として0.3質量部のトリエチレングリコールモノ2-エチルヘキサノエート、および0.048質量部の酢酸マグネシウム4水和物をラボプラストミルで160℃、8分間混練した。得られた混練物を厚さ0.38mmの型枠で160℃、50kg/cm2の条件で30分間プレスして厚さ0.38mmのシートAを得た。一方、100質量部のPVB-3、可塑剤(Bp)として60質量部のトリエチレングリコールジ2-エチルヘキサノエート、および分散剤(Bd)として0.2質量部のトリエチレングリコールモノ2-エチルヘキサノエートをラボプラストミルで160℃、8分間混練した。得られた混練物を厚さ0.15mmの型枠で160℃、50kg/cm2の条件で30分間プレスして厚さ0.15mmのシートBを得た。シートA及びシートBを、シートA/シートB/シートAの順に重ね、厚さ0.9mmの型枠で135℃、10kg/cm2の条件でプレスして、A層(0.38mm)/B層(0.14mm)/A層(0.38mm)からなる積層体-1を得た。
上記で得られた積層体-1を恒温恒湿器内で、35℃、80%RHの雰囲気で12時間調湿した。調湿した積層体-1をさらに下記(a)、(b)、(c)のそれぞれの条件で調湿を行い、以下の基準で評価したところ「18時間」であった。
条件(a):23℃、28%RHで18時間処理。
条件(b):29℃、55%RHで18時間処理後、続いて23℃、28%RHで18時間処理。
条件(c):32℃、68%RHで18時間処理後、続いて29℃、55%RHで18時間処理し、さらに続いて26℃、40%RHで18時間処理し、最後に続いて23℃、28%RHで18時間処理。
「18時間」:条件(a)で積層体が白濁および層間剥離を起こさず、含水率が0.7%以下になっているもの。
「36時間」:条件(a)では白濁や層間剥離が生じてしまうが、条件(b)で積層体が白濁および層間剥離を起こさず、含水率が0.7%以下になっているもの。
「72時間」:条件(a)及び条件(b)のいずれでも白濁や層間剥離が生じてしまうが、条件(c)で積層体が白濁または層間剥離を起こさず、含水率が0.7%以下になっているもの。
「18時間」は、急激に乾燥させても、積層体中で水や可塑剤がポリビニルアセタールと相分離しにくく、また水や可塑剤の層間へのブリードが起こりにくいことを示す。また、「36時間」、「72時間」となるにつれて、より緩やかな乾燥が必要になることを示す。
上記で得られた積層体-1を23℃、28%RHで5日間乾燥した後、35℃、80%RHでの雰囲気で処理した。積層体-1の処理を開始してから12時間後、24時間後、48時間後に目視で確認し、12時間後に可塑剤ブリードが無く、24時間後に可塑剤ブリードが発生しているものを「12時間」、24時間後に可塑剤ブリードが無く、48時間後に可塑剤ブリードが発生しているものを「24時間」、48時間後にも可塑剤ブリードが無いものを「48時間」として評価したところ、「48時間」であった。
30cm×30cmの積層体-1を23℃、28%RHの雰囲気下で5日間保管して調湿後、速やかに2枚のフロートガラス(30cm×30cm×2.2mm)で挟み、これを115℃に加熱後、ニップロールを用いて仮接着した。得られた仮接着体をオートクレーブに入れて135℃、1.2MPaの条件で60分間処理して合わせガラス-1を得た。
合わせガラス-1を60℃の熱水で12時間処理した後、23℃、28%RHの雰囲気下で108時間処理した(この処理を1サイクルとする)。当該処理を10回繰り返した後、合わせガラスの各端部から、積層体に含まれる成分抽出による欠点(ガラスと合わせガラス用中間膜の剥がれ、中間膜の層間の剥がれ)の発生の有無を目視により確認し、「無し」、「若干有」、「有」の3段階で評価したところ、「無し」であった。
表2および表4に示すようにA層およびB層の組成を変更した以外は実施例1と同様にして積層体及び合わせガラスを作製し、同様に評価した。結果を表3および表5に示す。
Claims (11)
- ポリビニルアセタール(A)、可塑剤(Ap)及び分散剤(Ad)を含むA層と、ポリビニルアセタール(B)及び可塑剤(Bp)を含み、分散剤(Bd)を含んでいても良いB層を備え、A層中の可塑剤(Ap)の含有量に対する分散剤(Ad)の含有量の質量比が、B層中の可塑剤(Bp)の含有量に対する分散剤(Bd)の含有量の質量比より大きく、可塑剤(Ap)がm価アルコール1分子(mは2~4の自然数を表す)と炭素数8~16の1価カルボン酸m分子とのエステル化反応で得られる化学構造を有するエステル化合物であり、分散剤(Ad)が可塑剤(Ap)の少なくとも1つのエステル結合を加水分解して得られる化学構造を有しかつ(m-1)~1個の水酸基と1~(m-1)個のエステル結合を有する化合物であり、可塑剤(Bp)がn価アルコール1分子(nは2~4の自然数を表す)と炭素数8~16の1価カルボン酸n分子とのエステル化反応で得られる化学構造を有するエステル化合物であり、分散剤(Bd)が可塑剤(Bp)の少なくとも1つのエステル結合を加水分解して得られる化学構造を有しかつ(n-1)~1個の水酸基と1~(n-1)個のエステル結合を有する化合物である、積層体。
- m価アルコールが縮合度が3~20であるエチレングリコールの縮合体である、請求項1記載の積層体。
- n価アルコールが縮合度が3~20であるエチレングリコールの縮合体である、請求項1または2に記載の積層体。
- ポリビニルアセタール(A)の平均残存水酸基量が20~40モル%である、請求項1~3のいずれかに記載の積層体。
- ポリビニルアセタール(B)の平均残存水酸基量が10~35モル%であり、平均残存ビニルエステル基量が0.01~25モル%である、請求項1~4のいずれかに記載の積層体。
- A層におけるポリビニルアセタール(A)100質量部に対する可塑剤(Ap)の含有量が、B層におけるポリビニルアセタール(B)100質量部に対する可塑剤(Bp)の含有量より少ない、請求項1~5のいずれかに記載の積層体。
- A層における可塑剤(Ap)の含有量がポリビニルアセタール(A)100質量部に対して20~60質量部である、請求項1~6のいずれかに記載の積層体。
- B層における可塑剤(Bp)の含有量がポリビニルアセタール(B)100質量部に対して30~80質量部である、請求項1~7のいずれかに記載の積層体。
- 前記1価カルボン酸が、カルボキシル基に隣接する炭素にカルボニル基以外の有機基が少なくとも2つ結合している、請求項1~8のいずれかに記載の積層体。
- 三層以上の層からなる積層体であり、積層体の外層の二層のうち少なくとも一層がA層である、請求項1~9のいずれかに記載の積層体。
- 請求項1~10のいずれかに記載の積層体を含む合わせガラス。
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JP2013525031A JP5373232B1 (ja) | 2013-05-22 | 2013-05-22 | 積層体 |
US14/892,915 US10029448B2 (en) | 2013-05-22 | 2013-05-22 | Laminate |
PCT/JP2013/064262 WO2014188545A1 (ja) | 2013-05-22 | 2013-05-22 | 積層体 |
CN201380076790.5A CN105228828B (zh) | 2013-05-22 | 2013-05-22 | 层叠体 |
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JP6113640B2 (ja) * | 2013-12-17 | 2017-04-12 | 株式会社クラレ | 積層体 |
JP6113642B2 (ja) * | 2013-12-17 | 2017-04-12 | 株式会社クラレ | 積層体 |
JP6113639B2 (ja) * | 2013-12-17 | 2017-04-12 | 株式会社クラレ | 積層体 |
JP6113643B2 (ja) * | 2013-12-17 | 2017-04-12 | 株式会社クラレ | 積層体 |
JP6113641B2 (ja) * | 2013-12-17 | 2017-04-12 | 株式会社クラレ | 積層体 |
JP6113645B2 (ja) * | 2013-12-17 | 2017-04-12 | 株式会社クラレ | 積層体 |
KR102351312B1 (ko) | 2014-01-15 | 2022-01-14 | 세키스이가가쿠 고교가부시키가이샤 | 접합 유리용 중간막 및 접합 유리 |
US10525675B2 (en) * | 2016-03-04 | 2020-01-07 | Solutia Inc. | Polymeric interlayers and multiple layer panels made therefrom exhibiting enhanced properties and performance |
KR20190060784A (ko) * | 2016-10-11 | 2019-06-03 | 쿠라라이 유럽 게엠베하 | 높은 가소제 함량을 갖는 폴리비닐 아세탈을 기반으로 한 다층 필름 |
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CN105228828A (zh) | 2016-01-06 |
JPWO2014188545A1 (ja) | 2017-02-23 |
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US10029448B2 (en) | 2018-07-24 |
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