WO2014188544A1 - Laminate having excellent sound-insulating properties - Google Patents

Laminate having excellent sound-insulating properties Download PDF

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Publication number
WO2014188544A1
WO2014188544A1 PCT/JP2013/064261 JP2013064261W WO2014188544A1 WO 2014188544 A1 WO2014188544 A1 WO 2014188544A1 JP 2013064261 W JP2013064261 W JP 2013064261W WO 2014188544 A1 WO2014188544 A1 WO 2014188544A1
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Prior art keywords
mass
laminate
laminated glass
compound
parts
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PCT/JP2013/064261
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French (fr)
Japanese (ja)
Inventor
芳聡 浅沼
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株式会社クラレ
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Priority to PCT/JP2013/064261 priority Critical patent/WO2014188544A1/en
Priority to JP2013525030A priority patent/JP5373231B1/en
Publication of WO2014188544A1 publication Critical patent/WO2014188544A1/en

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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

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 and mechanical strength.
  • the interlayer film for laminated glass is usually used in a state containing a small amount of water.
  • the moisture content of the interlayer film for laminated glass needs to be appropriately selected depending on the type of the laminated glass manufacturing process. For example, when producing laminated glass on a large scale, due to its high productivity, the glass and the laminated glass interlayer film are temporarily bonded with a nip roll, and then heated and pressurized with an autoclave to perform main bonding.
  • the method is widely used. Since this method does not include a reduced pressure treatment step in a series of steps, the risk of water volatilizing during the production of laminated glass and foaming in the interlayer film for laminated glass is low. Therefore, in this method, from the viewpoint of simplifying the humidity control process, a laminated glass interlayer film having a relatively high moisture content (for example, about 0.4 to 0.7%) is used.
  • a vacuum bag or a vacuum laminator is used for producing laminated glass, particularly when it is difficult to introduce a large and expensive apparatus.
  • a laminated glass is produced by heat-treating a glass and a laminated glass interlayer film under reduced pressure, so there is a risk that water will foam in the laminated glass interlayer film, resulting in bubbles and loss of appearance. high. Therefore, from the viewpoint of improving the yield in the production of laminated glass, the moisture content of the interlayer film for laminated glass is usually adjusted to be relatively low (for example, about 0.01 to 0.3%).
  • the interlayer film for laminated glass generally contains a plasticizer, but the plasticizer is extracted by water adhering to the exposed portion of the interlayer film at the end of the laminated glass, and the glass and the interlayer film are separated.
  • the appearance of the laminated glass may be impaired due to peeling or bubbles.
  • the plasticizer may volatilize from the edge of the laminated glass when a reduced pressure process is performed during the production of the laminated glass or when the laminated glass is used for a long time.
  • the present invention solves the above problems, and the plasticizer contained in the laminate is difficult to be extracted by water and hardly volatilized.
  • the plasticizer contained in the laminate is difficult to be extracted by water and hardly volatilized.
  • sound insulation is achieved even when the moisture content is changed. It aims at providing the laminated body from which a change of property does not occur.
  • the object described above is based on the general formula (I): 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 25 to 45 mol%: (Wherein R 1 and R 2 represent a hydrocarbon group having 7 to 11 carbon atoms, which may be the same or different, and m represents a natural number of 3 to 10) Content of Compound (I) a1 is 20 to 60 parts by mass, and the general formula (II): (Wherein R 3 is the same as either R 1 or R 2 , n represents a natural number of 3 to 10) and the content of the compound (II) is A2 parts by mass, The content b1 of the compound (I) is 35 to 75 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B) having an average residual hydroxyl group content of 10 to 35 mol%, and the content of the compound (II) is b2 parts by mass.
  • A2 is 0 or (b2 / b1) / (a2 / a1)> 1, (b1-a1)> 0, and a2 / a1 is 0 to 0. This is preferably achieved by providing a laminate having a ratio of 05 and b2 / b1 of 0.001 to 0.08.
  • the layer A preferably contains 0.001 to 0.1 parts by mass of a magnesium salt with respect to 100 parts by mass of the polyvinyl acetal (A).
  • M and n are preferably the same.
  • R 1 and R 2 are preferably the same.
  • R 1 and R 2 are preferably a 3-heptyl group.
  • both outermost layers are preferably A layers.
  • 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 when used as an interlayer film for laminated glass, the laminate does not cause a change in sound insulation even when the moisture content is changed. Can provide the body.
  • the average residual hydroxyl group content of the polyvinyl acetal (A) is 25 to 45 mol%, preferably 25 to 40 mol%, more preferably 25 to 35 mol%. If the average residual hydroxyl group content is less than 25 mol%, the mechanical strength of the laminate and the adhesion to glass may be reduced. If the average residual hydroxyl group content exceeds 45 mol%, the compound contained in the A layer The compatibility with (I) may be reduced.
  • the degree of acetalization of the polyvinyl acetal (A) is preferably 50 to 74 mol%, more preferably 60 to 74 mol%, and further preferably 65 to 74 mol%.
  • the average residual vinyl ester group amount of the polyvinyl acetal (A) is preferably 0.01 to 5 mol%, more preferably 0.01 to 4 mol%, and 0.01 to 3 mol%. More preferably. Polyvinyl acetal having an average residual vinyl ester group content of less than 0.01 mol% is difficult to produce industrially at low cost.
  • the average residual vinyl ester group amount of the polyvinyl acetal (A) exceeds 5 mol%, the average residual hydroxyl group amount of the polyvinyl acetal (A) is increased by hydrolysis of the vinyl ester group when the laminate is used over a long period of time.
  • the compatibility with compound (I) may change over time.
  • the average residual hydroxyl group content of the polyvinyl acetal (B) used in the present invention is 10 to 35 mol%, preferably 13 to 30 mol%, more preferably 15 to 25 mol%.
  • Polyvinyl acetal having an average residual hydroxyl group content of less than 10 mol% is difficult to produce industrially at low cost.
  • the average residual vinyl ester group amount of the polyvinyl acetal (B) exceeds 35 mol%, the compatibility with the compound (I) contained in the B layer may be lowered.
  • the degree of acetalization of the polyvinyl acetal (B) is preferably 60 to 85 mol%, more preferably 65 to 82 mol%, and further preferably 69 to 78 mol%.
  • the degree of acetalization of the polyvinyl acetal (A) is less than 60 mol%, the compatibility with the compound (I) contained in the B layer may be lowered.
  • Polyvinyl acetal having an acetalization degree exceeding 85 mol% is difficult to produce industrially at low cost.
  • the average residual vinyl ester group amount of the polyvinyl acetal (B) is preferably 0.01 to 20 mol%, more preferably 0.5 to 16 mol%, and 4 to 13 mol%. More preferably. Polyvinyl acetal having an average residual vinyl ester group content of less than 0.01 mol% is difficult to produce industrially at low cost.
  • the average residual vinyl ester group amount exceeds 20 mol%
  • the average residual hydroxyl group amount of the polyvinyl acetal (B) is increased by hydrolysis when used over a long period of time, and the compatibility with the compound (I) increases with time. May change significantly.
  • 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 800 to 2500, and more preferably 1000 to 2000. Is more preferable.
  • the viscosity average polymerization degree of polyvinyl alcohol is lower than 150, the resulting laminate tends to have insufficient mechanical strength, and when it is higher than 3000, the laminate is easy to handle, especially laminated glass for use as an interlayer film for laminated glass. The ease of manufacturing tends to decrease.
  • 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.
  • a basic compound is added to the reaction solution, 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. Preferably used.
  • 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.
  • R 1 and R 2 represent a hydrocarbon group having 7 to 11 carbon atoms which may be the same or different.
  • the hydrocarbon group has more preferably 7 to 10 carbon atoms, and more preferably 7 to 9 carbon atoms. If the carbon number is less than 7, the volatility of the compound (I) may be increased, which may be a problem. If the carbon number exceeds 11, the compatibility between the compound (I) and polyvinyl acetal may be reduced, or the compound ( The plasticizing effect of I) on polyvinyl acetal may be reduced.
  • the hydrocarbon group may be linear or branched, and may have an unsaturated bond. Moreover, some hydrogen atoms in the hydrocarbon group may be substituted with other atoms or substituents other than hydrogen atoms.
  • R 1 and R 2 include alkyl groups such as heptyl group, octyl group, nonyl group, decanyl group, isodecanyl group, and 3-heptyl group; alkenyl groups such as 3-hept-3-ene group; A chlorooctyl group etc. are mentioned. Among them, a hydrocarbon group having a branched structure is preferable in that it is not easily hydrolyzed. Particularly, when R 1 and R 2 are both 3-heptyl groups, compatibility with polyvinyl acetal and plasticization to polyvinyl acetal are preferable. It is particularly preferable from the viewpoint of effect.
  • R 1 and R 2 are preferably the same from the viewpoint of obtaining compound (I) at low cost.
  • the compound (I) contained in the A layer and the compound (I) contained in the B layer may be the same or different, but are preferably the same from the viewpoint of availability.
  • the compound (I) contained in the A layer and the B layer may be one kind alone or a mixture of two or more kinds.
  • M represents a natural number of 3 to 10, preferably 3 to 8, and more preferably 3 to 4.
  • a compound (I) has a low polarity and is preferable in that it is difficult to extract when the A layer and water contact. If m is less than 3, the volatility of the compound (I) may be increased, which may cause a problem. If m exceeds 10, the compatibility between the compound (I) and polyvinyl acetal may be reduced, or the compound (I) The plasticizing effect on polyvinyl acetal may decrease.
  • the compound (I) include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, octaethylene glycol di-2-ethylhexanoate, triethylene glycol di-2-octanoate. And triethylene glycol didodecanoate. Among them, triethylene glycol di-2-ethylhexanoate is preferable because it is excellent in compatibility with polyvinyl acetal, has excellent plasticizing effect on polyvinyl acetal, and is not easily hydrolyzed.
  • the content a1 of the compound (I) in the layer A is 20 to 60 parts by mass, preferably 25 to 55 parts by mass, more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A). It is. When a1 is less than 20 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A), sufficient sound insulation may not be exhibited when the obtained laminate is used for laminated glass. On the other hand, when a1 exceeds 60 parts by mass, sufficient mechanical strength may not be exhibited when the obtained laminate is used for laminated glass.
  • the content b1 of the compound (I) in the B layer is 35 to 75 parts by mass, preferably 40 to 72 parts by mass, more preferably 52 to 70 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B). is there.
  • b1 is less than 35 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B)
  • sufficient sound insulation may not be exhibited when the obtained laminate is used for laminated glass.
  • b1 exceeds 70 parts by mass, the compatibility between the polyvinyl acetal (B) and the compound (I) in the B layer is lowered, and the transparency of the resulting laminate is impaired, or sufficient mechanical strength is obtained. It may not develop.
  • (b1-a1)> 0 preferably 40> (b1-a1)> 7, more preferably 40> (b1-a1)> 15, and optimally 40 > (B1-a1)> 20.
  • (b1-a1)> 0 sufficient sound insulation is exhibited when the laminate is used for laminated glass.
  • (b1-a1) is 40 or more, sound insulation may be insufficient.
  • R 3 is the same as either R 1 or R 2 , and n represents a natural number of 3 to 10.
  • Compound (II) is similar to the chemical structure of Compound (I) and has excellent compatibility with Compound (I). Therefore, it is difficult to extract even when the laminate is in contact with water. It is also suitable for long-term use as an interlayer film. From the above viewpoint, it is particularly preferable that m of compound (I) and n of compound (II) are the same.
  • the compound (II) examples include triethylene glycol mono 2-ethylhexanoate, tetraethylene glycol mono 2-ethyl hexanoate, octaethylene glycol mono 2-ethyl hexanoate, triethylene glycol mono 2-octanoate. And triethylene glycol monododecanoate.
  • the preferred compound (I) used in the present invention is triethylene glycol di-2-ethylhexanoate, it is preferable to use triethylene glycol mono-2-ethylhexanoate as the compound (II).
  • the content a2 of the compound (II) in the A layer is preferably 0 to 2.5 parts by mass, more preferably 0.005 to 2.2 parts by mass, and more preferably 0.035 to 2.2 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A). 2 parts by mass is more preferred.
  • a2 is within the above range, the adhesiveness between the laminate and the glass hardly changes even when the amount of moisture changes. Further, when the laminate is used as an interlayer film for laminated glass, the compound (II) is hardly extracted into water even if the laminate is in contact with water.
  • the content b2 of the compound (II) in the B layer is preferably 0.01 to 3 parts by mass, more preferably 0.02 to 2.4 parts by mass, and further preferably 0.1 to 2.2 parts by mass.
  • b1 is less than 0.01 parts by mass, sound insulation may be lowered when the moisture content of the laminate is changed.
  • b1 is more than 3 parts by mass, for example, when the laminate is used for an interlayer film for laminated glass, when the laminate is in contact with water, a part of the compound (II) is extracted into water, and the appearance of the laminated glass The above disadvantages may occur.
  • the compound (II) contained in the A layer and the compound (II) contained in the B layer may be the same or different, but are preferably the same from the viewpoint of availability. Further, the compound (II) contained in each of the A layer and the B layer may be a single type or a mixture of two or more types.
  • a2 / a1 is 0 to 0.05, preferably 0.0007 to 0.045, and more preferably 0.001 to 0.04.
  • the sound insulation may be lowered when the moisture content of the laminate is changed when used as an interlayer film for laminated glass.
  • b2 / b1 is 0.001 to 0.08, preferably 0.0015 to 0.07, and more preferably 0.002 to 0.06.
  • the sound insulation may be lowered when the moisture content of the laminate is changed. .
  • a2 is 0 or (b2 / b1) / (a2 / a1)> 1.0.
  • a2 is 0 or when a2 is not 0, (b2 / b1) / (a2 / a1)> 1.1.
  • a2 is 0 or when a2 is not 0, [(b2 / b1) / (a2 / a1)]> 1.4.
  • [(b2 / b1) / (a2 / a1)] is 1.0 or less, when the moisture content of the laminate is changed and used as an interlayer film for laminated glass, sound insulation May decrease.
  • 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 in the range of 0.0001 to 5% by mass, 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.
  • 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 thereof is not particularly limited, but is usually 0.0001 to 5% by mass, 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.
  • the addition amount of the adhesion adjusting agent is 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A) from the viewpoint of penetration resistance of the laminated glass and prevention of glass piece 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.
  • the method for producing the laminate of the present invention is not particularly limited, and conventionally known methods can be applied.
  • the component constituting the A layer and the component constituting the B layer are each melt-kneaded with an extruder and subsequently co-extruded with a multilayer film forming machine; the A layer and the B prepared individually by hot pressing or casting after the melt-kneading
  • stacking a layer and sticking by hot press etc. as needed is mentioned.
  • the laminate of the present invention When the laminate of the present invention is used as an interlayer film for laminated glass, it exhibits a certain characteristic with a wide range of moisture content. Therefore, the moisture content of the interlayer film for laminated glass that is temporarily bonded by an autoclave after temporary bonding with a nip roll Laminated glass can be produced by a method in which the moisture content of the laminated glass interlayer film that is heat-treated under reduced pressure using a vacuum bag or a vacuum laminator is adjusted to a relatively low level.
  • the moisture content of the laminate of the present invention is preferably from 0.01 to 1.0% by mass, more preferably from 0.02 to 0.9% by mass, and even more preferably from 0.03 to 0.8% by mass.
  • the moisture content of the laminate of the present invention is less than 0.01% by mass because it takes a long time to adjust to such a moisture content, and the moisture content of the laminate of the present invention is not preferred.
  • the amount exceeds 1.0% by mass the adhesion of the laminate to the glass and the transparency may change, which is not preferable.
  • 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, further preferably 0.1 to 0.6 mm, and particularly preferably 0.12 to 0.5 mm. If the thickness is less than 0.05 mm, the mechanical strength of the laminate of the present invention tends to decrease, and for example, it may be insufficient for use as a laminated glass interlayer. When it is thicker than 1.2 mm, the laminate of the present invention tends to have insufficient flexibility. For example, in use as a laminated glass interlayer, the safety of the resulting laminated glass may be lowered.
  • the thickness of the B layer is usually preferably 0.01 to 1 mm, more preferably 0.02 to 0.6 mm, and further preferably 0.05 to 0.4 mm. If the thickness is less than 0.01 mm, the sound insulation performance of the laminated glass using the laminate of the present invention as an intermediate film may deteriorate, and even if it is thicker than 1 mm, the mechanical strength and sound insulation performance of the laminate of the present invention are more than that. There is a tendency not to improve.
  • the laminate of the present invention is used as an interlayer film for laminated glass
  • the laminate is composed of three or more layers, and the outermost layers are both A layers. It is preferable from the viewpoint of adjustment.
  • Examples of the laminate in which the outermost layers are both A layers include A layer / B layer / A layer, A layer / B layer / A layer / B layer / A layer, and the like.
  • the thickness of each layer may be the same or different.
  • two or more B layers are included, the thickness of each layer may be the same or different. .
  • 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. If the thickness of the laminate is thinner than 0.2 mm, the mechanical strength tends to be insufficient, and if 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 is mentioned, such as the method of not passing through the pressure reduction process to process.
  • An example of manufacturing conditions when using a vacuum laminator is as follows: treatment at a temperature of 100 to 200 ° C., preferably 130 to 160 ° C. for 10 to 300 minutes under a reduced pressure of 1 ⁇ 10 ⁇ 6 to 3 ⁇ 10 ⁇ 2 MPa. Then, an interlayer film for laminated glass is laminated with glass. In the case of using a vacuum bag, for example, it is laminated by treatment at 130 to 145 ° C. for 10 to 300 minutes under a pressure of 2 ⁇ 10 ⁇ 4 to 3 ⁇ 10 ⁇ 2 MPa.
  • the laminated glass is produced by the method of passing through these pressure reduction steps, it is preferable to use a laminate having a moisture content of 0.01 to 0.3% by mass, and bubbles are generated in the laminate during lamination. From the viewpoint of preventing this, it is preferable.
  • An example of the operating conditions of the nip roll in the method of pre-bonding with a nip roll and then processing with an autoclave is to heat the glass and the laminate to 50 to 120 ° C. with an infrared heater or the like, and then pressure-bond them temporarily with a roll.
  • the autoclaving step is performed, for example, at a temperature of 130 to 145 ° C. for 30 to 200 minutes under a pressure of 1.0 to 1.5 MPa.
  • the moisture content of the laminate is 0.4 to 0.7% by mass from the viewpoint of simplifying the humidity control (drying) step of the laminate. It is preferable to use one made to a degree.
  • PVB-1 polyvinyl butyral
  • PVB-3 (Preparation of PVB-3) In the preparation of PVB-1, after changing PVA-1 to 330 g PVA-2 (viscosity average polymerization degree 1700, saponification 92 mol%) and butyraldehyde use amount to 198 g, and further carrying out a butyralization reaction at 5 ° C. PVB-3 was obtained in the same manner except that the temperature was raised to 67 ° C. over 70 minutes and the reaction was carried out at 67 ° C. for 120 minutes. The PVB-3 thus obtained 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. %Met.
  • PVB-4 (Preparation of PVB-4)
  • PVA-2 was changed to 330 g of PVA-3 (viscosity average polymerization degree 1700, saponification 90 mol%)
  • butyraldehyde was used in an amount of 204 g
  • a butyralization reaction was carried out at 5 ° C.
  • PVB-4 was obtained in the same manner except that the temperature was raised to 67 ° C. over 70 minutes and the reaction was carried out at 67 ° C. for 120 minutes.
  • the properties of the obtained PVB-4 were measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 75 mol%, the average residual vinyl ester group amount was 9 mol%, and the average residual hydroxyl group amount was 16 mol. %Met.
  • Example 1 (Production of laminate) 100 parts by weight of PVB-1, 36 parts by weight of triethylene glycol di-2-ethylhexanoate as compound (I), 0.3 parts by weight of triethylene glycol mono-2-ethylhexanoate as compound (II) and 0.048 parts by mass of magnesium acetate tetrahydrate was 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.
  • Laminate-1 of 30 cm ⁇ 30 cm was stored in a desiccator adjusted to 23 ° C. and 5 to 10% RH for 5 days to adjust the humidity (dry).
  • the layered product-1 after humidity control is quickly sandwiched between two float glasses (30 cm x 30 cm x 2.2 mm), placed in a vacuum bag, and the inside of the vacuum bag is depressurized to 3 x 10 -3 MPa at room temperature. While maintaining the degree of vacuum, the mixture was heated to 135 ° C. over 30 minutes, and held at 135 ° C. for 2 hours to obtain laminated glass-1 (V).
  • the moisture content of laminate-1 in the obtained laminated glass-1 (V) was 0.11%.
  • the moisture content is as follows.
  • Laminated glass-1 is quickly taken out by hitting a portion of laminated glass-1 (V) that is more than 1 cm away from the edge with a hammer and breaking the glass.
  • V laminated glass-1
  • VA-200 water vaporizer
  • Laminated glass-1 (V) and laminated glass-1 (NA) were each cut to a size of 2.5 cm ⁇ 30 cm, and were shaken under an atmosphere of 25 ° C. (EMIC Corporation, small vibration generator 512-A).
  • the frequency response function at that time was detected with an FFT analyzer (DS-2100, manufactured by Ono Sokki Co., Ltd.), and at 3000 Hz using servo analysis software (DS-0242, manufactured by Ono Sokki Co., Ltd.).
  • the loss factor was calculated. The larger the loss factor, the better the sound insulation performance of the laminated glass.
  • Laminated glass cooling test Laminated glass-1 (V) and laminated glass-1 (NA) were held at 80 ° C. for 2 hours, then cooled from 80 ° C. to ⁇ 20 ° C. over 50 minutes, and further held at ⁇ 20 ° C. for 2 hours. The mixture was heated from ⁇ 20 ° C. to 80 ° C. over 50 minutes (this treatment is defined as one cycle). After repeating this cycle a total of 30 times, check if there is no separation between the glass and the laminate, and between the A layer and the B layer in the laminate. A sample having only a portion of 0 to 1 cm was designated as B, and a sample having peeling at a portion exceeding 1 cm from the edge of the glass was designated as C.
  • Laminated glass hot water treatment test Laminated glass-1 (NA) was immersed in warm water of 60 ° C. for 12 hours, and then allowed to stand 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, at the end of each laminated glass, the presence or absence of occurrence of defects (peeling of glass and interlayer film for laminated glass, peeling of interlayer of interlayer film) due to extraction of components contained in the laminate is visually observed. confirmed.
  • Examples 2 to 33, Comparative Examples 1 to 9 A laminate 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. The obtained laminated glass was evaluated in the same manner as in Example 1. The results are shown in Table 3 and Table 5.
  • the laminate of the present invention When the laminate of the present invention is used as an interlayer film for laminated glass, it is produced with a low moisture content by a vacuum laminator or a vacuum bag, or is produced with a high moisture content by an autoclave after temporary bonding with a nip roll. Can exhibit the same excellent characteristics.
  • the plasticizer contained in the laminate is difficult to be extracted by water and is not easily volatilized.
  • the plasticizer contained in the laminate is difficult to be extracted by water and is not easily volatilized.
  • the moisture content is changed, even if the moisture content is changed, a change in sound insulation properties does not occur. Absent.

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  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided is a laminate which exhibits excellent compatibility with polyvinyl acetal and an excellent polyvinyl acetal plasticization effect, and uses a plasticizer which is unlikely to be extracted using water and unlikely to volatilize, wherein changing the water content thereof does not produce a change in the sound-insulating properties thereof. A laminate comprising: an A-layer which contains 100 parts by mass of a polyvinyl acetal (A) having an average residual hydroxyl group amount in the range of 25-45 mol%, a compound (I) contained in the amount (a1) of 20-60 parts by mass and represented by formula (I), and a compound (II) contained in an amount (a2) and represented by formula (II); and a B-layer which contains 100 parts by mass of a polyvinyl acetal (B) having an average residual hydroxyl group amount in the range of 10-35 mol%, the compound (I) contained in the amount (b1) of 35-75 parts by mass, and the compound (II) contained in an amount (b2). Therein, a2 is 0 or (b2/b1)/(a2/a1)>1, (b1-a1)>0, a2/a1 is 0-0.05, and b2/b1 is 0.001-0.08.

Description

遮音性に優れる積層体Laminate with excellent sound insulation
　本発明はポリビニルアセタールを含有する積層体に関する。 The present invention relates to a laminate containing polyvinyl acetal.
　ポリビニルアセタール及び可塑剤を含むシートは、ガラスとの接着性や透明性、また力学強度に優れることから合わせガラス用中間膜として広範に利用されている。 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 and mechanical strength.
　合わせガラス用中間膜は通常、少量の水を含んだ状態で使用される。合わせガラス用中間膜の含水率は合わせガラスの製造工程の種類によって適宜選択する必要がある。例えば、合わせガラスを大規模で生産する場合には、その生産性の高さから、ガラスと合わせガラス用中間膜を重ねたものをニップロールで仮接着し、オートクレーブで加熱、加圧して本接着する方法が広く用いられている。この方法は一連の工程に減圧処理工程を含まないことから、合わせガラスの製造時に水が揮発して合わせガラス用中間膜中で発泡するリスクが低い。従って、この方法では、調湿工程簡略化の観点から合わせガラス用中間膜の含水率は比較的高め（例えば０．４～０．７％程度）に調整されたものが用いられる。 The interlayer film for laminated glass is usually used in a state containing a small amount of water. The moisture content of the interlayer film for laminated glass needs to be appropriately selected depending on the type of the laminated glass manufacturing process. For example, when producing laminated glass on a large scale, due to its high productivity, the glass and the laminated glass interlayer film are temporarily bonded with a nip roll, and then heated and pressurized with an autoclave to perform main bonding. The method is widely used. Since this method does not include a reduced pressure treatment step in a series of steps, the risk of water volatilizing during the production of laminated glass and foaming in the interlayer film for laminated glass is low. Therefore, in this method, from the viewpoint of simplifying the humidity control process, a laminated glass interlayer film having a relatively high moisture content (for example, about 0.4 to 0.7%) is used.
　一方、オートクレーブは高価であるため、特に大型で高価な装置の導入が困難な場合には、合わせガラスの生産にバキュームバッグまたは真空ラミネーターが用いられる。これらの方法ではガラスと合わせガラス用中間膜を重ねたものを減圧下に熱処理して合わせガラスを製造するため、合わせガラス用中間膜中で水が発泡し気泡となって外観が損なわれるリスクが高い。従って、合わせガラス製造時の歩留まり性向上の観点から、通常、合わせガラス用中間膜の含水率は比較的低め（例えば、０．０１～０．３％程度）に調整したものが使用される。 On the other hand, since an autoclave is expensive, a vacuum bag or a vacuum laminator is used for producing laminated glass, particularly when it is difficult to introduce a large and expensive apparatus. In these methods, a laminated glass is produced by heat-treating a glass and a laminated glass interlayer film under reduced pressure, so there is a risk that water will foam in the laminated glass interlayer film, resulting in bubbles and loss of appearance. high. Therefore, from the viewpoint of improving the yield in the production of laminated glass, the moisture content of the interlayer film for laminated glass is usually adjusted to be relatively low (for example, about 0.01 to 0.3%).
　近年、生活環境の質の向上を目的として、遮音、防音に関する関心が高まっている。特に自動車、鉄道、飛行機などの乗り物や、住居、商業ビルなどの建築物においては、窓ガラスからの音の侵入が問題になるため、遮音性合わせガラス用中間膜を用いた遮音性合わせガラスが使用されるケースが増えている。遮音性合わせガラス用中間膜としては、力学強度またはガラスとの接着性の発現を目的とした可塑剤含有量の低い層と、遮音性の発現のための可塑剤含有量の高い層とが積層された多層中間膜が一般的に使用されている（特許文献１、２参照）。 In recent years, interest in sound insulation and sound insulation has been increasing for the purpose of improving the quality of the living environment. In particular, in vehicles such as automobiles, railroads, airplanes, and buildings such as houses and commercial buildings, sound intrusion from window glass becomes a problem, so sound insulating laminated glass using an interlayer film for sound insulating laminated glass is used. More and more cases are used. As an interlayer film for sound insulating laminated glass, a layer with a low plasticizer content for the purpose of manifesting mechanical strength or adhesion to glass and a layer with a high plasticizer content for the expression of sound insulating properties are laminated. The multilayer interlayer film is generally used (see Patent Documents 1 and 2).
　ところで、遮音性合わせガラス用中間膜においては、それを使用する合わせガラスの遮音性が含水率により変化することが知られている（特許文献３参照）。前記した多層中間膜の含水率を０．０１～０．３％程度に調整して合わせガラスを製造すると、含水率を０．４～０．７％に調整した場合に比べて、遮音性が低下する。 By the way, in the interlayer film for sound insulating laminated glass, it is known that the sound insulating property of the laminated glass using it changes depending on the moisture content (see Patent Document 3). When the laminated glass is manufactured by adjusting the moisture content of the multilayer interlayer film to about 0.01 to 0.3%, the sound insulation is improved as compared with the case where the moisture content is adjusted to 0.4 to 0.7%. descend.
　また、合わせガラス用中間膜は一般的に可塑剤を含有するが、合わせガラスの端部で該中間膜がむき出しとなった部分に付着した水により可塑剤が抽出され、ガラスと該中間膜が剥離したり気泡が生じたりして合わせガラスの外観が損なわれる場合があった。また可塑剤の種類によっては、前記合わせガラスの製造の際に減圧工程を経る場合や、合わせガラスを長期使用した場合に、合わせガラス端部から可塑剤が揮発することがあった。 In addition, the interlayer film for laminated glass generally contains a plasticizer, but the plasticizer is extracted by water adhering to the exposed portion of the interlayer film at the end of the laminated glass, and the glass and the interlayer film are separated. The appearance of the laminated glass may be impaired due to peeling or bubbles. Further, depending on the type of plasticizer, the plasticizer may volatilize from the edge of the laminated glass when a reduced pressure process is performed during the production of the laminated glass or when the laminated glass is used for a long time.
特開２００７－３３１９５９号公報JP 2007-331959 A 国際公開第２０１０／０３８８０１号International Publication No. 2010/038801 国際公開第２０１０／００８０５３号International Publication No. 2010/008053
　本発明は上記課題を解決するものであり、積層体に含まれる可塑剤が水によって抽出されにくく、且つ揮発しにくく、合わせガラス用中間膜として用いた場合に、含水率を変化させても遮音性の変化が起こらない積層体を提供することを目的とする。 The present invention solves the above problems, and the plasticizer contained in the laminate is difficult to be extracted by water and hardly volatilized. When used as an interlayer film for laminated glass, sound insulation is achieved even when the moisture content is changed. It aims at providing the laminated body from which a change of property does not occur.
　本発明によれば、上記の目的は、平均残存水酸基量２５～４５モル％のポリビニルアセタール（Ａ）１００質量部に対し一般式（Ｉ）：
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ１およびＲ２は同一でも異なっていてもよい炭素数７～１１の炭化水素基を表し、ｍは３～１０の自然数を表す。）で示される化合物（Ｉ）の含有量ａ１が２０～６０質量部であり、一般式（ＩＩ）：
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ３はＲ１またはＲ２のいずれかと同一である。ｎは３～１０の自然数を表す。）で示される化合物（ＩＩ）の含有量がａ２質量部であるＡ層と、平均残存水酸基量１０～３５モル％のポリビニルアセタール（Ｂ）１００質量部に対し前記化合物（Ｉ）の含有量ｂ１が３５～７５質量部であり、前記化合物（ＩＩ）の含有量がｂ２質量部であるＢ層との積層体であって、ａ２が０又は（ｂ２／ｂ１）／（ａ２／ａ１）＞１であり、（ｂ１－ａ１）＞０であり、ａ２／ａ１が０～０．０５であり、且つｂ２／ｂ１が０．００１～０．０８である、積層体を提供することで好適に達成される。 According to the present invention, the object described above is based on the general formula (I): 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 25 to 45 mol%:
Figure JPOXMLDOC01-appb-C000003
 (Wherein R 1 and R 2 represent a hydrocarbon group having 7 to 11 carbon atoms, which may be the same or different, and m represents a natural number of 3 to 10) Content of Compound (I) a1 is 20 to 60 parts by mass, and the general formula (II):
Figure JPOXMLDOC01-appb-C000004
 (Wherein R 3 is the same as either R 1 or R 2 , n represents a natural number of 3 to 10) and the content of the compound (II) is A2 parts by mass, The content b1 of the compound (I) is 35 to 75 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B) having an average residual hydroxyl group content of 10 to 35 mol%, and the content of the compound (II) is b2 parts by mass. A2 is 0 or (b2 / b1) / (a2 / a1)> 1, (b1-a1)> 0, and a2 / a1 is 0 to 0. This is preferably achieved by providing a laminate having a ratio of 05 and b2 / b1 of 0.001 to 0.08.
　Ａ層はポリビニルアセタール（Ａ）１００質量部に対してマグネシウム塩０．００１～０．１質量部を含有することが好ましい。 The layer A preferably contains 0.001 to 0.1 parts by mass of a magnesium salt with respect to 100 parts by mass of the polyvinyl acetal (A).
　ｍとｎは同一であることが好ましい。 M and n are preferably the same.
　Ｒ１とＲ２は同一であることが好ましい。 R 1 and R 2 are preferably the same.
　Ｒ１及びＲ２は３－ヘプチル基であることが好ましい。 R 1 and R 2 are preferably a 3-heptyl group.
　３層以上の層から構成され、最外層の双方がＡ層であることが好ましい。 It is preferably composed of three or more layers, and both outermost layers are preferably A layers.
　本発明によると、上記の目的は、前記積層体を含む合わせガラスを提供することで好適に達成される。 According to the present invention, the above object is suitably achieved by providing a laminated glass including the laminate.
　本発明によれば、積層体に含まれる可塑剤が水によって抽出されにくく且つ揮発しにくく、合わせガラス用中間膜として用いた場合に、含水率を変化させても遮音性の変化が起こらない積層体を提供できる。 According to the present invention, the plasticizer contained in the laminate is difficult to be extracted and volatilized by water, and when used as an interlayer film for laminated glass, the laminate does not cause a change in sound insulation even when the moisture content is changed. Can provide the body.
　まず、本発明の積層体を構成するＡ層およびＢ層がそれぞれ含有するポリビニルアセタール（Ａ）およびポリビニルアセタール（Ｂ）について説明する。 First, the polyvinyl acetal (A) and the polyvinyl acetal (B) contained in each of the A layer and the B layer constituting the laminate of the present invention will be described.
　ポリビニルアセタール（Ａ）の平均残存水酸基量は２５～４５モル％であり、２５～４０モル％であることが好ましく、２５～３５モル％であることがより好ましい。平均残存水酸基量が２５モル％未満であると、積層体の力学強度やガラスとの接着性が低下する場合があり、また平均残存水酸基量が４５モル％を超えると、Ａ層に含まれる化合物（Ｉ）との相溶性が低下する場合がある。ポリビニルアセタール（Ａ）のアセタール化度は、５０～７４モル％であることが好ましく、６０～７４モル％であることがより好ましく、６５～７４モル％であることがさらに好ましい。ポリビニルアセタール（Ａ）のアセタール化度が５０モル％未満のものは、Ａ層に含まれる化合物（Ｉ）との相溶性が低下する場合があり、また７４モル％を超えると、積層体の力学強度が不十分となる場合がある。ポリビニルアセタール（Ａ）の平均残存ビニルエステル基量は、０．０１～５モル％であることが好ましく、０．０１～４モル％であることがより好ましく、０．０１～３モル％であることがさらに好ましい。平均残存ビニルエステル基量が０．０１モル％未満のポリビニルアセタールは工業的に安価に生産することが困難である。ポリビニルアセタール（Ａ）の平均残存ビニルエステル基量が５モル％を超えると、積層体を長期間にわたって使用した時にビニルエステル基の加水分解によってポリビニルアセタール（Ａ）の平均残存水酸基量が増加し、化合物（Ｉ）との相溶性が経時的に変化する場合がある。 The average residual hydroxyl group content of the polyvinyl acetal (A) is 25 to 45 mol%, preferably 25 to 40 mol%, more preferably 25 to 35 mol%. If the average residual hydroxyl group content is less than 25 mol%, the mechanical strength of the laminate and the adhesion to glass may be reduced. If the average residual hydroxyl group content exceeds 45 mol%, the compound contained in the A layer The compatibility with (I) may be reduced. The degree of acetalization of the polyvinyl acetal (A) is preferably 50 to 74 mol%, more preferably 60 to 74 mol%, and further preferably 65 to 74 mol%. When the degree of acetalization of the polyvinyl acetal (A) is less than 50 mol%, the compatibility with the compound (I) contained in the A layer may be lowered. The strength may be insufficient. The average residual vinyl ester group amount of the polyvinyl acetal (A) is preferably 0.01 to 5 mol%, more preferably 0.01 to 4 mol%, and 0.01 to 3 mol%. More preferably. Polyvinyl acetal having an average residual vinyl ester group content of less than 0.01 mol% is difficult to produce industrially at low cost. When the average residual vinyl ester group amount of the polyvinyl acetal (A) exceeds 5 mol%, the average residual hydroxyl group amount of the polyvinyl acetal (A) is increased by hydrolysis of the vinyl ester group when the laminate is used over a long period of time. The compatibility with compound (I) may change over time.
　本発明で使用するポリビニルアセタール（Ｂ）の平均残存水酸基量は１０～３５モル％であり、１３～３０モル％であることが好ましく、１５～２５モル％であることがより好ましい。平均残存水酸基量が１０モル％未満のポリビニルアセタールは工業的に安価に生産することが困難である。ポリビニルアセタール（Ｂ）の平均残存ビニルエステル基量が３５モル％を越えると、Ｂ層に含まれる化合物（Ｉ）との相溶性が低下する場合がある。ポリビニルアセタール（Ｂ）のアセタール化度は６０～８５モル％であることが好ましく、６５～８２モル％であることがより好ましく、６９～７８モル％であることがさらに好ましい。ポリビニルアセタール（Ａ）のアセタール化度が６０モル％未満であると、Ｂ層に含まれる化合物（Ｉ）との相溶性が低下する場合がある。アセタール化度が８５モル％を超えるポリビニルアセタールは工業的に安価に生産することが困難である。また、ポリビニルアセタール（Ｂ）の平均残存ビニルエステル基量は、０．０１～２０モル％であることが好ましく、０．５～１６モル％であることがより好ましく、４～１３モル％であることがさらに好ましい。平均残存ビニルエステル基量が０．０１モル％未満のポリビニルアセタールは工業的に安価に生産することが困難である。また、平均残存ビニルエステル基量が２０モル％を超えるものは、長期間にわたって使用した時に加水分解によってポリビニルアセタール（Ｂ）の平均残存水酸基量が増加し、化合物（Ｉ）との相溶性が経時的に著しく変化することがある。 The average residual hydroxyl group content of the polyvinyl acetal (B) used in the present invention is 10 to 35 mol%, preferably 13 to 30 mol%, more preferably 15 to 25 mol%. Polyvinyl acetal having an average residual hydroxyl group content of less than 10 mol% is difficult to produce industrially at low cost. When the average residual vinyl ester group amount of the polyvinyl acetal (B) exceeds 35 mol%, the compatibility with the compound (I) contained in the B layer may be lowered. The degree of acetalization of the polyvinyl acetal (B) is preferably 60 to 85 mol%, more preferably 65 to 82 mol%, and further preferably 69 to 78 mol%. When the degree of acetalization of the polyvinyl acetal (A) is less than 60 mol%, the compatibility with the compound (I) contained in the B layer may be lowered. Polyvinyl acetal having an acetalization degree exceeding 85 mol% is difficult to produce industrially at low cost. The average residual vinyl ester group amount of the polyvinyl acetal (B) is preferably 0.01 to 20 mol%, more preferably 0.5 to 16 mol%, and 4 to 13 mol%. More preferably. Polyvinyl acetal having an average residual vinyl ester group content of less than 0.01 mol% is difficult to produce industrially at low cost. When the average residual vinyl ester group amount exceeds 20 mol%, the average residual hydroxyl group amount of the polyvinyl acetal (B) is increased by hydrolysis when used over a long period of time, and the compatibility with the compound (I) increases with time. May change significantly.
　本発明で使用するポリビニルアセタール（Ａ）およびポリビニルアセタール（Ｂ）は、ポリビニルアルコールを原料として製造される。ポリビニルアルコールは従来から公知の手法によって得ることができる。すなわち、ビニルエステル化合物を重合し、得られた重合体をけん化することによって得ることができる。ビニルエステル化合物を重合する方法としては、溶液重合法、塊状重合法、懸濁重合法、乳化重合法など、従来から公知の方法を適用できる。これらの重合方法で用いられる重合開始剤としてはアゾ系開始剤、過酸化物系開始剤、レドックス系開始剤などを適宜使用できる。けん化反応は、従来から公知のアルカリ触媒又は酸触媒を用いて、重合体のビニルエステル基を加アルコール分解又は加水分解させることで行われる。中でも、メタノールを溶剤として用い、苛性ソーダ（ＮａＯＨ）を触媒として用いるけん化反応が簡便であり最も好ましい。 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. As 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. Among them, the saponification reaction using methanol as a solvent and caustic soda (NaOH) as a catalyst is simple and most preferable.
　ビニルエステル化合物としては、例えばギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、酪酸ビニル、ステアリン酸ビニル、安息香酸ビニルなど従来から公知のカルボン酸ビニルエステルが挙げられるが、酢酸ビニルが好ましい。 Examples of the vinyl ester compound 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.
　また、ポリビニルアルコールは本発明の主旨に反しない限り、ビニルエステル化合物と、ビニルエステル化合物と共重合可能な単量体とを共重合させた共重合体をけん化させて得られる変性ポリビニルアルコールを使用することもできる。ビニルエステル化合物と共重合可能な単量体は、通常、ビニルエステル化合物に対して１０モル％未満の割合で用いられる。 Also, unless the polyvinyl alcohol is contrary to the gist of the present invention, 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. You can also 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.
　本発明で使用するポリビニルアセタールの原料となるポリビニルアルコールの粘度平均重合度は特に限定されず、用途に応じて適宜選択できるが、通常１５０～３０００が好ましく、８００～２５００がより好ましく、１０００～２０００がさらに好ましい。ポリビニルアルコールの粘度平均重合度が１５０より低いと得られる積層体の力学強度が不足する傾向となり、３０００より高いと得られる積層体の取り扱い性、特に合わせガラス用中間膜として使用する場合の合わせガラス製造の容易さが低下する傾向となる。 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 800 to 2500, and more preferably 1000 to 2000. Is more preferable. When the viscosity average polymerization degree of polyvinyl alcohol is lower than 150, the resulting laminate tends to have insufficient mechanical strength, and when it is higher than 3000, the laminate is easy to handle, especially laminated glass for use as an interlayer film for laminated glass. The ease of manufacturing tends to decrease.
　本発明で使用するポリビニルアセタールは従来から公知の方法で製造できる。例えば、次のような反応条件下で沈殿法により製造できる。まず濃度３～４０質量％のポリビニルアルコール水溶液を８０～１００℃の温度範囲で保持した後、１０～６０分かけて徐々に冷却する。温度が－１０～３０℃まで低下したところで、アルデヒドおよび酸触媒を添加し、温度を一定に保ちながら、３０～３００分間アセタール化反応を行う。その際、アセタール化度が一定水準に達したポリビニルアセタールが析出する。その後、反応液を３０～３００分かけて３０～８０℃の温度まで昇温し、その温度を１０～５００分保持する。次に、反応溶液に塩基性の化合物を添加することで酸触媒を中和して水洗し、乾燥することによりポリビニルアセタールが得られる。 The polyvinyl acetal used in the present invention can be produced by a conventionally known method. For example, it can be produced by a precipitation method under the following reaction conditions. First, 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. When the temperature drops to −10 to 30 ° C., an aldehyde and an acid catalyst are added, and an acetalization reaction is performed for 30 to 300 minutes while keeping the temperature constant. At that time, polyvinyl acetal having a certain degree of acetalization is deposited. Thereafter, 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. Next, a basic compound is added to the reaction solution, the acid catalyst is neutralized, washed with water, and dried to obtain polyvinyl acetal.
　アセタール化反応に用いる酸触媒としては特に限定されず、酢酸、パラトルエンスルホン酸などの有機酸又は硝酸、硫酸、塩酸等などの無機酸のいずれも使用可能であり、特に塩酸、硫酸、硝酸が好ましく用いられる。 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. Preferably used.
　アセタール化反応に用いるアルデヒドは特に限定されないが、炭素数１～８のアルデヒドでアセタール化することが好ましい。中でも炭素数４～６のアルデヒドを用いることが好ましく、ｎ－ブチルアルデヒドを用いることが特に好ましい。本発明においては、アルデヒドを２種類以上併用して得られるポリビニルアセタールを使用することもできる。 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.
　次に一般式（Ｉ）：
Figure JPOXMLDOC01-appb-C000005
 で示される、Ａ層およびＢ層が含有する化合物（Ｉ）について説明する。 Next, the general formula (I):
Figure JPOXMLDOC01-appb-C000005
 The compound (I) contained in the A layer and the B layer shown in FIG.
　式中、Ｒ１およびＲ２は同一でも異なっていてもよい炭素数７～１１の炭化水素基を表す。炭化水素基の炭素数は７～１０であることがより好ましく、７～９であることがより好ましい。炭素数が７未満であると化合物（Ｉ）の揮発性が高くなり問題となる場合があり、炭素数が１１を超えると化合物（Ｉ）とポリビニルアセタールとの相溶性が低下したり、化合物（Ｉ）のポリビニルアセタールへの可塑化効果が低下したりする場合がある。 In the formula, R 1 and R 2 represent a hydrocarbon group having 7 to 11 carbon atoms which may be the same or different. The hydrocarbon group has more preferably 7 to 10 carbon atoms, and more preferably 7 to 9 carbon atoms. If the carbon number is less than 7, the volatility of the compound (I) may be increased, which may be a problem. If the carbon number exceeds 11, the compatibility between the compound (I) and polyvinyl acetal may be reduced, or the compound ( The plasticizing effect of I) on polyvinyl acetal may be reduced.
　炭化水素基は直鎖状でも分岐構造を有していてもよく、不飽和結合を有していてもよい。また、炭化水素基中の水素原子の一部が水素原子以外の他の原子や置換基で置換されていてもよい。Ｒ１及びＲ２の具体例としては、ヘプチル基、オクチル基、ノニル基、デカニル基、イソデカニル基、３－ヘプチル基などのアルキル基；３－ヘプト－３－エン基などのアルケニル基；１－クロロオクチル基などが挙げられる。中でも、分岐構造を有する炭化水素基であると加水分解を受けにくい点で好ましく、特にＲ１、Ｒ２が共に３－ヘプチル基であると、ポリビニルアセタールとの相溶性、ポリビニルアセタールへの可塑化効果の観点からも特に好ましい。 The hydrocarbon group may be linear or branched, and may have an unsaturated bond. Moreover, some hydrogen atoms in the hydrocarbon group may be substituted with other atoms or substituents other than hydrogen atoms. Specific examples of R 1 and R 2 include alkyl groups such as heptyl group, octyl group, nonyl group, decanyl group, isodecanyl group, and 3-heptyl group; alkenyl groups such as 3-hept-3-ene group; A chlorooctyl group etc. are mentioned. Among them, a hydrocarbon group having a branched structure is preferable in that it is not easily hydrolyzed. Particularly, when R 1 and R 2 are both 3-heptyl groups, compatibility with polyvinyl acetal and plasticization to polyvinyl acetal are preferable. It is particularly preferable from the viewpoint of effect.
　Ｒ１とＲ２は同一である方が、化合物（Ｉ）を安価に得られる観点から好ましい。本発明においてＡ層が含有する化合物（Ｉ）とＢ層が含有する化合物（Ｉ）は同一であっても異なっていても良いが、入手容易性などの観点から同一であることが好ましい。なお、Ａ層及びＢ層が含有する化合物（Ｉ）は１種類単独でも、２種類以上を混合したものでも良い。 R 1 and R 2 are preferably the same from the viewpoint of obtaining compound (I) at low cost. In the present invention, the compound (I) contained in the A layer and the compound (I) contained in the B layer may be the same or different, but are preferably the same from the viewpoint of availability. The compound (I) contained in the A layer and the B layer may be one kind alone or a mixture of two or more kinds.
　また、ｍは３～１０、好ましくは３～８、さらに好ましくは３～４の自然数を表す。このような化合物（Ｉ）は低極性であり、Ａ層と水が接触した場合に抽出されにくい点で好適である。ｍが３未満であると化合物（Ｉ）の揮発性が高くなり問題になることがあり、ｍが１０を超えると化合物（Ｉ）とポリビニルアセタールとの相溶性が低下したり、化合物（Ｉ）のポリビニルアセタールへの可塑化効果が低下したりすることがある。 M represents a natural number of 3 to 10, preferably 3 to 8, and more preferably 3 to 4. Such a compound (I) has a low polarity and is preferable in that it is difficult to extract when the A layer and water contact. If m is less than 3, the volatility of the compound (I) may be increased, which may cause a problem. If m exceeds 10, the compatibility between the compound (I) and polyvinyl acetal may be reduced, or the compound (I) The plasticizing effect on polyvinyl acetal may decrease.
　化合物（Ｉ）の具体例としては、トリエチレングリコールジ２－エチルヘキサノエート、テトラエチレングリコールジ２－エチルヘキサノエート、オクタエチレングリコールジ２－エチルヘキサノエート、トリエチレングリコールジ２－オクタノエート、トリエチレングリコールジドデカノエートなどが挙げられる。中でも、ポリビニルアセタールとの相溶性に優れ、ポリビニルアセタールへの可塑化効果に優れ、かつ容易に加水分解されない点で、トリエチレングリコールジ２－エチルヘキサノエートが好ましい。 Specific examples of the compound (I) include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, octaethylene glycol di-2-ethylhexanoate, triethylene glycol di-2-octanoate. And triethylene glycol didodecanoate. Among them, triethylene glycol di-2-ethylhexanoate is preferable because it is excellent in compatibility with polyvinyl acetal, has excellent plasticizing effect on polyvinyl acetal, and is not easily hydrolyzed.
　Ａ層における化合物（Ｉ）の含有量ａ１は、ポリビニルアセタール（Ａ）１００質量部に対して２０～６０質量部であり、好ましくは２５～５５質量部であり、より好ましくは３０～５０質量部である。ポリビニルアセタール（Ａ）１００質量部に対してａ１が２０質量部未満であると、得られる積層体を合わせガラスに使用した場合に十分な遮音性が発現しないことがある。一方、ａ１が６０質量部を超えると、得られる積層体を合わせガラスに使用した場合に十分な力学強度が発現しないことがある。 The content a1 of the compound (I) in the layer A is 20 to 60 parts by mass, preferably 25 to 55 parts by mass, more preferably 30 to 50 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A). It is. When a1 is less than 20 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A), sufficient sound insulation may not be exhibited when the obtained laminate is used for laminated glass. On the other hand, when a1 exceeds 60 parts by mass, sufficient mechanical strength may not be exhibited when the obtained laminate is used for laminated glass.
　Ｂ層における化合物（Ｉ）の含有量ｂ１は、ポリビニルアセタール（Ｂ）１００質量部に対し３５～７５質量部であり、好ましくは４０～７２質量部であり、より好ましくは５２～７０質量部である。ポリビニルアセタール（Ｂ）１００質量部に対してｂ１が３５質量部未満であると、得られる積層体を合わせガラスに使用した場合に十分な遮音性が発現しないことがある。一方、ｂ１が７０質量部を超えると、Ｂ層においてポリビニルアセタール（Ｂ）と化合物（Ｉ）との相溶性が低下して、得られる積層体の透明性が損なわれたり、十分な力学強度が発現しなかったりする場合がある。 The content b1 of the compound (I) in the B layer is 35 to 75 parts by mass, preferably 40 to 72 parts by mass, more preferably 52 to 70 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B). is there. When b1 is less than 35 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B), sufficient sound insulation may not be exhibited when the obtained laminate is used for laminated glass. On the other hand, if b1 exceeds 70 parts by mass, the compatibility between the polyvinyl acetal (B) and the compound (I) in the B layer is lowered, and the transparency of the resulting laminate is impaired, or sufficient mechanical strength is obtained. It may not develop.
　また、本発明においては、（ｂ１－ａ１）＞０であり、好ましくは４０＞（ｂ１－ａ１）＞７であり、さらに好ましくは４０＞（ｂ１－ａ１）＞１５であり、最適には４０＞（ｂ１－ａ１）＞２０である。（ｂ１－ａ１）＞０であると、積層体を合わせガラスに使用した際に十分な遮音性が発現する。ただし、（ｂ１－ａ１）が４０以上であると遮音性が不十分となる場合がある。 In the present invention, (b1-a1)> 0, preferably 40> (b1-a1)> 7, more preferably 40> (b1-a1)> 15, and optimally 40 > (B1-a1)> 20. When (b1-a1)> 0, sufficient sound insulation is exhibited when the laminate is used for laminated glass. However, if (b1-a1) is 40 or more, sound insulation may be insufficient.
　次に本発明のＡ層、Ｂ層が含有する一般式（ＩＩ）：
Figure JPOXMLDOC01-appb-C000006
 で示される化合物（ＩＩ）について説明する。 Next, the general formula (II) contained in the A layer and the B layer of the present invention:
Figure JPOXMLDOC01-appb-C000006
 The compound (II) represented by the formula is described.
　式中、Ｒ３はＲ１またはＲ２のいずれかと同一であり、ｎは３～１０の自然数を表す。化合物（ＩＩ）は、化合物（Ｉ）の化学構造と類似し、化合物（Ｉ）との相溶性に優れるため、積層体が水と接した場合にも抽出されにくく、例えば積層体を合わせガラス用中間膜として長期間使用する場合にも好適である。上記観点から、化合物（Ｉ）のｍと化合物（ＩＩ）のｎが同一であることが特に好ましい。 In the formula, R 3 is the same as either R 1 or R 2 , and n represents a natural number of 3 to 10. Compound (II) is similar to the chemical structure of Compound (I) and has excellent compatibility with Compound (I). Therefore, it is difficult to extract even when the laminate is in contact with water. It is also suitable for long-term use as an interlayer film. From the above viewpoint, it is particularly preferable that m of compound (I) and n of compound (II) are the same.
　化合物（ＩＩ）の具体例としては、トリエチレングリコールモノ２－エチルヘキサノエート、テトラエチレングリコールモノ２－エチルヘキサノエート、オクタエチレングリコールモノ２－エチルヘキサノエート、トリエチレングリコールモノ２－オクタノエート、トリエチレングリコールモノドデカノエートなどがあげられる。中でも、本発明で使用する好適な化合物（Ｉ）がトリエチレングリコールジ２－エチルヘキサノエートであるので、化合物（ＩＩ）として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用いるのが好ましい。 Specific examples of the compound (II) include triethylene glycol mono 2-ethylhexanoate, tetraethylene glycol mono 2-ethyl hexanoate, octaethylene glycol mono 2-ethyl hexanoate, triethylene glycol mono 2-octanoate. And triethylene glycol monododecanoate. Among them, since the preferred compound (I) used in the present invention is triethylene glycol di-2-ethylhexanoate, it is preferable to use triethylene glycol mono-2-ethylhexanoate as the compound (II).
　Ａ層における化合物（ＩＩ）の含有量ａ２はポリビニルアセタール（Ａ）１００質量部に対して０～２．５質量部が好ましく、０．００５～２．２質量部がより好ましく、０．０３５～２質量部がさらに好ましい。ａ２が上記範囲内であると、水分量が変化した場合であっても積層体とガラスとの接着性が変化しにくい。また、積層体を合わせガラス用中間膜に使用した際、積層体が水に接しても化合物（ＩＩ）が水に抽出されにくい。また、Ｂ層における化合物（ＩＩ）の含有量ｂ２は０．０１～３質量部が好ましく、０．０２～２．４質量部がより好ましく、０．１～２．２質量部がさらに好ましい。ｂ１が０．０１質量部より少ないと、積層体の含水率を変化させたときに遮音性が低下することがある。また、ｂ１が３質量部より多いと、例えば積層体を合わせガラス用中間膜に使用した際に、積層体が水に接すると化合物（ＩＩ）の一部が水に抽出され、合わせガラスに外観上の欠点が生じることがある。 The content a2 of the compound (II) in the A layer is preferably 0 to 2.5 parts by mass, more preferably 0.005 to 2.2 parts by mass, and more preferably 0.035 to 2.2 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A). 2 parts by mass is more preferred. When a2 is within the above range, the adhesiveness between the laminate and the glass hardly changes even when the amount of moisture changes. Further, when the laminate is used as an interlayer film for laminated glass, the compound (II) is hardly extracted into water even if the laminate is in contact with water. Further, the content b2 of the compound (II) in the B layer is preferably 0.01 to 3 parts by mass, more preferably 0.02 to 2.4 parts by mass, and further preferably 0.1 to 2.2 parts by mass. When b1 is less than 0.01 parts by mass, sound insulation may be lowered when the moisture content of the laminate is changed. Further, when b1 is more than 3 parts by mass, for example, when the laminate is used for an interlayer film for laminated glass, when the laminate is in contact with water, a part of the compound (II) is extracted into water, and the appearance of the laminated glass The above disadvantages may occur.
　Ａ層が含有する化合物（ＩＩ）とＢ層が含有する化合物（ＩＩ）は同一でも異なっていても良いが、入手容易性などの観点から同一であることが好ましい。また、Ａ層及びＢ層のそれぞれが含有する化合物（ＩＩ）は、１種類単独でも２種類以上を混合したものでも良い。 The compound (II) contained in the A layer and the compound (II) contained in the B layer may be the same or different, but are preferably the same from the viewpoint of availability. Further, the compound (II) contained in each of the A layer and the B layer may be a single type or a mixture of two or more types.
　本発明の積層体においては、ａ２／ａ１は０～０．０５であり、好ましくは０．０００７～０．０４５であり、より好ましくは０．００１～０．０４である。ａ２／ａ１がこれらの数値範囲外であると、合わせガラス用中間膜として使用する際、積層体の含水率を変化させたときに遮音性が低下することがある。ｂ２／ｂ１は０．００１～０．０８であり、好ましくは０．００１５～０．０７、より好ましくは０．００２～０．０６である。ｂ２／ｂ１が前記数値範囲外である場合、積層体の含水率を変化させて合わせガラス用中間膜として使用する際、積層体の含水率を変化させたときに遮音性が低下することがある。 In the laminate of the present invention, a2 / a1 is 0 to 0.05, preferably 0.0007 to 0.045, and more preferably 0.001 to 0.04. When a2 / a1 is outside these numerical ranges, the sound insulation may be lowered when the moisture content of the laminate is changed when used as an interlayer film for laminated glass. b2 / b1 is 0.001 to 0.08, preferably 0.0015 to 0.07, and more preferably 0.002 to 0.06. When b2 / b1 is out of the above numerical range, when the moisture content of the laminate is changed and used as an interlayer film for laminated glass, the sound insulation may be lowered when the moisture content of the laminate is changed. .
　本発明の積層体では、ａ２が０であるか（ｂ２／ｂ１）／（ａ２／ａ１）＞１．０である。好ましくはａ２が０であるかまたはａ２が０でないときは（ｂ２／ｂ１）／（ａ２／ａ１）＞１．１である。より好ましくはａ２が０であるかまたはａ２が０でないときは［（ｂ２／ｂ１）／（ａ２／ａ１）］＞１．４である。ａ２が０でなくかつ［（ｂ２／ｂ１）／（ａ２／ａ１）］が１．０以下であると、積層体の含水率を変化させて合わせガラス用中間膜として使用した場合に、遮音性が低下することがある。 In the laminate of the present invention, a2 is 0 or (b2 / b1) / (a2 / a1)> 1.0. Preferably, when a2 is 0 or when a2 is not 0, (b2 / b1) / (a2 / a1)> 1.1. More preferably, when a2 is 0 or when a2 is not 0, [(b2 / b1) / (a2 / a1)]> 1.4. When a2 is not 0 and [(b2 / b1) / (a2 / a1)] is 1.0 or less, when the moisture content of the laminate is changed and used as an interlayer film for laminated glass, sound insulation May decrease.
　本発明の積層体は、酸化防止剤、紫外線吸収剤、接着性改良剤、その他添加剤をさらに含有していても良い。 The laminate of the present invention may further contain an antioxidant, an ultraviolet absorber, an adhesion improver, and other additives.
　本発明の積層体が含有していてもよい酸化防止剤の種類に特に限定はない。例えば、従来から公知のフェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤などを使用できる。中でも、フェノール系酸化防止剤が好ましい。酸化防止剤は単独でも２種以上を組み合わせて用いてもよい。酸化防止剤を含有させる場合、その量は特に限定されないが、積層体の質量に対して通常０．０００１～５質量％、好ましくは０．００１～１質量％の範囲である。０．０００１質量％より少ないと酸化防止剤としての十分な効果が得られないことがあり、また５質量％より多くしても格段の効果は望めない。 There is no particular limitation on the type of antioxidant that the laminate of the present invention may contain. For example, 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. When the antioxidant is contained, the amount thereof is not particularly limited, but is usually in the range of 0.0001 to 5% by mass, 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.
　本発明の積層体が含有していてもよい紫外線吸収剤の種類に特に限定はない。例えば、従来から公知のベンゾトリアゾール系紫外線吸収剤、シュウ酸アニリド系紫外線吸収剤、ベンゾエート系紫外線吸収剤などを使用できる。紫外線吸収剤は単独でも２種以上を組み合わせて用いてもよい。紫外線吸収剤を含有させる場合、その量は特に限定されないが、積層体の質量に対して通常０．０００１～５質量％、好ましくは０．００１～１質量％の範囲である。０．０００１質量％より少ないと紫外線吸収剤としての十分な効果が得られないことがあり、また５質量％より多くしても格段の効果は望めない。 There is no particular limitation on the type of ultraviolet absorber that the laminate of the present invention may contain. For example, 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. When the ultraviolet absorber is contained, the amount thereof is not particularly limited, but is usually 0.0001 to 5% by mass, 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.
　本発明の積層体は合わせガラス用中間膜として特に好適に使用される。その場合、ガラスと接着する層には接着性調整剤が添加されていることが好ましい。接着性調整剤としては、例えば酢酸、プロピオン酸、ブタン酸、ヘキサン酸、２－エチルブタン酸、２－エチルヘキサン酸などの有機酸のナトリウム塩、カリウム塩、マグネシウム塩などが用いられ、これらは２種類以上が添加されていてもよい。特にガラスと接着する層がＡ層である場合、含水率が変化した場合にも接着性が変化しない積層体を得る観点から、Ａ層に酢酸マグネシウム、酢酸マグネシウム４水和物、ブタン酸マグネシウム、２－エチルブタン酸マグネシウム、２－エチルヘキサン酸マグネシウムなどのマグネシウム塩が添加されていることが好ましく、Ａ層に酢酸マグネシウム４水和物が添加されていることが好ましい。 The laminate of the present invention is particularly preferably used as an interlayer film for laminated glass. In that case, it is preferable that an adhesion adjusting agent is added to the layer that adheres to the glass. Examples of 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. In particular, when the layer that adheres to the glass is the A layer, from the viewpoint of obtaining a laminate in which the adhesiveness does not change even when the moisture content changes, magnesium acetate, magnesium acetate tetrahydrate, magnesium butanoate, Magnesium salts such as magnesium 2-ethylbutanoate and magnesium 2-ethylhexanoate are preferably added, and magnesium acetate tetrahydrate is preferably added to the A layer.
　接着性調整剤の添加量は、合わせガラスの耐貫通性および合わせガラス破損時のガラス片飛散防止性の観点から、ポリビニルアセタール（Ａ）１００質量部に対して０．００１～０．１質量部が好ましく、０．００５～０．０８質量部がより好ましく、０．０１～０．０６質量部がさらに好ましく、０．０３～０．０５５質量部が特に好ましい。 The addition amount of the adhesion adjusting agent is 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A) from the viewpoint of penetration resistance of the laminated glass and prevention of glass piece 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.
　本発明の積層体を製造する方法は特に限定されず、従来公知の方法を適用できる。例えばＡ層を構成する成分、Ｂ層を構成する成分をそれぞれ押出機で溶融混練し引き続き多層製膜機で共押出する方法；溶融混練後に熱プレスまたはキャストなどで個別に作製したＡ層およびＢ層を重ねて必要に応じて熱プレス等により接着して積層する方法などが挙げられる。 The method for producing the laminate of the present invention is not particularly limited, and conventionally known methods can be applied. For example, the component constituting the A layer and the component constituting the B layer are each melt-kneaded with an extruder and subsequently co-extruded with a multilayer film forming machine; the A layer and the B prepared individually by hot pressing or casting after the melt-kneading The method of laminating | stacking by laminating | stacking a layer and sticking by hot press etc. as needed is mentioned.
　本発明の積層体は、合わせガラス用中間膜として使用する場合に、広範な含水率で一定の特性を発現するため、ニップロールで仮接着後にオートクレーブで本接着する合わせガラス用中間膜の含水率を比較的高めに調節する方法でも、バキュームバッグまたは真空ラミネータを用いて減圧下で熱処理する合わせガラス中間膜の含水率を比較的低めに調節する方法でも合わせガラスを製造できる。本発明の積層体の含水率は０．０１～１．０質量％が好ましく、０．０２～０．９質量％がより好ましく、０．０３～０．８質量％がさらに好ましい。本発明の積層体の含水率が０．０１質量％未満であるものは、そのような含水率に調節することに長大な時間を要するので好ましくなく、また、本発明の積層体の含水率が１．０質量％を超えるものは、積層体のガラスとの接着性、透明性が変化することがあり、好ましくない。 When the laminate of the present invention is used as an interlayer film for laminated glass, it exhibits a certain characteristic with a wide range of moisture content. Therefore, the moisture content of the interlayer film for laminated glass that is temporarily bonded by an autoclave after temporary bonding with a nip roll Laminated glass can be produced by a method in which the moisture content of the laminated glass interlayer film that is heat-treated under reduced pressure using a vacuum bag or a vacuum laminator is adjusted to a relatively low level. The moisture content of the laminate of the present invention is preferably from 0.01 to 1.0% by mass, more preferably from 0.02 to 0.9% by mass, and even more preferably from 0.03 to 0.8% by mass. The moisture content of the laminate of the present invention is less than 0.01% by mass because it takes a long time to adjust to such a moisture content, and the moisture content of the laminate of the present invention is not preferred. When the amount exceeds 1.0% by mass, the adhesion of the laminate to the glass and the transparency may change, which is not preferable.
　本発明の積層体におけるＡ層およびＢ層の厚さに特に限定はない。Ａ層の厚さは通常０．０５～１．２ｍｍが好ましく、０．０７～１ｍｍがより好ましく、０．１～０．６ｍｍがさらに好ましく、０．１２～０．５ｍｍが特に好ましい。０．０５ｍｍよりも薄いと本発明の積層体の力学強度が低下する傾向となり、例えば合わせガラス中間膜としての使用に不十分な場合がある。１．２ｍｍよりも厚いと本発明の積層体の柔軟性が不十分となる傾向となり、例えば合わせガラス中間膜としての使用において、得られる合わせガラスの安全性が低下する場合がある。 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, further preferably 0.1 to 0.6 mm, and particularly preferably 0.12 to 0.5 mm. If the thickness is less than 0.05 mm, the mechanical strength of the laminate of the present invention tends to decrease, and for example, it may be insufficient for use as a laminated glass interlayer. When it is thicker than 1.2 mm, the laminate of the present invention tends to have insufficient flexibility. For example, in use as a laminated glass interlayer, the safety of the resulting laminated glass may be lowered.
　Ｂ層の厚さは通常０．０１～１ｍｍが好ましく、０．０２～０．６ｍｍがより好ましく、０．０５～０．４ｍｍがさらに好ましい。０．０１ｍｍよりも薄いと本発明の積層体を中間膜とする合わせガラスの遮音性能が低下することがあり、１ｍｍよりも厚くしても本発明の積層体の力学強度や遮音性能がそれ以上向上しない傾向にある。 The thickness of the B layer is usually preferably 0.01 to 1 mm, more preferably 0.02 to 0.6 mm, and further preferably 0.05 to 0.4 mm. If the thickness is less than 0.01 mm, the sound insulation performance of the laminated glass using the laminate of the present invention as an intermediate film may deteriorate, and even if it is thicker than 1 mm, the mechanical strength and sound insulation performance of the laminate of the present invention are more than that. There is a tendency not to improve.
　本発明の積層体を合わせガラス用中間膜として使用する場合、積層体が３層以上の層から構成され、最外層が共にＡ層であることが、積層体とガラスとの接着性を適切に調節できる観点から好ましい。最外層が共にＡ層である積層体の例としては、Ａ層／Ｂ層／Ａ層、Ａ層／Ｂ層／Ａ層／Ｂ層／Ａ層などが挙げられる。Ａ層が２層以上含まれる場合、それぞれの層の厚さは同一でも異なっていても良く、またＢ層が２層以上含まれる場合、それぞれの層の厚さは同一でも異なっていても良い。 When the laminate of the present invention is used as an interlayer film for laminated glass, the laminate is composed of three or more layers, and the outermost layers are both A layers. It is preferable from the viewpoint of adjustment. Examples of the laminate in which the outermost layers are both A layers include A layer / B layer / A layer, A layer / B layer / A layer / B layer / A layer, and the like. When two or more A layers are included, the thickness of each layer may be the same or different. When two or more B layers are included, the thickness of each layer may be the same or different. .
　本発明の積層体を合わせガラス用中間膜として使用する場合、積層体の厚さに特に限定はないが、通常０．２～２ｍｍが好ましく、０．２５～１．８ｍｍがより好ましく、０．３～１．５ｍｍがさらに好ましい。積層体の厚さが０．２ｍｍよりも薄いと力学強度が不十分になる傾向にあり、２ｍｍよりも厚いと柔軟性が不十分となる傾向にある。 When the laminate of the present invention is used as an interlayer film for laminated glass, 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. If the thickness of the laminate is thinner than 0.2 mm, the mechanical strength tends to be insufficient, and if it is thicker than 2 mm, the flexibility tends to be insufficient.
　本発明の積層体を合わせガラス用中間膜として使用する場合のガラス材質は特に限定されず、フロート板ガラス、熱強化ガラス、化学強化ガラスなどの無機ガラス；ポリメタクリル酸メチル、ポリカーボネートなどの有機ガラスなどの従来公知のガラスを使用できる。これらは無色もしくは有色、または透明もしくは非透明のいずれでもよく、また２種以上を併用してもよい。ガラスの厚さに特に限定はないが、通常２０ｍｍ以下が好ましく、１０ｍｍ以下がより好ましい。 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.
　本発明の積層体を合わせガラス用中間膜として使用する場合、積層体の最表面の形状は特に限定されないが、合わせガラスを製造する際の取り扱い性（例えばラミネートにおける泡抜け性）を考慮すると、積層体の最表面にメルトフラクチャーやエンボスなどの従来から公知の方法で凹凸構造を形成したものが好ましい。 When using the laminated body of the present invention as an interlayer film for laminated glass, 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.
　本発明の積層体を合わせガラス用中間膜として用いて合わせガラスを製造する方法は特に限定されず、例えば真空ラミネーター装置やバキュームバッグを用いた減圧工程を経る方法；ニップロールで仮接着した後にオートクレーブで処理する減圧工程を経ない方法など、従来公知の方法が挙げられる。 The method of producing laminated glass using the laminate of the present invention as an interlayer film for laminated glass is not particularly limited. For example, a method of undergoing a decompression step using a vacuum laminator device or a vacuum bag; A conventionally well-known method is mentioned, such as the method of not passing through the pressure reduction process to process.
　真空ラミネーター装置を用いる場合の作製条件の一例を示すと、１×１０－６～３×１０－２ＭＰａの減圧下、１００～２００℃、好ましくは１３０～１６０℃の温度で１０～３００分処理してガラスと合わせガラス用中間膜がラミネートされる。バキュームバッグを用いる場合は、例えば、２×１０－４～３×１０－２ＭＰａの圧力下、１３０～１４５℃で１０～３００分処理してラミネートされる。これら減圧工程を経る方法で合わせガラスを作製する場合には、積層体の含水率は０．０１～０．３質量％にしたものを用いることが、ラミネート中に積層体中で気泡が発生することを防ぐ観点から好ましい。 An example of manufacturing conditions when using a vacuum laminator is as follows: treatment at a temperature of 100 to 200 ° C., preferably 130 to 160 ° C. for 10 to 300 minutes under a reduced pressure of 1 × 10 −6 to 3 × 10 −2 MPa. Then, an interlayer film for laminated glass is laminated with glass. In the case of using a vacuum bag, for example, it is laminated by treatment at 130 to 145 ° C. for 10 to 300 minutes under a pressure of 2 × 10 −4 to 3 × 10 −2 MPa. When the laminated glass is produced by the method of passing through these pressure reduction steps, it is preferable to use a laminate having a moisture content of 0.01 to 0.3% by mass, and bubbles are generated in the laminate during lamination. From the viewpoint of preventing this, it is preferable.
　ニップロールで仮接着した後にオートクレーブで処理する方法におけるニップロールの運転条件の一例は、ガラスと積層体を赤外線ヒーターなどで５０～１２０℃に加熱した後、ロールで圧着して仮接着させる。オートクレーブ処理する工程は、例えば１．０～１．５ＭＰａの圧力下、１３０～１４５℃の温度で３０～２００分実施される。このような減圧工程を経ない方法で合わせガラスを作製する場合には、積層体の調湿（乾燥）工程を簡略化する観点から、積層体の含水率は０．４～０．７質量％程度にしたものを使用することが好ましい。 An example of the operating conditions of the nip roll in the method of pre-bonding with a nip roll and then processing with an autoclave is to heat the glass and the laminate to 50 to 120 ° C. with an infrared heater or the like, and then pressure-bond them temporarily with a roll. The autoclaving step is performed, for example, at a temperature of 130 to 145 ° C. for 30 to 200 minutes under a pressure of 1.0 to 1.5 MPa. In the case of producing a laminated glass by a method that does not go through such a decompression step, the moisture content of the laminate is 0.4 to 0.7% by mass from the viewpoint of simplifying the humidity control (drying) step of the laminate. It is preferable to use one made to a degree.
　以下、実施例などにより本発明をさらに詳しく説明するが、本発明はこれらの実施例によって何ら限定されない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
（ＰＶＢ－１の調製）
　還流冷却器、温度計、イカリ型攪拌翼を備えた５Ｌ（リットル）のガラス製容器に、イオン交換水４０５０ｇ、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％）３３０ｇを仕込み（ＰＶＡ濃度７．５％）、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、５℃まで約３０分かけて徐々に冷却後、ブチルアルデヒド１８８ｇと３５％の塩酸１４０ｇ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、室温まで冷却した。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塩酸を中和し、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の特性を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。 (Preparation of PVB-1)
In a 5 L (liter) glass container equipped with a reflux condenser, thermometer, and squid type stirring blade, 4050 g of ion-exchanged water, 330 g of polyvinyl alcohol (PVA-1) (viscosity average polymerization degree 1700, saponification degree 99 mol%) (PVA concentration 7.5%), and the contents were heated to 95 ° C. and completely dissolved. Next, after gradually cooling to 5 ° C. over about 30 minutes with stirring at 120 rpm, 188 g of butyraldehyde and 140 g of 35% hydrochloric acid were added, and a butyralization reaction was performed for 30 minutes. Thereafter, the temperature was raised to 60 ° C. over 60 minutes, held at 60 ° C. for 120 minutes, and then cooled to room temperature. After washing the polyvinyl acetal resin with ion-exchanged water, the remaining hydrochloric acid was neutralized with an aqueous sodium hydroxide solution, further washed with ion-exchanged water, dehydrated and dried to obtain polyvinyl butyral (PVB-1). The properties of the obtained PVB-1 were measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 68 mol%, the average residual vinyl ester group amount was 1 mol%, and the average residual hydroxyl group amount was 31 mol. %Met.
（ＰＶＢ－２の調製）
　ＰＶＢ－１の調製において、ブチルアルデヒド使用量を１９４ｇ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の特性を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。 (Preparation of PVB-2)
In the preparation of PVB-1, the reaction was carried out in the same manner except that the amount of butyraldehyde used was changed to 194 g to obtain PVB-2. The properties of the obtained PVB-2 were measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 71 mol%, the average residual vinyl ester group amount was 1 mol%, and the average residual hydroxyl group amount was 28 mol. %Met.
（ＰＶＢ－３の調製）
　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９２モル％）３３０ｇに、ブチルアルデヒド使用量を１９８ｇに変更し、さらに５℃でブチラール化反応を実施した後、６７℃まで７０分かけて昇温し、６７℃で１２０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の特定を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。 (Preparation of PVB-3)
In the preparation of PVB-1, after changing PVA-1 to 330 g PVA-2 (viscosity average polymerization degree 1700, saponification 92 mol%) and butyraldehyde use amount to 198 g, and further carrying out a butyralization reaction at 5 ° C. PVB-3 was obtained in the same manner except that the temperature was raised to 67 ° C. over 70 minutes and the reaction was carried out at 67 ° C. for 120 minutes. The PVB-3 thus obtained 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. %Met.
（ＰＶＢ－４の調製）
　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９０モル％）３３０ｇに、ブチルアルデヒド使用量を２０４ｇに変更し、さらに５℃でブチラール化反応を実施した後、６７℃まで７０分かけて昇温し、６７℃で１２０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の特性を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。 (Preparation of PVB-4)
In the preparation of PVB-3, PVA-2 was changed to 330 g of PVA-3 (viscosity average polymerization degree 1700, saponification 90 mol%), butyraldehyde was used in an amount of 204 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 67 ° C. over 70 minutes and the reaction was carried out at 67 ° C. for 120 minutes. The properties of the obtained PVB-4 were measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 75 mol%, the average residual vinyl ester group amount was 9 mol%, and the average residual hydroxyl group amount was 16 mol. %Met.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
（実施例１）
（積層体の作製）
　１００質量部のＰＶＢ－１、化合物（Ｉ）として３６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、化合物（ＩＩ）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、化合物（Ｉ）として５８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化合物（ＩＩ）として１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０．９１ｍｍの型枠で１３５℃、１０ｋｇ／ｃｍ２の条件でプレスして、Ａ層（０．３８ｍｍ）／Ｂ層（０．１５ｍｍ）／Ａ層（０．３８ｍｍ）からなる積層体－１を得た。 (Example 1)
(Production of laminate)
100 parts by weight of PVB-1, 36 parts by weight of triethylene glycol di-2-ethylhexanoate as compound (I), 0.3 parts by weight of triethylene glycol mono-2-ethylhexanoate as compound (II) and 0.048 parts by mass of magnesium acetate tetrahydrate was 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.
On the other hand, 100 parts by mass of PVB-3, 58 parts by mass of triethylene glycol di-2-ethylhexanoate as compound (I) and 1 part by mass of triethylene glycol mono-2-ethylhexanoate as compound (II) It knead | mixed for 160 minutes at 160 degreeC with the Laboplast mill. The obtained kneaded material was pressed for 30 minutes in a 0.15 mm thick mold at 160 ° C. and 50 kg / cm 2 to obtain a sheet B having a thickness of 0.15 mm. Sheet A and sheet B are stacked in the order of sheet A / sheet B / sheet A, and pressed in a 0.91 mm thick formwork at 135 ° C. and 10 kg / cm 2 , and layer A (0.38 mm) / A layered product-1 consisting of B layer (0.15 mm) / A layer (0.38 mm) was obtained.
（バキュームバッグを用いた低含水率合わせガラスの作製）
　３０ｃｍ×３０ｃｍの積層体－１を２３℃、５～１０％ＲＨに調節したデシケーター内に５日間保管して調湿（乾燥）した。調湿後の積層体－１を速やかに２枚のフロートガラス（３０ｃｍ×３０ｃｍ×２．２ｍｍ）で挟み、これをバキュームバッグに入れ、バキュームバッグ内を室温で３×１０－３MＰａに減圧し、その減圧度を保持しながら３０分かけて１３５℃にまで加熱し、１３５℃で２時間保持して合わせガラス－１（Ｖ）を得た。得られた合わせガラス－１（Ｖ）における積層体－１の含水率は０．１１％であった。なお、含水率は合わせガラス－１（Ｖ）の端部から１ｃｍよりも離れている部分をハンマーで叩いてガラスを割って速やかに積層体－１を取り出し、当該サンプル０．５ｇを株式会社三菱化学アナリティック製カールフィッシャー水分計（ＫＦ－２００（容量法水分計）とＶＡ－２００（水分気化装置）を組み合わせて使用）を用いて、２００℃で１０分間加熱し、その間に気化した水分を定量することで測定した。 (Production of low moisture content laminated glass using a vacuum bag)
Laminate-1 of 30 cm × 30 cm was stored in a desiccator adjusted to 23 ° C. and 5 to 10% RH for 5 days to adjust the humidity (dry). The layered product-1 after humidity control is quickly sandwiched between two float glasses (30 cm x 30 cm x 2.2 mm), placed in a vacuum bag, and the inside of the vacuum bag is depressurized to 3 x 10 -3 MPa at room temperature. While maintaining the degree of vacuum, the mixture was heated to 135 ° C. over 30 minutes, and held at 135 ° C. for 2 hours to obtain laminated glass-1 (V). The moisture content of laminate-1 in the obtained laminated glass-1 (V) was 0.11%. The moisture content is as follows. Laminated glass-1 is quickly taken out by hitting a portion of laminated glass-1 (V) that is more than 1 cm away from the edge with a hammer and breaking the glass. Using a chemical analytic Karl Fischer moisture meter (KF-200 (capacitance method moisture meter) and VA-200 (water vaporizer) combined) heated at 200 ° C for 10 minutes, Measured by quantification.
（ニップロールで仮接着後に、オートクレーブで本接着する、高含水率合わせガラスの作製）
　３０ｃｍ×３０ｃｍのシート－１を２３℃、２８％ＲＨの雰囲気下で５日間保管して調湿した。調湿後の積層体－１を速やかに２枚のフロートガラス（３０ｃｍ×３０ｃｍ×２．２ｍｍ）で挟み、これを８０℃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いれ、１３５℃、１．２ＭＰａの条件で６０分処理して合わせガラス－１（ＮＡ）を得た。得られた合わせガラス－１（ＮＡ）における積層体－１の含水率は０．５２％であった。なお、含水率は合わせガラス－１（Ｖ）と同様の方法で求めた。 (Preparation of high moisture content laminated glass that is temporarily bonded with a nip roll and then fully bonded with an autoclave)
The sheet-1 of 30 cm × 30 cm was stored for 5 days in an atmosphere of 23 ° C. and 28% RH to adjust the humidity. The layered product-1 after humidity adjustment was quickly sandwiched between two float glasses (30 cm × 30 cm × 2.2 mm), heated to 80 ° C., and temporarily bonded using a nip roll. The obtained temporary adhesive was placed in an autoclave and treated for 60 minutes at 135 ° C. and 1.2 MPa to obtain laminated glass-1 (NA). The moisture content of laminate-1 in the obtained laminated glass-1 (NA) was 0.52%. The water content was determined by the same method as for laminated glass-1 (V).
（遮音性測定）
　合わせガラス－１（Ｖ）、合わせガラス－１（ＮＡ）をそれぞれ２．５ｃｍ×３０ｃｍの大きさに切断し、２５℃雰囲気下で加振機（ＥＭＩＣ社製、小型振動発生機５１２－Ａ）により加振し、その際の周波数応答関数をＦＦＴアナライザー（小野測器社製、ＤＳ－２１００）にて検出し、サーボ解析ソフト（小野測器社製、ＤＳ－０２４２）を使用して３０００Ｈｚにおける損失係数を算出した。損失係数の大きいものほど合わせガラスの遮音性能が優れることを表す。 (Sound insulation measurement)
Laminated glass-1 (V) and laminated glass-1 (NA) were each cut to a size of 2.5 cm × 30 cm, and were shaken under an atmosphere of 25 ° C. (EMIC Corporation, small vibration generator 512-A). The frequency response function at that time was detected with an FFT analyzer (DS-2100, manufactured by Ono Sokki Co., Ltd.), and at 3000 Hz using servo analysis software (DS-0242, manufactured by Ono Sokki Co., Ltd.). The loss factor was calculated. The larger the loss factor, the better the sound insulation performance of the laminated glass.
（耐貫通性評価）
　上記で得られた３０ｃｍ×３０ｃｍの合わせガラス－１（Ｖ）、合わせガラス－１（ＮＡ）を２３℃で２４時間調温した。質量２２６０ｇ、直径８２ｍｍの鉄球（剛球）を、６ｍの高さから合わせガラスの中心部分に落下させた。同様の評価を４枚の合わせガラスについて行い、３枚以上の合わせガラスについて、剛球が衝突した後、５秒以内に剛球が貫通しなかった場合をＡとし、２枚以上の合わせガラスについて、剛球が衝突した後、５秒以内に剛球が貫通しなかった場合をＢとし、それ以外の場合をＣとした。 (Penetration resistance evaluation)
The 30 cm × 30 cm laminated glass-1 (V) and laminated glass-1 (NA) obtained above were conditioned at 23 ° C. for 24 hours. An iron ball (hard sphere) having a mass of 2260 g and a diameter of 82 mm was dropped from a height of 6 m onto the central portion of the laminated glass. The same evaluation was performed for four laminated glasses, and for three or more laminated glasses, A was the case where the hard sphere did not penetrate within 5 seconds after the hard sphere collided. The case where the hard sphere did not penetrate within 5 seconds after the collision occurred was designated as B, and the other cases were designated as C.
（合わせガラス冷熱試験）
　合わせガラス－１（Ｖ）及び合わせガラス－１（ＮＡ）を、８０℃で２時間保持した後、８０℃から－２０℃に５０分かけて冷却し、さらに－２０℃で２時間保持した後、－２０℃から８０℃に５０分かけて加熱した（この処理を１サイクルとする）。このサイクルを合計３０回繰り返した後、ガラスと積層体、および積層体におけるＡ層とＢ層との間に剥離が無いか確認して、剥離がないものをＡとし、剥離がガラス端部から０～１ｃｍの部分のみにあるものをＢとし、剥離がガラス端部から１ｃｍを超える部分にあるものをＣとした。 (Laminated glass cooling test)
Laminated glass-1 (V) and laminated glass-1 (NA) were held at 80 ° C. for 2 hours, then cooled from 80 ° C. to −20 ° C. over 50 minutes, and further held at −20 ° C. for 2 hours. The mixture was heated from −20 ° C. to 80 ° C. over 50 minutes (this treatment is defined as one cycle). After repeating this cycle a total of 30 times, check if there is no separation between the glass and the laminate, and between the A layer and the B layer in the laminate. A sample having only a portion of 0 to 1 cm was designated as B, and a sample having peeling at a portion exceeding 1 cm from the edge of the glass was designated as C.
（合わせガラスの温水処理試験）
　合わせガラス－１（ＮＡ）を６０℃の温水で１２時間浸漬後、２３℃、２８％ＲＨの雰囲気下で１０８時間静置した（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、各合わせガラス端部における、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た。 (Laminated glass hot water treatment test)
Laminated glass-1 (NA) was immersed in warm water of 60 ° C. for 12 hours, and then allowed to stand 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, at the end of each laminated glass, the presence or absence of occurrence of defects (peeling of glass and interlayer film for laminated glass, peeling of interlayer of interlayer film) due to extraction of components contained in the laminate is visually observed. confirmed.
（実施例２～３３、比較例１～９）
　表２および表４に示すようにＡ層及び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た。得られた合わせガラスについて実施例１と同様に評価した。結果を表３および表５に示す。 (Examples 2 to 33, Comparative Examples 1 to 9)
A laminate 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. The obtained laminated glass was evaluated in the same manner as in Example 1. The results are shown in Table 3 and Table 5.
　本発明の積層体を合わせガラス用中間膜として使用する場合、真空ラミネーターやバキュームバッグによって低めの含水率で作製したもの、またニップロールで仮接着後にオートクレーブにより高めの含水率で作製したもの、いずれにおいても同等の優れた特性を発現させることが可能である。
When the laminate of the present invention is used as an interlayer film for laminated glass, it is produced with a low moisture content by a vacuum laminator or a vacuum bag, or is produced with a high moisture content by an autoclave after temporary bonding with a nip roll. Can exhibit the same excellent characteristics.
Figure JPOXMLDOC01-appb-T000008
 
Figure JPOXMLDOC01-appb-T000008
 
Figure JPOXMLDOC01-appb-T000009
  
Figure JPOXMLDOC01-appb-T000009
  
Figure JPOXMLDOC01-appb-T000010
  
Figure JPOXMLDOC01-appb-T000010
  
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　本発明の積層体は、積層体に含まれる可塑剤が水によって抽出されにくく、且つ揮発しにくく、合わせガラス用中間膜として用いた場合に、含水率を変化させても遮音性の変化が起こらない。 In the laminate of the present invention, the plasticizer contained in the laminate is difficult to be extracted by water and is not easily volatilized. When used as an interlayer film for laminated glass, even if the moisture content is changed, a change in sound insulation properties does not occur. Absent.

Claims (7)

  1. 平均残存水酸基量２５～４５モル％のポリビニルアセタール（Ａ）１００質量部に対し一般式（Ｉ）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１およびＲ２は同一でも異なっていてもよい炭素数７～１１の炭化水素基を表し、ｍは３～１０の自然数を表す。）で示される化合物（Ｉ）の含有量ａ１が２０～６０質量部であり、一般式（ＩＩ）：
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ３はＲ１またはＲ２のいずれかと同一である。ｎは３～１０の自然数を表す。）で示される化合物（ＩＩ）の含有量がａ２質量部であるＡ層と、平均残存水酸基量１０～３５モル％のポリビニルアセタール（Ｂ）１００質量部に対し前記化合物（Ｉ）の含有量ｂ１が３５～７５質量部であり、前記化合物（ＩＩ）の含有量がｂ２質量部であるＢ層との積層体であって、ａ２が０又は（ｂ２／ｂ１）／（ａ２／ａ１）＞１であり、（ｂ１－ａ１）＞０であり、ａ２／ａ１が０～０．０５であり、かつｂ２／ｂ１が０．００１～０．０８である、積層体。     General formula (I): 100 parts by mass of polyvinyl acetal (A) having an average residual hydroxyl group content of 25 to 45 mol%:
    Figure JPOXMLDOC01-appb-C000001
     (Wherein R 1 and R 2 represent a hydrocarbon group having 7 to 11 carbon atoms, which may be the same or different, and m represents a natural number of 3 to 10) Content of Compound (I) a1 is 20 to 60 parts by mass, and the general formula (II):
    Figure JPOXMLDOC01-appb-C000002
     (Wherein R 3 is the same as either R 1 or R 2 , n represents a natural number of 3 to 10) and the content of the compound (II) is A2 parts by mass, The content b1 of the compound (I) is 35 to 75 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B) having an average residual hydroxyl group content of 10 to 35 mol%, and the content of the compound (II) is b2 parts by mass. A2 is 0 or (b2 / b1) / (a2 / a1)> 1, (b1-a1)> 0, and a2 / a1 is 0 to 0. 05, and b2 / b1 is 0.001 to 0.08.
  2. Ａ層がポリビニルアセタール（Ａ）１００質量部に対してマグネシウム塩０．００１～０．１質量部を含有する請求項１記載の積層体。 The laminate according to claim 1, wherein the layer A contains 0.001 to 0.1 parts by mass of a magnesium salt with respect to 100 parts by mass of the polyvinyl acetal (A).
  3. ｍとｎが同一である、請求項１または２に記載の積層体。 The laminate according to claim 1 or 2, wherein m and n are the same.
  4. Ｒ１とＲ２が同一である、請求項１～３のいずれかに記載の積層体。 The laminate according to any one of claims 1 to 3, wherein R 1 and R 2 are the same.
  5. Ｒ１及びＲ２が３－ヘプチル基である、請求項１～４のいずれかに記載の積層体。 The laminate according to any one of claims 1 to 4, wherein R 1 and R 2 are 3-heptyl groups.
  6. ３層以上の層から構成され、最外層の双方がＡ層である請求項１～５のいずれかに記載の積層体。 The laminate according to any one of claims 1 to 5, wherein the laminate is composed of three or more layers, and both outermost layers are A layers.
  7. 請求項１～６のいずれかに記載の積層体を含む合わせガラス。 A laminated glass comprising the laminate according to any one of claims 1 to 6.
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JPH11323055A (en) * 1998-05-18 1999-11-26 Sekisui Chem Co Ltd Plasticizer
WO2011078314A1 (en) * 2009-12-25 2011-06-30 積水化学工業株式会社 Intermediate film for laminated glass, and laminated glass

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KR20180128036A (en) 2016-03-28 2018-11-30 주식회사 쿠라레 Interlayer for laminated glass
US11325354B2 (en) 2016-03-28 2022-05-10 Kuraray Co., Ltd. Interlayer film for laminated glass
WO2018061861A1 (en) 2016-09-27 2018-04-05 株式会社クラレ Intermediate film for laminated glass
KR20190061016A (en) 2016-09-27 2019-06-04 주식회사 쿠라레 Interlayer for laminated glass

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