JP2015117142A - Laminate having excellent sound insulation properties - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyvinyl acetal resin laminate which is used for an intermediate film of a laminated glass and causes no change in sound insulation properties when changing the moisture content.SOLUTION: There is provided a laminate which comprises: an A layer of compounds represented by the following formula I and a specific formula having a content of Waand Wapts.wt. based on 100 pts.wt. of a polyvinyl acetal (A) having an average residual hydroxyl group amount of 25 to 45 mol%; and a B layer of compounds represented by the following formula I and a specific formula having a content of Wband Wbpts.wt. based on 100 pts.wt. of a polyvinyl acetal (B) having an average residual hydroxyl group amount of 10 to 35 mol%, where Wais 0 or (Wb/Wb)/(Wa/Wa)>1 and (Wb-Wa)>0, Wa/Wais o to 0.05, Wb/Wbis 0.001 to 0.08 and at least one surface of the laminate has a ten point average roughness (Rz) of 10 to 70 μm.

Description

  The present invention relates to a laminate containing polyvinyl acetal.

  Sheets containing polyvinyl acetal and a plasticizer are widely used as interlayer films for laminated glass because of their 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, the water content of the interlayer film for laminated glass is adjusted to be relatively high (for example, about 0.4 to 0.7%) from the viewpoint of simplifying the humidity control process.

  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, usually, the water content of the interlayer film for laminated glass is adjusted to be relatively low (for example, about 0.01 to 0.3%).

  In recent years, interest in sound insulation and soundproofing has been increasing for the purpose of improving the quality of the living environment. In particular, in vehicles such as automobiles, railways, airplanes, and buildings such as houses and commercial buildings, sound intrusion from window glass becomes a problem. 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).

  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 a 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 less than when the moisture content is adjusted to 0.4 to 0.7%. For example, when the ambient temperature becomes relatively high (for example, about 30 ° C.), sufficient sound insulation performance may not be exhibited depending on the moisture content of the multilayer interlayer film.

  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.

  By the way, when producing a laminated glass, after placing an interlayer film for laminated glass between the glass on both sides, the entire interlayer film for laminated glass is melted and fluidized by heating and pressing the whole, and the glass and Filling the gaps in the interlayer film for laminated glass is performed. However, depending on the shape of the interlayer film for laminated glass, air escape is not sufficient, and bubbles may be generated at the end of the laminated glass, resulting in defective products.

JP 2007-331959 A International Publication No. 2010/038801 International Publication No. 2010/008053

  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. It is another object of the present invention to provide a laminate that can be easily adjusted to a moisture content that can exhibit excellent sound insulation performance. Furthermore, it aims at providing the laminated body which is excellent in the bubble-removing property at the time of producing a laminated glass.

（式中、Ｒ^１およびＲ^２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）の含有量がＷ_ａ１質量部であり、一般式（ＩＩ）：

（式中、Ｒ^３はＲ^１またはＲ^２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Ｗ_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）の含有量がＷ_ｂ１質量部であり、前記化合物（ＩＩ）の含有量がＷ_ｂ２質量部であるＢ層との積層体であって、Ｗ_ａ２が０又は（Ｗ_ｂ２／Ｗ_ｂ１）／（Ｗ_ａ２／Ｗ_ａ１）＞１であり、（Ｗ_ｂ１−Ｗ_ａ１）＞０であり、Ｗ_ａ２／Ｗ_ａ１が０〜０．０５であり、かつＷ_ｂ２／Ｗ_ｂ１が０．００１〜０．０８であり、積層体の少なくとも一方の表面の十点平均粗さ（Ｒｚ）が１０〜７０μｍである、積層体提供することで好適に達成される。 According to the present invention, the above object is achieved by adding the general formula (I) to 100 parts by mass of the polyvinyl acetal (A) having an average residual hydroxyl group content of 25 to 45 mol%:

(Wherein R ¹ and R ² represent the same or different hydrocarbon groups having 7 to 11 carbon atoms, and m represents a natural number of 3 to 10). Content of Compound (I) Is W _a1 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 compound (II) represented by W _a2 parts by mass is layer A The content of the compound (I) is W _b1 parts by mass and the content of the compound (II) is W _b2 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%. W _a2 is 0 or (W _b2 / W _b1 ) / (W _a2 / W _a1 )> 1 and (W _b1 −W _a1 )> 0, W _a2 / _{W a1} is 0 to 0.05, and _W b2 _{/ W b1} is 0.001 to 0.08, ten-point average roughness of at least one surface of the laminate (Rz) is 10~70μm This is preferably achieved by providing a laminate.

It is preferable that W _a1 is 10 to 60 parts by mass and W _b1 is 10 to 70 parts by mass.

  It is preferable that A layer contains 0.001-0.1 mass part of magnesium salts with respect to 100 mass parts of 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.

  It is preferably composed of three or more layers, and both outermost layers are preferably A layers.

  According to the present invention, the above object is preferably achieved by providing a laminated glass including the laminate.

  According to the present invention, when the plasticizer contained in the laminate is difficult to be extracted and volatilized by water and used as an interlayer film for laminated glass, the water content is changed within a range of, for example, 0.1 to 1%. However, it is possible to provide a laminate that does not change the sound insulation. Moreover, according to this invention, the laminated body easy to adjust to the moisture content which can express the outstanding sound-insulation performance can be provided. Furthermore, according to this invention, the laminated body which is excellent in the bubble-removing property at the time of producing a laminated glass can be provided.

  First, the polyvinyl acetal (A) and the polyvinyl acetal (B) contained in the layer A and the layer B constituting the laminate of the present invention will be described.

  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.

  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%, and 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. If the average residual hydroxyl group content 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) increases 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. 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 a vinyl acetate group of a 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.

  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.

  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.

  The viscosity average polymerization degree 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 according to the use, but is usually preferably 150 to 3000, more preferably 800 to 2500, and 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.

  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, a polyvinyl alcohol aqueous 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 is lowered 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.

  The acid catalyst used in the acetalization reaction is not particularly limited, and any of organic acids such as acetic acid and p-toluenesulfonic acid or inorganic acids such as nitric acid, sulfuric acid and hydrochloric acid can be used. Preferably used.

  Although the aldehyde used for acetalization reaction is not specifically limited, It is preferable to acetalize with a C1-C8 aldehyde. Among them, it is preferable to use an aldehyde having 4 to 6 carbon atoms, and it is particularly preferable to use n-butyraldehyde. In the present invention, polyvinyl acetal obtained by using two or more aldehydes in combination can also be used.

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):

The compound (I) contained in the A layer and the B layer shown in FIG.

Wherein represents a hydrocarbon group of R ¹ and R ² 7-11 carbon atoms, which may be the same or different. As for carbon number of a hydrocarbon group, it is more preferable that it is 7-10, and it is more preferable that it is 7-9. 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. 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 difficult to undergo hydrolysis, and 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. 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.

  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.

  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 an excellent plasticizing effect on polyvinyl acetal, and is not easily hydrolyzed.

The content W _a1 of the compound (I) in the A layer is preferably 10 to 60 parts by mass, more preferably 10 to 55 parts by mass, and still more preferably 100 parts by mass of the polyvinyl acetal (A). It is 25-45 mass parts. When _Wa1 is less than 10 parts by mass relative 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 W _a1 exceeds 60 parts by mass, sufficient mechanical strength may not be exhibited when the obtained laminate is used for laminated glass.

It is preferable that content _Wb1 of compound (I) in B layer is 10-70 mass parts with respect to 100 mass parts of polyvinyl acetal (B), More preferably, it is 30-70 mass parts, More preferably, it is 45. -70 mass parts. When _Wb1 is less than 10 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, when W _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. May not be expressed.

In the present invention, (W _b1 −W _a1 )> 0, preferably 40> (W _b1 −W _a1 )> 7, and more preferably 40> (W _b1 −W _a1 )> 15. Yes, optimally 40> (W _b1 −W _a1 )> 20. When (W _b1 −W _a1 )> 0, sufficient sound insulation is exhibited when the laminate is used for laminated glass. However, if (W _b1 −W _a1 ) is 40 or more, the sound insulation may be insufficient.

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:

The compound (II) represented by the formula will be described.

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.

  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 these, 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).

The content W _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 with respect to 100 parts by mass of the polyvinyl acetal (A), and 0.035. More preferably, ˜2 parts by mass. When W _a2 is within the above range, the adhesiveness between the laminate and the glass hardly changes even when the moisture content 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 _{W b2} is preferably 0.01 to 3 parts by weight of the compound in the B layer (II), more preferably from 0.02 to 2.4 parts by weight, more preferably 0.1 to 2.2 parts by weight . When W _b1 is less than 0.01 parts by mass, sound insulation may be lowered when the moisture content of the laminate is changed. Moreover, when _Wb1 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 laminated glass Appearance defects 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.

In the laminate of the present invention, W _a2 / W _a1 is 0 to 0.05, preferably 0.0007 to 0.045, and more preferably 0.001 to 0.04. When W _a2 / W _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. W _b2 / W _b1 is 0.001 to 0.08, preferably 0.0015 to 0.07, and more preferably 0.002 to 0.06. When W _b2 / W _b1 is outside 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 performance is reduced when the moisture content of the laminate is changed. There is.

In the laminate of the present invention, W _a2 is 0 or (W _b2 / W _b1 ) / (W _a2 / W _a1 )> 1.0. Preferably, when W _a2 is 0 or W _a2 is not 0, (W _b2 / W _b1 ) / (W _a2 / W _a1 )> 1.1. More preferably, when W _a2 is 0 or W _a2 is not 0, [(W _b2 / W _b1 ) / (W _a2 / W _a1 )]> 1.4. When W _a2 was not 0 and [(W _b2 / W _b1 ) / (W _a2 / W _a1 )] was 1.0 or less, the moisture content of the laminate was changed and used as an interlayer film for laminated glass. In some cases, sound insulation may be reduced.

  The laminate of the present invention may further contain an antioxidant, an ultraviolet absorber, an adhesion improver, and other additives.

  There is no limitation in particular in the kind of antioxidant which the laminated body of this 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 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 antioxidant may not be obtained, and when the amount is more than 5% by mass, a remarkable effect cannot be expected.

  There is no limitation in particular in the kind of ultraviolet absorber which the laminated body of this 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.

  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.

  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 preferable, 0.005-0.08 mass part is more preferable, 0.01-0.06 mass part is further more preferable, 0.03-0.055 mass part is especially preferable.

  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.

  The laminate of the present invention can be used as an interlayer film for laminated glass. In such a case, a vacuum bag or a vacuum laminator can be used even if the moisture content of the interlayer film for laminated glass, which is temporarily bonded with an autoclave after temporary bonding with a nip roll, is adjusted to a relatively high level in order to develop certain characteristics with a wide range of moisture content. Laminated glass can also be produced by a method in which the moisture content of the interlayer film for laminated glass that is heat-treated under reduced pressure is adjusted to be relatively low. The moisture content of the laminate of the present invention is preferably 0.01 to 1.0% by mass, more preferably 0.02 to 0.9% by mass, and further preferably 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.

  There is no limitation in particular in the thickness of A layer and B layer in the laminated body of this invention. 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 it is thinner than 0.05 mm, the mechanical strength of the laminate of the present invention tends to decrease, and it may be insufficient for use as an interlayer film for laminated glass, for example. When it is thicker than 1.2 mm, the flexibility of the laminate of the present invention tends to be insufficient. For example, in use as an interlayer film for laminated glass, the safety of the obtained 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 still more 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.

  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. .

  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 0.05 to 2.4 mm, more preferably 0.1 to 1.8 mm, 0.3 to 1.2 mm is more preferable. If the thickness of the laminate is less than 0.05 mm, the mechanical strength tends to be insufficient. If the thickness is greater than 2.4 mm, the flexibility is insufficient, and the moisture content exhibits excellent sound insulation performance. It tends to be difficult to adjust.

  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 surface roughness of the laminate is determined by a ten-point average roughness Rz obtained from a laser microscope. Ten-point average roughness Rz is the height of the highest peak from the highest peak to the fifth measured from the average curve of the roughness curve in the direction of the average line. Is the sum of the average value of the absolute values of the values and the average value of the absolute values of the elevations from the lowest valley floor to the fifth, and this value is expressed in micrometers (μm). JIS B0601 (1994) )

  In the laminate of the present invention, the ten-point average roughness (Rz) of at least one surface is 10 to 70 μm. The ten-point average roughness (Rz) is preferably 10 to 60 μm, and more preferably 10 to 50 μm. When the ten-point average roughness (Rz) is less than 10 μm, the bubble-removability is not good in the production of laminated glass using the laminate, and when the ten-point average roughness (Rz) exceeds 70 μm, When using a laminated body for the intermediate film for laminated glasses, it may become difficult to adjust to the target moisture content, which is not preferable.

  The method for obtaining a laminate satisfying such a range of 10-point average roughness (Rz) is not particularly limited. For example, an uneven structure is formed on the outermost surface of the laminate by a conventionally known method such as melt fracture or embossing. can do.

  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.

An example of the production conditions when using a vacuum laminator apparatus is 10 to 300 minutes at a temperature of 100 to 200 ° C., preferably 130 to 160 ° C. under a reduced pressure of 1 × 10 ^{−6 to} 3 × 10 ⁻² MPa. Then, an interlayer film for laminated glass is laminated with glass. When using a vacuum bag, it laminates by processing for 10 to 300 minutes at 130-145 degreeC under the pressure of ² * 10 ^{< -4} > ^-3 * 10 ^<-2 > MPa, for example. When producing laminated glass by the method of passing through these decompression steps, it is necessary 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 processing with an autoclave after temporarily bonding with the nip roll is that the glass and the laminate are heated to 50 to 120 ° C. with an infrared heater or the like, and then pressure bonded with the roll and temporarily bonded. The process of autoclaving is performed at a temperature of 130 to 145 ° C. for 30 to 200 minutes, for example, under a pressure of 1.0 to 1.5 MPa. When producing 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.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited at all by these Examples.

(Preparation of PVB-1)
In a 5 L (liter) glass container equipped with a reflux condenser, thermometer, and squid type stirring blade, ion-exchanged water 4050 g, polyvinyl alcohol (PVA-1) (viscosity average polymerization degree 1700, saponification degree 99 mol%) 330 g (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 K6728-1977 (hereinafter referred to as JIS K6728). As shown in Table 1, the average degree of acetalization was 69 mol%, the average amount of residual vinyl acetate groups (average The amount of residual vinyl ester groups) was 1 mol%, and the average amount of residual hydroxyl groups was 30 mol%.

(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 acetate group amount was 1 mol%, and the average residual hydroxyl group amount was 28 mol. %Met.

(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. The temperature was raised to 67 ° C over 70 minutes, and PVB-3 was obtained in the same manner except that the reaction was carried out at 67 ° C for 120 minutes. When the specificity of the obtained PVB-3 was measured according to JIS K6728, as shown in Table 1, the average degree of acetalization was 74 mol%, the average residual vinyl acetate group amount was 9 mol%, and the average residual hydroxyl group amount was 17 mol. %Met.

(Preparation of PVB-4)
In the preparation of PVB-3, after changing PVA-2 to 330 g of PVA-3 (viscosity average polymerization degree 1700, saponification 90 mol%) and butyraldehyde use amount to 204 g, and further carrying out a butyralization reaction at 5 ° C. The temperature was raised to 67 ° C. over 70 minutes, and PVB-4 was obtained in the same manner except that 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 74 mol%, the average amount of residual vinyl acetate groups was 7 mol%, and the average amount of residual hydroxyl groups was 19 mol. %Met.

Example 1
(Production of laminate)
100 parts by weight of PVB-1, 30 parts by weight of triethylene glycol di-2-ethylhexanoate as compound (I), and 0.1 parts by weight of triethylene glycol mono 2-ethylhexanoate as compound (II) 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, 48 parts by mass of triethylene glycol di-2-ethylhexanoate as compound (I) and 0.4 parts by mass of triethylene glycol mono-2-ethylhexanoate as compound (II) The ate was kneaded in a Laboplast mill at 160 ° C. for 8 minutes. 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, pressed and laminated in a 0.91 mm thick formwork at 135 ° C. and 10 kg / cm ² , and two more embossed sheets To obtain a laminate-1 consisting of A layer (0.38 mm) / B layer (0.14 mm) / A layer (0.38 mm) and having a ten-point average roughness Rz = 35 μm.

(Measurement of ten-point average roughness (Rz))
According to JIS B0601 (1994) and JIS B0031 (1994), ten-point average roughness Rz obtained from a laser microscope (manufactured by Keyence Corporation, VK-X200) was determined for laminate-1. Ten-point average roughness Rz is the height of the highest peak from the highest peak to the fifth measured from the average curve of the roughness curve in the direction of the average line. The sum of the average absolute value and the average absolute value of the altitude of the bottom valley from the lowest valley bottom to the fifth is obtained, and this value is expressed in micrometers (μm).

(Production of low moisture content laminated glass using a vacuum bag)
The laminate-1 of 30 cm × 30 cm was stored in a desiccator adjusted to 23 ° C. and 5 to 15% 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 vacuum bag is depressurized to 3 x ^10-3 MPa at room temperature. While maintaining the degree of decompression, 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 0.12%. Further, in the laminated glass-1 (V), no bubbles remained between the glass and the laminate 1, and the bubble removal property was good. In addition, the moisture content hits the part which is separated from 1 cm from the edge part of laminated glass-1 (V) with a hammer, breaks glass, takes out laminated body-1 rapidly, and the said sample 0.5g is Mitsubishi Corporation. Using a Karl Fischer moisture meter (KF-200 (capacitance method moisture meter) and VA-200 (moisture vaporizer) in combination) manufactured by Chemical Analytic, heated at 200 ° C. for 10 minutes, Measured by quantification.

(Preparation of high moisture content laminated glass that is temporarily bonded with a nip roll and then fully bonded with an autoclave)
The laminate 1 of 30 cm × 30 cm was stored for 5 days in an atmosphere of 23 ° C. and 50 to 70% RH to adjust the humidity. Laminated body-1 after moisture conditioning (water content 0.65%: measured with the same method using the same Karl Fischer moisture meter as described above) immediately with two float glasses (30 cm × 30 cm × 2.2 mm) After being sandwiched and heated to 80 ° C., it was temporarily bonded using a nip roll. The obtained temporary adhesive body was put into an autoclave and treated for 60 minutes under conditions of 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 0.60%, and the change in the moisture content before and after the production of the laminated glass was 0.05%. When the change in the moisture content of the interlayer film for laminated glass is small, the desired moisture content may be adjusted at the time of producing the laminate, and the moisture content can be easily adjusted. In addition, the moisture content was calculated | required by the method similar to laminated glass-1 (V). Further, in the laminated glass-1 (NA), no bubbles remained between the glass and the laminate 1, and the bubble removal property was good.

(Sound insulation measurement)
Laminated glass-1 (V) and laminated glass-1 (NA) are each cut into a size of 2.5 cm × 30 cm, and shaker (EMIC Corporation, small vibration generator 512-A) in an atmosphere of 30 ° C. The frequency response function at that time is 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.

(Examples 2 to 16, Comparative Examples 1 to 5)
As shown in Table 2, a laminate and a laminated glass were produced in the same manner as in Example 1 except that the composition of the A layer and the B layer was changed. The obtained laminated glass was evaluated in the same manner as in Example 1. The results are shown in Table 3.

(Comparative Example 6)
In the method for producing Laminate-1, Comparative Example Laminate-6 was obtained using a smooth PET (polyethylene terephthalate) film instead of the embossed sheet. The ten-point average roughness of Comparative Example Laminate-6 was 3 μm or less. When the obtained Comparative Example Laminate-6 was evaluated in the same manner as in Example-1, the bubble removal property was poor and bubbles remained at the end of the laminated glass. The results are shown in Table 3.

(Comparative Example 7)
In the method for producing Laminate-1, the embossed sheet was replaced with another to obtain Comparative Example Laminate-7. The ten-point average roughness of Comparative Example Laminate-7 was 120 μm or less. The obtained Comparative Example laminate-7 was evaluated in the same manner as in Example-1. The results are shown in Table 3.

  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. Moreover, the laminated body of this invention is easy to adjust to the moisture content which can express the outstanding sound-insulation performance, and is excellent in the bubble removal property at the time of producing a laminated glass.

  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. Moreover, the laminated body of this invention is easy to adjust to the moisture content which can express the outstanding sound-insulation performance. Furthermore, the laminated body of this invention is excellent in the bubble-removing property at the time of producing a laminated glass.

Claims (8)

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 the same or different hydrocarbon groups having 7 to 11 carbon atoms, and m represents a natural number of 3 to 10). Content of Compound (I) Is W _a1 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 compound (II) represented by W _a2 parts by mass is layer A ,
The content of the compound (I) is W _b1 parts by mass and the content of the compound (II) is W _b2 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%. A laminate with a certain B layer,
W _a2 is 0 or (W _b2 / W _b1 ) / (W _a2 / W _a1 )> 1, (W _b1 −W _a1 )> 0, and W _a2 / W _a1 is 0 to 0.05. And W _b2 / W _b1 is 0.001 to 0.08,
The laminated body whose 10-point average roughness (Rz) of the surface of at least one of a laminated body is 10-70 micrometers. The laminate according to claim 1, wherein W _a1 is 10 to 60 parts by mass and W _b1 is 10 to 70 parts by mass. The laminate according to claim 1 or 2, wherein the A layer 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). The laminated body in any one of Claims 1-3 whose m and n are the same. R ¹ and ^{R 2} are the same, the laminated body according to any one of claims 1 to 4. R ¹ and ^{R 2} is 3-heptyl, laminate according to any one of claims 1 to 5. The laminate according to any one of claims 1 to 6, comprising three or more layers, wherein both outermost layers are A layers. The laminated glass containing the laminated body in any one of Claims 1-7.