JP2015116681A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate to be used as an interlayer of a glass laminate, where a plasticizer contained in the laminate is not easily extracted with water and does not evaporate easily; water and the plasticizer do not phase-separate easily from polyvinyl acetal in the laminate, even when a laminate having a high moisture content is dried rapidly in a low temperature and low moisture environment; and interlayer bleeding of water and the plasticizer does not occur easily.SOLUTION: Provided is a laminate comprising layer A which comprises polyvinyl acetal (A) having an average residual hydroxyl group amount X of 15 to 50 mole% and a plasticizer (Ap); and layer B which comprises polyvinyl acetal (B) having an average residual hydroxyl group amount Y of 10 to 45 mole% and a plasticizer (Bp), where X≥Y, and a hydroxyl value of the plasticizer (Ap), HV(Ap) mg KOH/g, and a hydroxyl value of the plasticizer (Bp), HV(Bp) mg KOH/g, satisfy a relationship: HV(Ap)>HV(Bp).

Description

  The present invention relates to a laminate containing polyvinyl acetal.

  A sheet containing polyvinyl acetal and a plasticizer is widely used as an interlayer film for laminated glass because of its excellent adhesion and transparency to glass, mechanical strength and flexibility.

  When the moisture content of the interlayer film for laminated glass increases, the plasticizer may bleed (exudation), and when stored in a warehouse or the like, when the outside air temperature increases to 25 ° C to 40 ° C such as in summer. Under such a high temperature, the intermediate film is likely to be deformed or the interlayer films are likely to be blocked. Usually, it is stored in a warehouse, etc., adjusted to low temperature and low humidity so that plasticizer bleed, deformation and blocking do not occur by air conditioning equipment.

  However, when storing the interlayer film for laminated glass, the inside of the warehouse may become high temperature and high humidity due to, for example, a failure of the air conditioning equipment, and the moisture content of the interlayer film for laminated glass may become extremely high. If the interlayer film for laminated glass having a high water content is left as it is, water and plasticizer may be phase-separated in the interlayer film, or the plasticizer may bleed on the surface of the interlayer film. The transparency and mechanical properties of the interlayer film may deteriorate.

  By the way, in recent years, an interlayer film for multilayer laminated glass has been studied as an interlayer film for laminated glass having sound insulation properties. The interlayer film for sound insulating laminated glass includes a layer having a low plasticizer content for the purpose of expressing mechanical strength or exhibiting adhesiveness to glass, and a layer having a high plasticizer content for expressing sound insulating properties. In general, an interlayer film for sound-insulating multilayer laminated glass is used (see Patent Documents 1 and 2).

  When the interlayer film for multilayer laminated glass is also stored for a long time in a state of high moisture content, the moisture content becomes remarkably high, and water and plasticizer are phase-separated in the interlayer film, and the plasticizer bleeds on the surface of the interlayer film Therefore, it is necessary to dry the interlayer film for multilayer laminated glass having a high moisture content in a low temperature and low humidity atmosphere. However, when an interlayer film for multilayer laminated glass having a high water content is rapidly dried in an atmosphere of low temperature and low humidity, the interlayer film becomes opaque due to phase separation of water and plasticizer from polyvinyl acetal in the interlayer film. In addition, water or a plasticizer may bleed between the interlayers of the intermediate film to cause delamination or decrease in transparency. In order to avoid these, there is a method of drying while gradually decreasing the temperature and humidity, but there is a problem that it takes a long time for drying.

  In addition, the interlayer film for laminated glass containing a plasticizer is extracted by the water adhering to the portion where the interlayer film is exposed at the edge of the laminated glass, and the glass and the interlayer film are peeled off or bubbles are generated. In some cases, the appearance of the laminated glass may be impaired. Depending on the type of plasticizer, the plasticizer may volatilize from the edge of the laminated glass when a laminated glass is produced through a decompression step or when used for a long time.

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

  The present invention solves the above problems, and the plasticizer contained in the laminate is difficult to be extracted and volatilized by water, and a laminate having a high moisture content can be rapidly dried in an atmosphere of low temperature and low humidity. It is an object of the present invention to provide a laminate in which water and plasticizer are less likely to phase separate from polyvinyl acetal in the laminate and water or plasticizer is less likely to bleed between layers.

According to the present invention, the above-mentioned problems are that the average residual hydroxyl group amount X is 15 to 50 mol%, the A layer containing polyvinyl acetal (A) and the plasticizer (Ap), and the average residual hydroxyl group amount Y is 10 to 45. It comprises a B layer containing a polyvinyl acetal (B) and a plasticizer (Bp) that are mol%, X ≧ Y, and the plasticizer (Ap) is one molecule of m-valent alcohol (Aa) (m is 2 to 4). An ester compound (Ae ₁ ) having a chemical structure obtained by an esterification reaction of a monovalent carboxylic acid (Ac) m molecule having 8 to 20 carbon atoms with one molecule of the m-valent alcohol (Aa). And an ester compound (Ae ₂ ) having a chemical structure obtained by an esterification reaction with the monovalent carboxylic acid (Ac) 1 to (m-1) molecule, and the plasticizer (Bp) is an n-valent alcohol ( Ba) 1 molecule (n represents a natural number of 2 to 4) And an ester compound (Be ₁ ) having a chemical structure obtained by an esterification reaction of a monovalent carboxylic acid (Bc) n molecule having 8 to 20 carbon atoms with one molecule of the n-valent alcohol (Ba) Ester compound (Be ₂ ) having a chemical structure obtained by esterification reaction with a polyvalent carboxylic acid (Bc) 1 to (n-1) molecule, and a hydroxyl value HV (Ap) mgKOH / g and the hydroxyl value HV (Bp) mgKOH / g of the plasticizer (Bp) are solved by the laminate satisfying HV (Ap)> HV (Bp).

  The m-valent alcohol (Aa) and / or the n-valent alcohol (Ba) is preferably a compound having 3 to 30 carbon atoms.

  The m-valent alcohol (Aa) and / or the n-valent alcohol (Ba) is preferably an alcohol selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, an ethylene glycol oligomer having 8 to 30 carbon atoms, and glycerin. .

  The monovalent carboxylic acid (Ac) and / or the monovalent carboxylic acid (Bc) is preferably a carboxylic acid selected from the group consisting of 2-ethylhexanoic acid, palmitic acid, stearic acid, and ricinoleic acid.

The ester compound (Ae ₁ ) and / or the ester compound (Be ₁ ) is preferably a compound having a molecular weight of 400 to 1200.

The ester compound (Ae ₂ ) is an ester compound of one molecule of an m-valent alcohol (Aa) and a monovalent carboxylic acid (Ac) (m−1) molecule, and the ester compound (Be ₂ ) is an n-valent alcohol (Ba ) It is preferably an ester compound of one molecule and a monovalent carboxylic acid (Bc) (n-1) molecule.

The ester compound (Ae ₂ ) and / or the ester compound (Be ₂ ) is preferably a compound having a molecular weight of 250 to 800.

The mass ratio of the ester compound (Ae ₁ ) and the ester compound (Ae ₂ ) contained in the plasticizer (Ap) is such that the ester compound (Ae ₁ ) / ester compound (Ae ₂ ) = 20/80 to 99.5 / 0. 5 is preferable.

The mass ratio of the ester compound (Be ₁ ) and the ester compound (Be ₂ ) contained in the plasticizer (Bp) is ester compound (Be ₁ ) / ester compound (Be ₂ ) = 30/70 to 100/0. Is preferred.

  HV (Ap) is preferably 1 to 100 mgKOH / g.

  HV (Bp) is preferably 0 to 80 mgKOH / g.

  It is preferable that content of the plasticizer (Ap) with respect to 100 mass parts of polyvinyl acetal (A) in A layer is less than content of the plasticizer (Bp) with respect to 100 mass parts of polyvinyl acetal (B) in B layer.

  It is preferable that content of the plasticizer (Ap) in A layer is 20-70 mass parts with respect to 100 mass parts of polyvinyl acetal (A).

  It is preferable that content of the plasticizer (Bp) in B layer is 30-80 mass parts with respect to 100 mass parts of polyvinyl acetal (B).

  It is preferable that the laminate is a laminate composed of three or more layers, and at least one of the two outer layers of the laminate is an A layer.

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

  According to the present invention, the plasticizer contained in the laminate is difficult to be extracted and volatilized by water, and even if the laminate having a high water content is rapidly dried in an atmosphere of low temperature and low humidity, It is possible to provide a laminate in which the plasticizer is less likely to phase separate from the polyvinyl acetal and is less likely to bleed between water and the plasticizer.

  The laminate of the present invention has a layer A containing polyvinyl acetal (A) and a plasticizer (Ap) having an average residual hydroxyl group amount X of 15 to 50 mol%, and an average residual hydroxyl group amount Y of 10 to 45 mol%. A B layer containing polyvinyl acetal (B) and a plasticizer (Bp) is provided.

  First, the polyvinyl acetal used in the present invention will be described.

  The average residual hydroxyl group amount X of the polyvinyl acetal (A) used in the present invention is 15 to 50 mol%. The average residual hydroxyl group amount X is preferably 17 to 40 mol%, more preferably 18 to 35 mol%, and further preferably 26 to 30 mol%. If the average residual hydroxyl group amount X is less than 15 mol%, the mechanical strength of the resulting laminate and the adhesion to glass may be reduced, and if it exceeds 50 mol%, it is in phase with the plasticizer (Ap). Solubility may be significantly reduced.

  The average degree of acetalization of the polyvinyl acetal (A) is not limited, but is usually preferably 45 to 82 mol%, more preferably 60 to 80 mol%, further preferably 68 to 76 mol%, and particularly preferably 69 to 73 mol%. . If the average degree of acetalization is less than 45 mol%, the compatibility with the plasticizer (Ap) may be significantly reduced, and if it exceeds 82 mol%, the mechanical strength of the resulting laminate may be reduced. is there.

  The average residual vinyl ester group amount of the polyvinyl acetal (A) is not particularly limited, but is usually preferably 0.01 to 15 mol%, more preferably 0.01 to 10 mol%, and still more preferably 0.01 to 5 mol%. . When the average residual vinyl ester group amount is less than 0.01 mol%, it is difficult to produce industrially inexpensively. When the average vinyl ester group amount exceeds 15 mol%, when the resulting laminate is used for a long period of time, vinyl ester groups are not formed. The laminated body is likely to be colored due to hydrolysis.

  The average residual hydroxyl group amount Y of the polyvinyl acetal (B) used in the present invention is 10 to 45 mol%. The average residual hydroxyl group amount Y is preferably 13 to 33 mol%, more preferably 15 to 30 mol%, and still more preferably 16 to 25 mol%. When the average residual hydroxyl group amount Y is less than 10 mol%, the mechanical strength and the adhesion to glass may be remarkably reduced, and when it exceeds 45 mol%, the compatibility with the plasticizer (Bp) may be reduced. is there.

  The average degree of acetalization of the polyvinyl acetal (B) is not limited, but is usually preferably 50 to 84 mol%, more preferably 65 to 82 mol%, further preferably 68 to 80 mol%, and particularly preferably 70 to 78 mol%. . If the average degree of acetalization is less than 50 mol%, the compatibility with the plasticizer (Bp) may be reduced, and if it exceeds 84 mol%, the mechanical strength of the resulting laminate may be reduced.

  The average residual vinyl ester group amount of the polyvinyl acetal (B) is not particularly limited, but is usually preferably 0.01 to 25 mol%, more preferably 3 to 16 mol%, still more preferably 3 to 15 mol%, and 4 to 13 Mole% is particularly preferred. Those having an average residual vinyl ester group amount of less than 0.01 mol% are difficult to produce industrially at low cost, and the compatibility with the plasticizer (Bp) may be lowered. On the other hand, when the content exceeds 25 mol%, the laminate is likely to be colored due to hydrolysis of the vinyl ester group when the resulting laminate is used for a long period of time.

  The average residual hydroxyl group amount X of the polyvinyl acetal (A) is the same as or larger than the average residual hydroxyl group amount Y of the polyvinyl acetal (B). The average residual hydroxyl group amount X is more preferably 3 to 20 mol% and particularly preferably 5 to 15 mol% larger than the average residual hydroxyl group amount Y. When satisfying the relationship of the average residual hydroxyl group content, water and plasticizers are difficult to phase separate from polyvinyl acetal in the laminate even if the laminate having a high water content is rapidly dried in an atmosphere of low temperature and low humidity. Further, it is preferable that bleeding between layers of water or a plasticizer does not easily occur, and it is preferable from the viewpoint of sound insulation performance when the laminate is used as an interlayer film for sound insulation laminated glass.

  The polyvinyl acetal (A) and the polyvinyl acetal (B) used in the present invention are produced using polyvinyl alcohol as a raw material. Polyvinyl alcohol can be obtained by a 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, 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 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 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 preferably 150 to 3000, more preferably 200 to 2500, and 1000 to 2000. Is more preferable. When the viscosity average degree of polymerization of polyvinyl alcohol is lower than 150, the mechanical strength of the obtained laminate tends to be insufficient, and when it is higher than 3000, the handleability of the obtained laminate may be deteriorated.

  The polyvinyl acetal used in the present invention can be produced by a 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, by adding a basic compound 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, and hydrochloric acid, sulfuric acid and nitric acid are particularly preferable. .

  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.

  Next, the plasticizer (Ap) used in the present invention will be described.

The plasticizer (Ap) contained in the layer A constituting the laminate of the present invention is one molecule of m-valent alcohol (Aa) (m represents a natural number of 2 to 4) and a monovalent carboxylic acid of 8 to 20 carbon atoms. (Ac) An ester compound (Ae ₁ ) having a chemical structure obtained by an esterification reaction with an m molecule, one molecule of the m-valent alcohol (Aa), and the monovalent carboxylic acid (Ac) 1 to (m−1) And an ester compound (Ae ₂ ) having a chemical structure obtained by an esterification reaction with a molecule.

  The m-valent alcohol (Aa) is not limited as long as it is a polyhydric alcohol having m hydroxyl groups, but is particularly a compound having 3 to 30 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. From the viewpoint of the compatibility between the plasticizer (Ap) and the polyvinyl acetal (A) used in the present invention and the plasticizing effect of the plasticizer (Ap) on the polyvinyl acetal (A). Specifically, the m-valent alcohol (Aa) is ethylene glycol, diethylene glycol, triethylene glycol, an ethylene glycol oligomer having 8 to 30 carbon atoms, propylene glycol, an oligomer of propylene glycol, and a compound having 6 to 30 carbon atoms. Glycerin, diglycerin and the like, but are not limited thereto. Ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol oligomers having 8 to 30 carbon atoms, and glycerin are particularly excellent in compatibility between the plasticizer (Ap) and polyvinyl acetal (A) used in the present invention. ) Is preferable from the viewpoint of particularly excellent plasticizing effect on polyvinyl acetal (A), and triethylene glycol, ethylene glycol oligomers having 8 to 30 carbon atoms, and glycerin are more preferable.

  Examples of the monovalent carboxylic acid having 8 to 20 carbon atoms include octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexadecanoic acid, 2-methylheptanoic acid, 2-ethylheptanoic acid, 2,2 -Dimethylhexanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid and the like. Among them, the monovalent carboxylic acid having 8 to 16 carbon atoms, more preferably 8 to 12 carbon atoms, and particularly preferably 8 to 10 carbon atoms is compatible with the polyvinyl acetal (A) of the obtained plasticizer (Ap) and It is preferable at the point which is excellent in the plasticization effect. Further, a monovalent carboxylic acid having 12 to 20 carbon atoms, preferably 16 to 20 carbon atoms, is extracted with water even when the obtained plasticizer (Ap) has a particularly high boiling point and the laminate is in contact with water. It is preferable from the viewpoint of difficulty.

The ester compound (Ae ₁ ) in the present invention is an ester compound having a chemical structure obtained by an esterification reaction between one molecule of m-valent alcohol (Aa) and one monovalent carboxylic acid (Ac) m molecule having 8 to 20 carbon atoms. is there. m is a natural number of 2 to 4, and preferably a natural number of 2 to 3. When m is less than ₂ , a compound (1- (m-1) molecule) corresponding to an ester compound (Ae ₂ ) which is an essential component in the laminate of the present invention described later is not included in the laminate. Therefore, it is inappropriate. When m exceeds 4, the compatibility of the plasticizer (Ap) with the polyvinyl acetal (A) and the plasticizing effect on the polyvinyl acetal (A) may decrease, which is not preferable.

Ester compound (Ae ₁₎ molecular weight of is not particularly limited, but is preferably 400 to 1200, more preferably from 400 to 800, more preferably from 400 to 600. When the molecular weight is less than 400, the ester compound (Ae ₁ ) may easily volatilize during long-term use. When the molecular weight exceeds 1200, the resulting plasticizer (Ap) is in phase with the polyvinyl acetal (A). The solubility and the plasticizing effect on the polyvinyl acetal (A) may be lowered, which is not preferable.

Specifically, the ester compound (Ae ₁ ) is, for example, triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, triethylene glycol distearate, triethylene glycol dioleate. Art, glycerin tri (2-ethylhexanoic acid) ester, glycerin tri (stearic acid) ester and the like can be mentioned, but are not limited thereto. Also these ester compounds (Ae ₁₎ is used alone or in combination of two or more thereof.

The ester compound (Ae ₂ ) in the present invention is a chemistry obtained by an esterification reaction between one molecule of m-valent alcohol (Aa) and one monovalent carboxylic acid (Ac) 1 to (m−1) molecule having 8 to 20 carbon atoms. An ester compound having a structure. That is, the ester compound (Ae ₂ ) is selected from m-valent alcohol (Aa) and monovalent carboxylic acid (Ac) having 8 to 20 carbon atoms, which are the same as those used for constituting the ester compound (Ae ₁ ). It is a compound having at least one hydroxyl group obtained by esterification reaction of alcohol and carboxylic acid. By using the ester compound (Ae ₂ ) having the above specific chemical structure, the effect of the present invention is exhibited.

Ester compound (Ae ₂₎ molecular weight of is not particularly limited, but is preferably 250 to 800, more preferably from 250 to 600, more preferably from 250 to 450. When the molecular weight is less than 250, the ester compound (Ae ₂ ) may easily volatilize during long-term use. When the molecular weight exceeds 800, the plasticizer (Ap) is compatible with the polyvinyl acetal (A), The plasticizing effect to polyvinyl acetal (A) may fall, and is not preferable.

Specific examples of the ester compound (Ae ₂ ) in the present invention include triethylene glycol mono-2-ethylhexanoate, tetraethylene glycol mono-2-ethylhexanoate, triethylene glycol monostearate, triethylene glycol monooleate. Art, glycerin di (2-ethylhexanoic acid) ester, glycerin mono (2-ethylhexanoic acid) ester, glycerin di (stearic acid) ester, glycerin mono (stearic acid) ester, and the like are exemplified, but not limited thereto. Also these ester compounds (Ae ₂₎ is used alone or in combination of two or more thereof.

The A layer in the present invention contains a plasticizer (Ap) composed of an ester compound (Ae ₁ ) and an ester compound (Ae ₂ ). Although the content ratio of the ester compound (Ae ₁ ) and the ester compound (Ae ₂ ) in the plasticizer (Ap) is not particularly limited, the mass ratio of the ester compound (Ae ₁ ) / ester compound (Ae ₂ ) = 20/80 to It is preferably 99.9 / 0.1, more preferably 30/70 to 99.7 / 0.3, further preferably 50/50 to 99.5 / 0.5, 80 Particularly preferred is / 20 to 99.5 / 0.5. If the mass ratio of the ester compound (Ae ₁ ) / ester compound (Ae ₂ ) is smaller than 20/80, the ester compound (Ae ₂ ) may be volatilized or extracted with water when the laminate of the present invention is used for a long time. When the mass ratio of the ester compound (Ae ₁ ) / ester compound (Ae ₂ ) is larger than 99.9 / 0.1, a laminate having a high water content is rapidly increased in an atmosphere of low temperature and low humidity. When dried, water and plasticizer in the laminate may phase separate from polyvinyl acetal, and bleeding between water and plasticizer layers may occur.

  The hydroxyl value HV (Ap) of the plasticizer (Ap) is not particularly limited, but is preferably 1 to 100 mgKOH / g, more preferably 1 to 80 mgKOH / g, and 1 to 60 mgKOH / g. Further preferred. When HV (Ap) is less than 1 mgKOH / g, when a laminate having a high water content is rapidly dried in an atmosphere of low temperature and low humidity, water and plasticizer may phase separate from polyvinyl acetal in the laminate. In addition, bleeding between layers of water or a plasticizer may occur, which is not preferable. If it exceeds 100 mgKOH / g, the laminate easily absorbs water, and the laminate of the present invention is used for a long time. In addition, extraction of the components contained in the plasticizer (Ap) with water may be a problem, which is not preferable. The hydroxyl value HV (Ap) of the plasticizer (Ap) and the hydroxyl value HV (Bp) of the plasticizer (Bp) are measured according to JIS K1557.

  Although content of the plasticizer (Ap) in A layer which comprises the laminated body of this invention is not specifically limited, 20-70 mass parts is preferable normally with respect to 100 mass parts of polyvinyl acetal (A), and 25-60 mass parts. Is more preferable, and 30-50 mass parts is further more preferable. When the content of the plasticizer (Ap) is less than 20 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (A), the resulting laminate tends to have insufficient flexibility and impact as an interlayer film for laminated glass. Absorption may be a problem. On the other hand, when the amount is more than 70 parts by mass, the resulting laminated body tends to have insufficient mechanical strength.

  Next, the plasticizer (Bp) in the present invention will be described.

The plasticizer (Bp) is obtained by an esterification reaction of one molecule of an n-valent alcohol (Ba) (n represents a natural number of 2 to 4) and a monovalent carboxylic acid (Bc) of 8 to 20 carbon atoms. Obtained by an esterification reaction of an ester compound (Be ₁ ) having a chemical structure with one molecule of the n-valent alcohol (Ba) and a monovalent carboxylic acid (Bc) 1 to (n-1) molecule having 8 to 20 carbon atoms. An ester compound (Be ₂ ) having a chemical structure is included.

  The n-valent alcohol (Ba) is not limited as long as it is a polyhydric alcohol having n hydroxyl groups, but in particular, a compound having 3 to 30 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms. It is preferable from the viewpoint of the compatibility between the obtained plasticizer (Bp) and the polyvinyl acetal (B) and the plasticizing effect of the plasticizer (Bp) on the polyvinyl acetal (B). The n-valent alcohol (Ba) is specifically an ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol oligomer having 8 to 30 carbon atoms, propylene glycol, propylene glycol oligomer, and a compound having 6 to 30 carbon atoms. Glycerin, diglycerin and the like, but are not limited thereto. Ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol oligomer having 8 to 30 carbon atoms, and glycerin are particularly excellent in compatibility between the plasticizer (Bp) and the polyvinyl acetal (B) used in the present invention. ) Is preferable from the viewpoint of particularly excellent plasticizing effect on polyvinyl acetal (B), and triethylene glycol, ethylene glycol oligomers having 8 to 30 carbon atoms, and glycerin are more preferable.

  Examples of the monovalent carboxylic acid having 8 to 20 carbon atoms include octanoic acid, 2-ethylhexanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, hexadecanoic acid, 2-methylheptanoic acid, 2-ethylheptanoic acid, 2,2 -Dimethylhexanoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid and the like. Among these, monovalent carboxylic acids having 8 to 16 carbon atoms, more preferably 8 to 12 carbon atoms, and particularly preferably 8 to 10 carbon atoms are compatible with the plasticizer (Bp) and the polyvinyl acetal (B) and plasticizing effect. It is preferable in that it is particularly excellent. Further, monovalent carboxylic acids having 12 to 20 carbon atoms, preferably 16 to 20 carbon atoms, are preferable from the viewpoint that the plasticizer (Bp) has a particularly high boiling point, and even when the laminate is in contact with water, it is particularly difficult to extract with water. .

The ester compound (Be ₁ ) is a compound having a chemical structure obtained by an esterification reaction between one molecule of an n-valent alcohol (Ba) and one molecule of a monovalent carboxylic acid (Bc) having 8 to 20 carbon atoms. Here, n is a natural number of 2 to 4, preferably a natural number of 2 to 3. When n is less than ₂ , a compound corresponding to the ester compound (Be ₂ ), which is an essential component in the laminate of the present invention described later, is not included in the laminate, which is inappropriate. When n exceeds 4, the compatibility of the plasticizer (Bp) with the polyvinyl acetal (B) and the plasticizing effect on the polyvinyl acetal (B) may be reduced, which is not preferable.

The ester compound the molecular weight of (Be ₁₎ is not particularly limited, but is preferably 400 to 1200, more preferably from 400 to 800, more preferably from 400 to 600. When the molecular weight is less than 400, the ester compound (Be ₁ ) may easily volatilize during long-term use, and when the molecular weight exceeds 1200, the plasticizer (Bp) is compatible with the polyvinyl acetal (B), The plasticizing effect to polyvinyl acetal (B) may fall, and is not preferable.

Specific examples of the ester compound (Be ₁ ) in the present invention include triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-2-ethylhexanoate, triethylene glycol distearate, triethylene glycol dioleate. Art, glycerin tri (2-ethylhexanoic acid) ester, glycerin tri (stearic acid) ester and the like can be mentioned, but are not limited thereto. These ester compounds (Be ₁ ) may be used alone or in combination of two or more.

The ester compound (Be ₂ ) in the present invention is obtained by an esterification reaction of 1 molecule of an n-valent alcohol (Ba) and a monovalent carboxylic acid (Bc) 1 to (n-1) molecule having 8 to 20 carbon atoms. A compound having a chemical structure. That is, the ester compound (Be ₂ ) is selected from n-valent alcohol (Ba) and monovalent carboxylic acid (Bc) having 8 to 20 carbon atoms, which are the same as those used for constituting the ester compound (Be ₁ ). And a compound having at least one hydroxyl group, which is obtained by an esterification reaction between an alcohol and a carboxylic acid. In the present invention, the object of the present invention can be suitably achieved by using an ester compound (Be ₂ ) having such a specific chemical structure.

The ester compound the molecular weight of (Be ₂₎ is not particularly limited, but is preferably 250 to 800, more preferably from 250 to 600, more preferably from 250 to 450. When the molecular weight is less than 250, the ester compound (Be ₂ ) may be easily volatilized during long-term use. When the molecular weight exceeds 800, the plasticizer (Bp) is compatible with the polyvinyl acetal (B), The plasticizing effect to polyvinyl acetal (B) may fall, and is not preferable.

Specific examples of the ester compound (Be ₂ ) in the present invention include triethylene glycol mono-2-ethylhexanoate, tetraethylene glycol mono-2-ethylhexanoate, triethylene glycol monostearate, triethylene glycol monooleate. Art, glycerin di (2-ethylhexanoic acid) ester, glycerin mono (2-ethylhexanoic acid) ester, glycerin di (stearic acid) ester, glycerin mono (stearic acid) ester and the like may be mentioned, but are not limited thereto. These ester compounds (Be ₂ ) may be used alone or in combination of two or more.

The B layer in the laminate of the present invention contains a plasticizer (Bp) composed of an ester compound (Be ₁ ) and an ester compound (Be ₂ ). Although the content rate of the ester compound (Be ₁ ) and the ester compound (Be ₂ ) in the plasticizer (Bp) is not particularly limited, the ester compound (Be ₁ ) / ester compound (Be ₂ ) = 30/70 to mass ratio. 100/0 is preferable, 50/50 to 100/0 is more preferable, 80/20 to 100/0 is further preferable, and 85/15 to 100/0 is particularly preferable. . When the mass ratio of the ester compound (Be ₁ ) / ester compound (Be ₂ ) is smaller than 30/70, the ester compound (Be ₂ ) may be volatilized or extracted with water when the laminate of the present invention is used for a long period of time. It may cause problems and is not preferable. The mass ratio of ester compound (Be ₁ ) / ester compound (Be ₂ ) is 100/0 means that the plasticizer (Bp) is composed of the ester compound (Be ₁ ) and the ester compound (Be ₂ ) It means not containing.

  The hydroxyl value HV (Bp) of the plasticizer (Bp) is not particularly limited, but is preferably 0 to 80 mgKOH / g, more preferably 0 to 60 mgKOH / g, and 1 to 40 mgKOH / g. Further preferred. When HV (Bp) exceeds 80 mgKOH / g, the laminate easily absorbs water, and when the laminate of the present invention is used for a long period of time, extraction of components contained in the plasticizer (Bp) with water becomes a problem. This is not preferable.

  Although content of the plasticizer (Bp) in B layer which comprises the laminated body of this invention is not specifically limited, Usually 30-80 mass parts is preferable with respect to 100 mass parts of polyvinyl acetal (B), 33-75 mass parts. Is more preferable, and 40-70 mass parts is further more preferable. When the content of the plasticizer (Bp) is less than 30 parts by mass with respect to 100 parts by mass of the polyvinyl acetal (B), a desired sound insulation is exhibited when the obtained laminate is used for an interlayer film for sound insulation laminated glass. There are cases where it is not possible. On the other hand, when the amount is more than 80 parts by mass, the resulting laminated body tends to have insufficient mechanical strength.

  In the present invention, the relationship between the content of the plasticizer (Ap) in the A layer and the content of the plasticizer (Bp) in the B layer is not strictly limited, but the polyvinyl acetal (A) 100 in the A layer is not limited. It is preferable that content of the plasticizer (Ap) with respect to a mass part is less than content of the plasticizer (Bp) with respect to 100 mass parts of polyvinyl acetal (B) in B layer. From the standpoint that sound insulation can be exhibited in the laminated glass using the laminate of the present invention, the plasticizer (Ap) content relative to 100 parts by mass of the polyvinyl acetal (A) is a plasticizer relative to 100 parts by mass of the polyvinyl acetal (B) ( The content of Bp) is preferably 5 to 60 parts by mass and more preferably 10 to 40 parts by mass.

  In the laminate of the present invention, the hydroxyl value HV (Ap) and the hydroxyl value HV (Bp) satisfy the relationship of HV (Ap)> HV (Bp). Preferably, HV (Ap)> HV (Bp) +1, more preferably HV (Ap)> HV (Bp) +3, more preferably HV (Ap)> HV (Bp) +5, particularly preferably HV (Ap)> HV (Bp) +10, optimally HV (Ap)> HV (Bp) +15. When HV (Ap) and HV (Bp) do not satisfy the relationship of HV (Ap)> HV (Bp), a laminate with a high water content is rapidly dried in a low temperature and low humidity atmosphere. In this case, water or a plasticizer is phase-separated from polyvinyl acetal and becomes opaque, or water or a plasticizer bleeds between layers of the laminate to cause delamination or decrease in transparency.

The plasticizer (Ap) and the plasticizer (Bp) in the present invention may be used in any combination as long as the above-mentioned regulations are satisfied. From the standpoint of minimizing the type of compound used as a raw material and minimizing the acquisition cost and storage cost of the compound, when the laminate of the present invention is used for a long period of time, the property is less likely to change with time. It is preferable that the compound contained in the plasticizer (Ap) and the compound contained in the plasticizer (Bp) have as similar chemical structures as possible, and more preferably the same compound. Accordingly, in the present invention, the m-valent alcohol (Aa) and the n-valent alcohol (Ba) are preferably the same compound, and the monovalent carboxylic acid (Ac) and the plasticizer ( The monovalent carboxylic acid (Bc) used for Bp) is preferably the same compound. The ester compound (Ae ₁ ) and the ester compound (Be ₁ ) are more preferably the same compound, and the ester compound (Ae ₂ ) and the ester compound (Be ₂ ) are more preferably the same compound.

  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, a well-known phenolic antioxidant, phosphorus antioxidant, sulfur antioxidant, etc. can be used. Of these, phenolic antioxidants are preferred. Antioxidants may be used alone or in combination of two or more. When it contains antioxidant, the quantity is not specifically limited, However 0.0001-5 mass% is preferable normally with respect to the mass of a laminated body, and 0.001-1 mass% is more preferable. 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, 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 is not particularly limited, but is usually preferably 0.0001 to 5% by mass, and more preferably 0.001 to 1% by mass with respect to the mass of the laminate. When the amount is less than 0.0001% by mass, a sufficient effect as an ultraviolet absorber may not be obtained, and when the amount is more than 5% by mass, a remarkable effect cannot be expected.

  The laminate of the present invention is particularly preferably used as an interlayer film for laminated glass. 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 addition, when using the laminated body of the present invention as an interlayer film for laminated glass, if there is a layer that does not contact with glass, an adhesion modifier may not be added to the layer, or the amount added may be reduced. It is preferable from the viewpoint of suppressing whitening when the body absorbs water.

  In particular, when the layer that adheres to the glass is the A layer, a magnesium salt such as magnesium acetate, magnesium acetate tetrahydrate, magnesium butanoate, magnesium 2-ethylbutanoate, magnesium 2-ethylhexanoate is added to the A layer. It is preferable. The addition amount of the adhesion 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 fragment 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. Magnesium salt absorbs less water than potassium salt and sodium salt, so when magnesium salt is added to layer A as an adhesive strength modifier, a laminate with a high moisture content is rapidly applied in a low temperature and low humidity atmosphere. Even when dried, water and plasticizer are difficult to phase separate from polyvinyl acetal in the laminate, and water and plasticizer are difficult to bleed between layers of the laminate.

  The method for producing the laminate of the present invention is not particularly limited, and conventionally known methods can be applied. For example, after the components constituting the A layer and the components constituting the B layer are melt-kneaded with an extruder and then co-extruded with a multilayer film forming machine; the A layer individually prepared by hot pressing or casting after the melt-kneading And a method of laminating and laminating the B layers and adhering them by hot pressing or the like, if necessary.

  The moisture content of the laminate of the present invention is not particularly limited, but if the moisture content is too high, the plasticizer may bleed from the laminate. -0.8 mass% is more preferable, and 0.2-0.7 mass% is further more 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, and further preferably 0.1 to 0.7 mm. If it is thinner than 0.05 mm, the mechanical strength of the laminate of the present invention tends to decrease, and if it is thicker than 1.2 mm, the flexibility of the laminate of the present invention tends to be insufficient, as an interlayer film for laminated glass. In use, the safety of the resulting laminated glass may be reduced.

  The thickness of the B layer is usually preferably 0.01 to 1 mm, more preferably 0.02 to 0.8 mm, and even more preferably 0.05 to 0.5 mm. If it is thinner than 0.01 mm, the sound insulation performance of the laminated glass having the laminate of the present invention as an intermediate film may be deteriorated, and even if it is thicker than 1 mm, the mechanical strength of the laminate of the present invention does not tend to improve any more. It is in.

  Further, the ratio of the thickness of the A layer and the thickness of the B layer is not particularly limited, but is preferably 0.05 to 4, more preferably 0.07 to 2, more preferably 0.1 to 2, from the viewpoint of the mechanical strength and the sound insulation. 0.8 is more preferable.

  In the laminate of the present invention, at least one of the outermost layers of the laminate is preferably an A layer. Examples of such laminates are A layer / B layer / A layer, A layer / B layer / A layer / B layer / A layer and the like. A laminate in which one of the outermost layers such as A layer / B layer / A layer / B layer is the A layer can be mentioned. In particular, when the laminate of the present invention is used as an interlayer film for laminated glass, it is preferable that both outermost layers are A layers because the adhesiveness between the laminate and the glass can be adjusted appropriately.

  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 usually 0.2 to 2 mm is preferable, 0.25 to 1.8 mm is more preferable, and 3-1.5 mm is more preferable. When the thickness of the laminate is thinner than 0.2 mm, the mechanical strength tends to be insufficient, and when it is thicker than 2 mm, the flexibility tends to be insufficient.

  The glass material when using the laminate of the present invention as an interlayer film for laminated glass is not particularly limited, inorganic glass such as float plate glass, heat tempered glass, chemically tempered glass; organic glass such as polymethyl methacrylate, polycarbonate, etc. Conventionally known glass can be used. These may be colorless or colored, transparent or non-transparent, and two or more of them may be used in combination. Although there is no limitation in particular in the thickness of glass, Usually, 20 mm or less is preferable and 10 mm or less is more preferable.

  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), What formed the uneven structure in the outermost surface of the laminated body by well-known methods, such as a melt fracture and embossing, is preferable.

  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; Conventionally known methods such as a processing method can be mentioned.

An example of the production conditions when using a vacuum laminator apparatus is as follows: glass at a temperature of 100 to 200 ° C., preferably 130 to 160 ° C. under a reduced pressure of 1 × 10 ^{−6 to} 3 × 10 ⁻² MPa. An interlayer film for laminated glass is laminated. A method using a vacuum bag is described, for example, in EP 1356683. For example, lamination is performed at 130 to 145 ° C. under a pressure of about 2 × 10 ⁻² MPa.

  In the method of processing by an autoclave after temporarily bonding with a nip roll, an example of the operating condition of the nip roll is that the glass and the laminate are heated to 30 to 70 ° C. with an infrared heater or the like, and then deaerated by being sandwiched between rolls and further 50 to 50- After heating to 120 ° C., the film is temporarily bonded by pressing with a roll. The process of processing by an autoclave is implemented for 30 minutes-200 minutes at the temperature of 130-145 degreeC under the pressure of 1.0-1.5 MPa, for example.

  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 3 L (liter) glass container equipped with a reflux condenser, thermometer, and squid type stirring blade, ion exchange water 2000 g, polyvinyl alcohol (PVA-1) (viscosity average polymerization degree 1700, saponification degree 99 mol%) 200 g (PVA concentration 9.1%), and the contents were heated to 95 ° C. and completely dissolved. Next, the mixture was gradually cooled to 7 ° C. over about 30 minutes with stirring at 120 rpm, 113 g of butyraldehyde and 70 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 immediately cooled in a cold water bath. After washing the polyvinyl acetal resin with ion-exchanged water, the remaining acid catalyst was neutralized with an aqueous sodium hydroxide solution, further washed with ion-exchanged water, dehydrated and dried to obtain polyvinyl butyral (PVB-1). . When the obtained PVB-1 was measured according to JIS K6728-1977 (hereinafter referred to as JIS K6728), as shown in Table 1, the average degree of acetalization was 68 mol%, and the average residual vinyl ester group amount was 1 mol%. The average residual hydroxyl group amount was 31 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 118 g to obtain PVB-2. The obtained PVB-2 was 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%. there were.

(Preparation of PVB-3)
In the preparation of PVB-1, PVA-1 was changed to 200 g of PVA-2 (viscosity average polymerization degree 1700, saponification degree 92 mol%), and butyraldehyde usage was changed to 120 g, and a butyralization reaction was further carried out at 5 ° C. After the implementation, the temperature was raised to 68 ° C. over 70 minutes, and PVB-3 was obtained in the same manner except that the reaction was performed at 68 ° C. for 110 minutes. The obtained PVB-3 was measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 74 mol%, the average residual vinyl ester group amount was 7 mol%, and the average residual hydroxyl group amount was 19 mol%. there were.

(Preparation of PVB-4)
In the preparation of PVB-3, PVA-2 was changed to 200 g of PVA-3 (viscosity average polymerization degree 1700, saponification degree 89 mol%), but butyraldehyde was used in an amount of 117 g, and a butyralization reaction was carried out at 5 ° C. After the implementation, the temperature was raised to 65 ° C. over 70 minutes, and PVB-4 was obtained in the same manner except that the reaction was performed at 65 ° C. for 140 minutes. The obtained PVB-4 was measured according to JIS K6728. As shown in Table 1, the average degree of acetalization was 75 mol%, the average residual vinyl ester group amount was 9 mol%, and the average residual hydroxyl group amount was 16 mol%. there were.

Example 1
(Production of laminate)
100 parts by mass of PVB-1 and 39 parts by mass of glycerin tri (2-ethylhexanoic acid) ester 85% by mass and glycerin di (2-ethylhexanoic acid) ester 15% by mass of plasticizer (Ap) Then, the mixture was kneaded at 150 ° C. for 8 minutes in a lab plast mill. The obtained kneaded material was pressed for 30 minutes in a mold having a thickness of 0.38 mm at 150 ° 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 and 60 parts by mass of glycerin tri (2-ethylhexanoic acid) ester 95% by mass and glycerin di (2-ethylhexanoic acid) ester 5% by mass plasticizer (Bp ) Was kneaded in a Laboplast mill at 150 ° C. for 8 minutes. The obtained kneaded material was pressed with a 0.14 mm-thick mold at 160 ° C. and 50 kg / cm ² for 30 minutes 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 0.9 mm thick formwork at 135 ° C. and 10 kg / cm ² , and layer A (0.38 mm) / Laminated body-1 consisting of B layer (0.14 mm) / A layer (0.38 mm) was obtained.

(Humidity control of high moisture content laminates)
The layered product-1 obtained above was conditioned for 12 hours in an atmosphere of 35 ° C. and 80% RH in a thermo-hygrostat. The humidity-adjusted laminate-1 was further subjected to humidity control under the following conditions (a), (b), and (c), and the humidity control time was evaluated according to the following three-stage criteria. there were.
(conditions)
Condition (a): Treated at 23 ° C. and 28% RH for 12 hours.
Condition (b): treatment at 29 ° C. and 55% RH for 12 hours, followed by treatment at 23 ° C. and 28% RH for 12 hours.
Condition (c): After 12 hours of treatment at 32 ° C. and 68% RH, followed by treatment at 29 ° C. and 55% RH for 12 hours, followed by treatment at 26 ° C. and 40% RH for 12 hours, and finally Treated at 23 ° C. and 28% RH for 12 hours.
(Standard)
“12 hours”: The laminate does not cause white turbidity and delamination under the condition (a), and the moisture content is 0.7% or less.
“24 hours”: In the condition (a), white turbidity and delamination occur, but in the condition (b), the laminate does not cause white turbidity and delamination, and the moisture content is 0.7% or less.
“48 hours”: White turbidity and delamination occur in both conditions (a) and (b), but the laminate does not cause white turbidity or delamination in condition (c), and the moisture content is 0.7%. What is below.

  “12 hours” in the above criteria indicates that even when dried rapidly, water and plasticizer are not easily phase-separated from polyvinyl acetal in the laminate, and bleeding between layers of water and plasticizer hardly occurs. Further, it indicates that more gradual drying is required as “24 hours” and “48 hours” are reached.

(Plasticizer bleed test at high water content)
The laminate-1 obtained above was dried at 23 ° C. and 28% RH for 5 days, and then treated in an atmosphere at 35 ° C. and 80% RH. Visual confirmation after 12 hours, 24 hours and 48 hours after the start of the treatment of the laminate-1 indicates that there is no plasticizer bleed after 12 hours and plasticizer bleed occurs after 24 hours. “12 hours”, when no plasticizer bleed occurs after 24 hours, and when plasticizer bleed occurs after 48 hours, “24 hours”, and when no plasticizer bleed occurs after 48 hours, “48 hours” , “48 hours”.

(Production of laminated glass)
The laminate-1 of 30 cm × 30 cm was stored for 5 days in an atmosphere of 23 ° C. and 28% RH, and after humidity adjustment, it was quickly sandwiched between two float glasses (30 cm × 30 cm × 2.2 mm). After heating to ° C., temporary bonding was performed using a nip roll. The obtained temporary adhesive body was put in an autoclave and treated for 60 minutes under conditions of 135 ° C. and 1.2 MPa to obtain a laminated glass-1.

(Hot water boiling test for laminated glass)
Laminated glass-1 was treated with hot water at 40 ° C. for 12 hours and then treated in an atmosphere of 23 ° C. and 28% RH for 108 hours (this treatment is defined as one cycle). After repeating this process 10 times, from each end of the laminated glass, visually check for defects (exfoliation of the glass and the interlayer film for laminated glass, peeling of the interlayer of the interlayer film) due to extraction of components contained in the laminate. According to the above, it was evaluated as “none” when evaluated in three stages of “none”, “somewhat present”, and “present”.

(Examples 2-27, Comparative Examples 1-10)
A laminated body and a laminated glass were produced in the same manner as in Example 1 except that the compositions of the A layer and the B layer were changed as shown in Table 2, Table 3, and Table 5, and were similarly evaluated. The results are shown in Table 4 or Table 6.

  As shown in the examples and comparative examples, the laminate of the present invention has a high moisture content at a high temperature and high humidity, and then is rapidly dried in a low temperature and low humidity atmosphere. Water and plasticizer are difficult to phase separate from polyvinyl acetal, and water and plasticizer bleed do not occur between the layers of the laminate.

  The reason why the laminate of the present invention exhibits such characteristics is unknown, but the hydroxyl value HV (Ap) of the plasticizer (Ap) in the A layer is the hydroxyl value HV (Bp) of the plasticizer (Bp) in the B layer. When the moisture content of the laminate in which the outermost layers are both A layers is high due to the fact that the water content is higher, moisture is transferred from the B layer to the A layer as the water from the A layer evaporates. As a result of the migration, it is considered that the water content of the B layer also decreases before phase separation or bleeding occurs.

  The laminated body of the present invention is such that the plasticizer contained in the laminated body is difficult to be extracted and volatilized by water, and even if the laminated body having a high water content is rapidly dried in an atmosphere of low temperature and low humidity, And the plasticizer is difficult to phase separate from the polyvinyl acetal, and bleeding between layers of water and the plasticizer is difficult to occur.

Claims (16)

A layer containing a polyvinyl acetal (A) having an average residual hydroxyl group content X of 15 to 50 mol% and a plasticizer (Ap), and a plastic having a polyvinyl acetal (B) having an average residual hydroxyl group content Y of 10 to 45 mol% A B layer containing an agent (Bp),
X ≧ Y,
A plasticizer (Ap) is obtained by an esterification reaction of one molecule of m-valent alcohol (Aa) (m represents a natural number of 2 to 4) and a monovalent carboxylic acid (Ac) m molecule of 8 to 20 carbon atoms. It has a chemical structure obtained by an esterification reaction of an ester compound (Ae ₁ ) having a chemical structure, one molecule of the m-valent alcohol (Aa) and the monovalent carboxylic acid (Ac) 1 to (m−1) molecule. An ester compound (Ae ₂ ),
A plasticizer (Bp) is obtained by an esterification reaction of one molecule of n-valent alcohol (Ba) (n represents a natural number of 2 to 4) and a monovalent carboxylic acid (Ba) n molecule of 8 to 20 carbon atoms. It has a chemical structure obtained by an esterification reaction between an ester compound (Be ₁ ) having a chemical structure, one molecule of the n-valent alcohol (Ba) and one molecule of the monovalent carboxylic acid (Bc) 1 to (n-1). An ester compound (Be ₂ ),
The hydroxyl value HV (Ap) mgKOH / g of the plasticizer (Ap) and the hydroxyl value HV (Bp) mgKOH / g of the plasticizer (Bp) satisfy HV (Ap)> HV (Bp).
Laminated body. The laminate according to claim 1, wherein the m-valent alcohol (Aa) and / or the n-valent alcohol (Ba) is a compound having 3 to 30 carbon atoms. The m-valent alcohol (Aa) and / or the n-valent alcohol (Ba) is an alcohol selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, an ethylene glycol oligomer having 8 to 30 carbon atoms, and glycerin. The laminate according to 1 or 2. The monovalent carboxylic acid (Ac) and / or the monovalent carboxylic acid (Bc) is a carboxylic acid selected from the group consisting of 2-ethylhexanoic acid, palmitic acid, stearic acid, and ricinoleic acid. The laminated body in any one of. Ester compound (Ae ₁₎ and / or ester compounds (Be _1), a compound having a molecular weight 400 to 1200 A laminate according to any one of claims 1 to 4. The ester compound (Ae ₂ ) is an ester compound of 1 molecule of m-valent alcohol (Aa) and a monovalent carboxylic acid (Ac) (m-1) molecule,
The ester compound (Be ₂ ) is an ester compound of an n-valent alcohol (Ba) molecule and a monovalent carboxylic acid (Bc) (n-1) molecule,
The laminated body in any one of Claims 1-5. Ester compound (Ae ₂₎ and / or ester compounds (Be _2), a compound having a molecular weight 250 to 800, the laminated body according to any one of claims 1 to 6. The mass ratio of the ester compound (Ae ₁ ) and the ester compound (Ae ₂ ) contained in the plasticizer (Ap) is such that the ester compound (Ae ₁ ) / ester compound (Ae ₂ ) = 20/80 to 99.5 / 0. The laminate according to any one of claims 1 to 7, which is 5. The mass ratio of the ester compound (Be ₁ ) and the ester compound (Be ₂ ) contained in the plasticizer (Bp) is ester compound (Be ₁ ) / ester compound (Be ₂ ) = 30/70 to 100/0. The laminated body in any one of Claims 1-8. The laminated body in any one of Claims 1-9 whose HV (Ap) is 1-100 mgKOH / g. The laminated body in any one of Claims 1-10 whose HV (Bp) is 0-80 mgKOH / g. Content of the plasticizer (Ap) with respect to 100 mass parts of polyvinyl acetal (A) in A layer is less than content of the plasticizer (Bp) with respect to 100 mass parts of polyvinyl acetal (B) in B layer. The laminated body in any one of. The laminated body in any one of Claims 1-12 whose content of the plasticizer (Ap) in A layer is 20-70 mass parts with respect to 100 mass parts of polyvinyl acetal (A). The laminated body in any one of Claims 1-13 whose content of the plasticizer (Bp) in B layer is 30-80 mass parts with respect to 100 mass parts of polyvinyl acetal (B). The laminate according to any one of claims 1 to 14, which is a laminate comprising three or more layers, and at least one of the two outer layers of the laminate is an A layer. Laminated glass containing the laminate according to any one of claims 1 to 15.