JP2019025885A - Laminate - Google Patents

Abstract

To provide a laminate which can hold initial self-adhesiveness even when stored for a long period of time and exhibits excellent safety performance when used as an intermediate film for laminated glass.SOLUTION: There is provided a laminate which has a layer (1) and a layer (2) on at least one surface of the layer (1), where the layer (1) contains a polymer compound (I) and the layer (2) contains a polymer compound (II), and when a stress at the time of 10% elongation at 23°C of the laminate is defined as SMPa, a stress at the time of 10% elongation at 23°C after the laminate has been stored at 23°C and 50% RH for 5 weeks is defined as SMPa and a stress at the time of 10% elongation at 23°C after the laminate has been treated at 140°C and 50% RH for 30 minutes, cooled to 23°C in one hour after the treatment and stored at 23°C and 50% RH for 5 weeks after the cooling is defined as SMPa, S/S≥0.2 and/or S-S≤1.0, S/S≤0.9 and/or S-S≥0.2 and S-S>0 are satisfied.SELECTED DRAWING: None

Description

  The present invention relates to a laminate that is less likely to be handled at the initial stage of production and after being stored for a long period of time, and that exhibits excellent safety performance when used as an interlayer film for laminated glass.

  Laminated glass obtained by sandwiching an interlayer film for laminated glass, which has excellent strength, transparency, flexibility, and adhesiveness with glass, is used in various safety glasses such as automobile windshields. .

  By the way, as the interlayer film for laminated glass, it is preferable to use a flexible film at a use temperature, for example, a temperature near room temperature, from the viewpoint of suppressing an impact when a person or an object collides with the laminated glass. For example, in Patent Document 1, it is preferable that a laminated glass used for a windshield of an automobile has a head impact index (HIC value) of less than 1000, and the HIC value of the laminated glass is such low. In order to obtain a value, it is described that it is preferable to use a flexible interlayer film for laminated glass containing a plasticizer in a specific amount or more with respect to polyvinyl acetal.

JP-A-2005-206445

  However, the interlayer film for laminated glass with improved flexibility as in Patent Document 1 generally tends to have high adhesiveness, and the interlayer film for laminated glass made of plasticized polyvinyl acetal is stored in a state of being wound on a roll. Then, there is a problem that blocking due to self-adhesion occurs and handling becomes difficult. Thus, in the interlayer film for laminated glass, the self-adhesiveness and flexibility are in a trade-off relationship, and it is difficult to achieve both properties at a high level.

  Therefore, the present invention is a laminate that can maintain the initial self-adhesiveness even when stored for a long period of time and has a small stress change with time, and is used as an interlayer film for laminated glass. An object of the present invention is to provide a laminate having improved flexibility and exhibiting excellent safety performance.

According to the invention, the object is
[1] A laminate comprising a layer (1) and a layer (2) on at least one side of the layer (1),
The layer (1) contains the polymer compound (I),
The layer (2) contains the polymer compound (II),
The stress at 10% elongation of the laminate at 23 ° C. is S ₁ MPa,
After the laminate is stored at 23 ° C. and 50% RH for 5 weeks, the stress at 10% elongation at 23 ° C. is S ₂ MPa,
The laminate was treated at 140 ° C. for 30 minutes, cooled to 23 ° C. within 1 hour after the treatment, and after cooling, the stress at 10% elongation at 23 ° C. after storage at 23 ° C. and 50% RH for 5 weeks. S ₃ MPa
A laminated body satisfying the following formulas (1) to (3).
_{(1): S 2 / S} 1 ≧ 0.2 and / or _S 1 -S ₂ ≦ 1.0
(2): S ₃ / S ₁ ≦ 0.9 and / or S ₁ -S ₃ ≧ 0.2
(3): S ₂ -S ₃ >0;
[2] The laminate according to [1], which has a laminate structure having three or more layers and at least one of the outermost layers being the layer (1);
[3] A laminate of [1] or [2], wherein at least one of layer (1) or layer (2) comprises at least one plasticizer;
[4] At least one plasticizer is plasticizer A,
When the hydroxyl value of the plasticizer A is HV (A) mgKOH / g, the laminate of [3] wherein HV (A) ≧ 30;
[5] At least one of the layer (1) and the layer (2) is subjected to a dynamic viscoelasticity test and a dynamic viscoelasticity test at a frequency of 0.3 Hz in accordance with JIS K7244-4: 1999. The laminated body according to any one of [1] to [4], wherein the temperature at which the tan δ measured at is maximum is 20 ° C. or higher;
[6] A laminate according to any one of [1] to [5], wherein at least one of the polymer compound (I) or the polymer compound (II) is polyvinyl acetal;
[7] The polymer compound (I) is polyvinyl acetal (1), and the polymer compound (II) is polyvinyl acetal (2),
When the average residual hydroxyl group amount of the polyvinyl acetal (1) is H (1) and the average residual hydroxyl group amount of the polyvinyl acetal (2) is H (2), | H (1) −H (2) | The laminate of [6], which is not more than mol%;
[8] The total amount of plasticizers contained in the layer (1) with respect to 100 parts by mass of the polymer compound (I) is X _i parts by mass, and the layer (2 with respect to 100 parts by mass of the polymer compound (II) ) When the total amount of plasticizers contained in Y _{i is} part by mass,
A laminated body according to any one of [3] to [7], wherein 0 <Y _i −X _i ;
[9] In a laminated glass obtained by sandwiching between two glasses and processing at a temperature of 120 ° C. or higher for at least 20 minutes,
The laminate according to any one of [1] to [8], wherein the maximum value of the loss coefficient at 20 ° C. and 2000 to 6000 Hz is 0.05 or more;
[10] The laminate according to any one of [1] to [9], wherein the thickness of the layer (1) is equal to or less than the thickness of the layer (2);
[11] After being melt-kneaded at 150 ° C. for 5 minutes, formed into a sheet having a thickness of 0.8 mm and sandwiched between two glasses,
The laminated body according to any one of [1] to [10], wherein the haze of the laminated glass is less than 3%;
[12] An interlayer film for laminated glass comprising the laminate of any one of [1] to [11];
[13] Laminated glass in which the interlayer film for laminated glass of [12] is sandwiched between two glasses;
[14] A method for producing a laminated glass obtained by sandwiching the interlayer film for laminated glass of [12] between two pieces of glass and treating at a temperature exceeding 100 ° C. for 10 minutes or more;
Is achieved by providing

  Even when the laminate of the present invention is stored at room temperature for a long period of time, it can retain the initial self-adhesion property, and the change over time of the stress is small, so that it is excellent in handleability during storage. Moreover, when the laminated body of the present invention is used as an interlayer film for laminated glass, flexibility is improved and safety performance can be expressed.

The present invention is a laminate comprising a layer (1) and a layer (2) on at least one side of the layer (1), wherein the layer (1) comprises the polymer compound (I), and the layer (2) Relates to a laminate comprising the polymer compound (II). Further, the stress at 10% elongation at 23 ° C. of the laminate was S ₁ MPa, and the stress at 10% elongation at 23 ° C. after storing the laminate at 23 ° C. and 50% RH for 5 weeks was S ₂ MPa. The laminate was treated at 140 ° C. for 30 minutes, cooled to 23 ° C. within 1 hour after the treatment, and after cooling, stored at 23 ° C. and 50% RH for 5 weeks, stress at 10% elongation at 23 ° C. Is S ₃ MPa, the laminate of the present invention is characterized by satisfying the following formulas (1) to (3).
_{(1): S 2 / S} 1 ≧ 0.2 and / or _S 1 -S ₂ ≦ 1.0
(2): S ₃ / S ₁ ≦ 0.9 and / or S ₁ -S ₃ ≧ 0.2
(3): S ₂ -S ₃ > 0

[Layer (1)]
The laminate of the present invention has at least one layer (1) containing the polymer compound (I). The polymer compound contained in the layer (1) may be the polymer compound (I) alone or a plurality of polymer compounds.

  Examples of the polymer compound (I) include thermoplastic resins and thermosetting resins. From the viewpoint of having a suitable strength and excellent moldability when used as an interlayer film for laminated glass, the polymer compound (I) is preferably a thermoplastic resin. The thermoplastic resin may have a crosslink for the purpose of adjusting the melt viscosity at the time of melt molding, for example, as long as it does not contradict the gist of the present invention.

  Examples of the thermoplastic resin include polyvinyl acetal, poly (meth) acrylic ester, polycarbonate, polyvinyl chloride, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, and ethylene-vinyl alcohol copolymer. , Ethylene- (meth) acrylic acid ester copolymer, polystyrene, styrene-polyene block copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, nylon, polyurethane, polyvinyl acetate, polyvinyl alcohol, etc. Is mentioned. Among them, it is a thermoplastic resin having one or more functional groups selected from a hydroxyl group and an ester group from the viewpoint that the compatibility with the plasticizer A described later is good and the plasticizer A hardly migrates to other layers. Is preferred.

  Examples of the thermoplastic resin having a hydroxyl group include the thermoplastic resins having a hydroxyl group, specifically, polyvinyl acetal having a hydroxyl group, an ethylene-vinyl alcohol copolymer, polyvinyl alcohol, and the like. Is mentioned. Moreover, what carried out modification | denaturation which introduce | transduces a hydroxyl group with respect to the said poly (meth) acrylic acid ester etc. can also be used. As a method for introducing a hydroxyl group, for example, when a poly (meth) acrylate is synthesized by polymerizing (meth) acrylate, a monomer having a hydroxyl group, such as 2-hydroxyethyl (meth) acrylate, etc. And a method such as copolymerization or graft polymerization.

  The hydroxyl value of the thermoplastic resin having a hydroxyl group is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more, further preferably 90 mgKOH / g or more, and 110 mgKOH / g or more. Particularly preferred is 160 mg KOH / g or more. The hydroxyl value is preferably 1300 mgKOH / g or less, more preferably 500 mgKOH / g or less, further preferably 400 mgKOH / g or less, and particularly preferably 300 mgKOH / g or less. When the hydroxyl value is less than 50 mgKOH / g, the compatibility with the plasticizer A is lowered, and the plasticizer A tends to bleed or the plasticizer A tends to migrate to another layer. On the other hand, when the hydroxyl value exceeds 1300 mgKOH / g, the resulting laminate has poor moisture resistance, and it tends to absorb water, or the compatibility with the plasticizer A tends to decrease.

  The hydroxyl value is the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of the sample, and can be measured according to JIS K1557: 2007.

  Examples of the thermoplastic resin having an ester group include the above-described thermoplastic resins having an ester group, specifically, polyvinyl acetal having an ester group, poly (meth) acrylic acid ester , Ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid ester copolymer, polyvinyl acetate, polyvinyl alcohol having an ester group, and the like. Moreover, what carried out modification | denaturation which introduce | transduces ester group with respect to the polyvinyl acetal mentioned above etc. can also be used. Examples of the method for introducing an ester group include a method in which a monomer having a poly (meth) acrylic acid ester is graft-polymerized on polyvinyl acetal.

  The ester value of the thermoplastic resin having an ester group is preferably 5 mgKOH / g or more, more preferably 8 mgKOH / g or more, further preferably 15 mgKOH / g or more, and 30 mgKOH / g or more. It is particularly preferable that it is 50 mgKOH / g or more. The ester value is preferably 700 mgKOH / g or less, more preferably 500 mgKOH / g or less, further preferably 400 mgKOH / g or less, particularly preferably 300 mgKOH / g or less, and 200 mgKOH. / G or less is most preferable. When the ester value is less than 5 mgKOH / g, the compatibility with the plasticizer A is lowered, and the plasticizer A tends to bleed or the plasticizer A tends to migrate to another layer. On the other hand, when the ester value exceeds 700 mgKOH / g, the compatibility with the plasticizer A may be lowered.

  The ester value is the number of mg of potassium hydroxide required to completely saponify the ester contained in 1 g of the sample, and can be measured according to JIS K 0070: 1992.

  Examples of the above-mentioned thermoplastic resin having a hydroxyl group and an ester group include the above-described thermoplastic resin having a hydroxyl group and an ester group, specifically, polyvinyl acetal having a hydroxyl group and an ester group. Polyvinyl acetate partially saponified with vinyl acetate units, ethylene-vinyl acetate copolymer partially saponified with vinyl acetate units, and poly (meth) acrylic copolymerized with acrylate monomers having hydroxyl groups Examples include acid esters.

  Polyvinyl acetal is preferably used as the polymer compound (I) from the viewpoint of excellent adhesion to glass, transparency, mechanical strength, and flexibility. Hereinafter, the polyvinyl acetal contained in the layer (1) is referred to as a polyvinyl acetal (1). For the polyvinyl acetal (1), the average residual hydroxyl group amount is H (1), the average residual vinyl ester group amount is VE (1), The average degree of acetalization is A (1), and the degree of polymerization of the starting polyvinyl alcohol is P (1).

  The average residual hydroxyl group amount, average residual vinyl ester group amount, average acetalization degree, and polymerization degree of the starting polyvinyl alcohol can be measured according to JIS K6728: 1977.

  H (1) in the polyvinyl acetal (1) is preferably 15 mol% or more, more preferably 17 mol% or more, further preferably 19 mol% or more, and 20 mol% or more. Is particularly preferred. Further, H (1) is preferably 50 mol% or less, more preferably 40 mol% or less, further preferably 35 mol% or less, and further preferably 33 mol% or less, More preferably, it is 32 mol% or less, Most preferably, it is 31 mol% or less, Most preferably, it is 30 mol% or less. When H (1) is less than 15 mol%, the mechanical strength of the laminate of the present invention tends to be reduced. On the other hand, when H (1) exceeds 50 mol%, the plasticizer tends to move between layers or bleed when the laminate of the present invention is stored.

  The VE (1) of the polyvinyl acetal (1) is preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and less than 2 mol%. Is particularly preferred. When VE (1) exceeds 20 mol%, it tends to be colored when the laminate of the present invention is used for a long period of time. Further, VE (1) is preferably 0.01 mol% or more, and more preferably 0.1 mol% or more.

  A (1) of the polyvinyl acetal (1) is preferably 50 mol% or more, more preferably 60 mol% or more, further preferably 64 mol% or more, and 67 mol% or more. Is more preferably 68 mol% or more, particularly preferably 69 mol% or more, and most preferably 70 mol% or more. Further, A (1) is preferably 85 mol% or less, more preferably 78 mol% or less, and further preferably 74 mol% or less. When A (1) is less than 50 mol%, the plasticizer tends to move between layers or bleed when the laminate of the present invention is stored. Moreover, when A (1) exceeds 85 mol%, it exists in the tendency for the intensity | strength of the laminated body of this invention to become inadequate.

  The value of H (1) + A (1) in the polyvinyl acetal (1) is preferably 95 mol% or more, more preferably 96 mol% or more, further preferably 98 mol% or more, It is especially preferable that it is 99 mol% or more. When H (1) + A (1) is 95 mol% or more, the weather resistance and stability of the laminate of the present invention are improved, and for example, when stored for a long period of time, the occurrence of discoloration and odor tends to be suppressed. is there.

  P (1) of the polyvinyl acetal (1) is preferably 1100 or more, more preferably 1200 or more, and further preferably 1600 or more. Further, P (1) is preferably 3500 or less, and more preferably 3000 or less. When P (1) is less than 1100, the penetration resistance of the laminate of the present invention is reduced, the laminate of the present invention is easily attached (blocked), or the strength of the laminate is insufficient. In particular, when the laminate of the present invention is used as an interlayer film for laminated glass, it tends to be a problem. Moreover, when P (1) exceeds 3500, when using the laminated body of this invention as an intermediate film for laminated glasses, it exists in the tendency for the productivity of a laminated glass to fall.

  The polyvinyl acetal (1) is usually produced using polyvinyl alcohol as a raw material. The polyvinyl alcohol can be obtained by a conventionally known method, that is, by polymerizing a carboxylic acid vinyl ester compound such as vinyl acetate and saponifying the obtained polymer. As a method for polymerizing the carboxylic acid 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 the polymerization initiator, an azo initiator, a peroxide initiator, a redox initiator, or the like can be appropriately selected depending on the polymerization method. For the saponification reaction, a conventionally known alcoholysis or hydrolysis reaction using an alkali catalyst or an acid catalyst can be applied.

  Further, the polyvinyl alcohol may be a saponified copolymer obtained by copolymerizing a carboxylic acid vinyl ester compound and another monomer as long as it does not contradict the gist of the present invention. Examples of other monomers include α-olefins such as ethylene, propylene, n-butene, and isobutylene; methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, Acrylic esters such as 2-ethylhexyl acrylate, dodecyl acrylate, octadecyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate , Methacrylate esters such as dodecyl methacrylate and octadecyl methacrylate; acrylamide, N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide, diacetone acrylamide, acrylamide propane sulfone Acrylamide and its derivatives such as acid and its salt, acrylamidopropyldimethylamine, its salt and its quaternary salt, N-methylolacrylamide and its derivative; methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, methacrylamidepropane Methacrylamide and its derivatives such as sulfonic acid and its salt, methacrylamide propyldimethylamine, its salt and its quaternary salt, N-methylol methacrylamide and its derivatives; methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, i-butyl Vinyl ethers such as vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether; acrylonitrile, methacrylonitrile, etc. Nitriles; Vinyl halides such as vinyl chloride and vinyl fluoride; Vinylidene halides such as vinylidene chloride and vinylidene fluoride; Allyl compounds such as allyl acetate and allyl chloride; Maleic acid esters or maleic anhydride, vinyltrimethoxysilane, etc. And vinyl silyl compounds; isopropenyl acetate and the like. When these other monomers are copolymerized, they are usually used in a proportion of less than 10 mol% with respect to the carboxylic acid vinyl ester compound.

  Polyvinyl acetal (1) can be obtained, for example, by the following method. First, an aqueous polyvinyl alcohol solution having a concentration of 3 to 30% by mass is maintained in a temperature range of 80 to 100 ° C., and then the temperature is 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. Thereafter, the reaction solution is heated to a temperature of 20 to 80 ° C. over 30 to 200 minutes, and the temperature is maintained for 10 to 300 minutes. Next, the reaction liquid is neutralized by adding an alkaline neutralizing agent such as sodium hydroxide as necessary, and the resin is washed with water and dried to obtain polyvinyl acetal (1).

  As the acid catalyst used in the acetalization reaction, any of organic acids and inorganic acids can be used, and examples include acetic acid, paratoluenesulfonic acid, nitric acid, sulfuric acid, hydrochloric acid and the like. Of these, hydrochloric acid, sulfuric acid, and nitric acid are preferably used.

  The aldehyde used for the acetalization reaction is preferably an aldehyde having 1 to 8 carbon atoms. Examples of the aldehyde having 1 to 8 carbon atoms include formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, n-hexylaldehyde, 2-ethylbutyraldehyde, n-octylaldehyde, 2-ethylhexylaldehyde, benzaldehyde and the like. Can be mentioned. These may be used alone or in combination of two or more. Among these, n-butyraldehyde is preferred from the balance of mechanical properties and handleability of the polyvinyl acetal (1) obtained.

  When the polyvinyl acetal (1) uses an aldehyde having n carbon atoms as a raw material, n is preferably 2 or more, and more preferably 4 or more. When n is less than 2, the handleability of aldehyde is poor and the production of polyvinyl acetal (1) tends to be difficult. Further, n is preferably 8 or less, and more preferably 5 or less. When n exceeds 8, the water solubility of the aldehyde is lowered, and it becomes difficult to remove the unreacted aldehyde by washing with water after the production of the polyvinyl acetal (1), and the remaining aldehyde tends to generate odor. Of these, n is most preferably 4.

  In the laminate of the present invention, the plasticizer A may be contained in the layer (1). Here, the plasticizer A means a plasticizer having an HV (A) of 30 or more when the hydroxyl value is HV (A) mgKOH / g. The plasticizer A has a property that it hardly transfers to another layer during storage, quickly transfers to another layer during heat treatment, and hardly transfers to another layer after heat treatment. Therefore, by using the plasticizer A, it is possible to achieve both weak self-adhesion during storage and high flexibility after the laminated glass is produced.

  HV (A) is 30 or more, preferably 50 or more, more preferably 80 or more, further preferably 100 or more, particularly preferably 150 or more, and 200 or more. Is most preferred. Further, HV (A) is preferably 500 or less, more preferably 450 or less, further preferably 400 or less, particularly preferably 350 or less, and most preferably 300 or less. . HV (A) is 30 or more from the viewpoint of suppressing the plasticizer A from volatilizing from the laminate, and when the laminate is stored for a long period of time, the plasticizer A moves to another layer. It is preferable from a viewpoint which suppresses the physical property fall of a laminated body. Moreover, HV (A) being 500 or less means that when the laminate is stored for a long period of time, the viewpoint of suppressing the interlayer transition and bleeding of the plasticizer A and the moisture resistance of the laminate of the present invention are sufficient. From the viewpoint of

  Examples of the plasticizer A include a polyester diol composed of an alternating copolymer of adipic acid and 3-methyl-1,5-pentanediol, a polyester diol obtained by addition polymerization of ε-caprolactone to propylene glycol, a polycaprolactone diol, Alternatively, a polyester compound such as polycaprolactone monool, a polyether compound such as polyethylene glycol, polypropylene glycol, bisphenol A ethylene oxide adduct, or bisphenol A propylene oxide adduct, or a glycerin ester such as castor oil. In addition, the hydroxyl value of a plasticizer can be measured based on JISK1557: 2007.

  The number average molecular weight of the plasticizer A is preferably 200 or more, more preferably 330 or more, still more preferably 360 or more, still more preferably 380 or more, and more preferably 420 or more. More preferably, it is particularly preferably 460 or more, and most preferably 500 or more. The number average molecular weight of the plasticizer A is preferably 2000 or less, more preferably 1200 or less, still more preferably 900 or less, and particularly preferably 750 or less. If the number average molecular weight of the plasticizer A is less than 200, the plasticizer A tends to volatilize or the plasticizer A tends to migrate to another layer when the laminate is stored for a long period of time. . Further, when the number average molecular weight of the plasticizer A exceeds 2000, the compatibility with the polymer compound may be poor, and the transparency of the resulting sheet may be impaired, and the plasticizing effect on the polymer compound is sufficient. May not develop.

  Among these, from the viewpoint of suppressing the volatilization of the plasticizer A from the laminate and suppressing the physical properties of the laminate from being lowered by the plasticizer A moving to another layer when the laminate is stored for a long period of time. In addition, 5 to 100% by mass of the plasticizer A is preferably a compound having a number average molecular weight of 360 or more, more preferably 5 to 100% by mass is a compound having a number average molecular weight of 380 or more, and 5 to 100% by mass. More preferably, the compound has a number average molecular weight of 400 or more. Further, 30 to 100% by mass of the plasticizer A is more preferably a compound having a number average molecular weight of 360 or more, more preferably 50 to 100% by mass is a compound having a number average molecular weight of 360 or more, and 70 to 100% by mass. % Is particularly preferably a compound having a number average molecular weight of 360 or more, and most preferably 90 to 100% by mass is a compound having a number average molecular weight of 360 or more.

  Among the plasticizers A, compounds having a molecular weight of 360 or more include, for example, polyester diol composed of an alternating copolymer of adipic acid and 3-methyl-1,5-pentanediol, or addition polymerization of ε-caprolactone to propylene glycol. Polyester compounds such as polyester diol having a molecular weight of 360 or more, polyether compounds such as polyethylene glycol, polypropylene glycol, bisphenol A propylene oxide adduct, or bisphenol A ethylene oxide adduct, and having a molecular weight of 360 or more Or a glycerin ester such as castor oil having a molecular weight of 360 or more.

  The plasticizer A preferably has at least one hydroxyl group per molecule, and more preferably has at least two hydroxyl groups. When the plasticizer A has a hydroxyl group, the compatibility with the polymer compound is improved, so that bleeding of the plasticizer A is suppressed, or the migration of the plasticizer A to other layers tends to be suppressed. is there.

  The plasticizer A preferably has at least one ether bond or ester bond. When the plasticizer A has an ether bond or an ester bond, the compatibility with the polymer compound is improved to suppress the bleeding of the plasticizer A or to suppress the migration of the plasticizer A to other layers. There is a tendency to do.

  When the layer (1) contains the plasticizer A, the content of the plasticizer A is preferably 4 parts by mass or more with respect to 100 parts by mass of the polymer compound (I), and is 10 parts by mass or more. Is more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, and particularly preferably 30 parts by mass or more. Most preferably, it is at least part by mass. The content of the plasticizer A is preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and 130 parts by mass or less with respect to 100 parts by mass of the polymer compound (I). Is more preferably 110 parts by mass or less, particularly preferably 90 parts by mass or less, and most preferably 70 parts by mass or less. When the content of the plasticizer A is 4 parts by mass or more with respect to 100 parts by mass of the polymer compound (I), the flexibility of the laminate is improved, or the laminate of the present invention contains a plasticizer B described later. In this case, the plasticizer B tends to be suppressed from moving to another layer, or the plasticizer B is prevented from bleeding from the laminate of the present invention. Further, when the content of the plasticizer A is 200 parts by mass or less with respect to 100 parts by mass of the polymer compound (I), the strength and transparency of the laminate are improved, or the plasticizer A is added to other layers. There is a tendency to suppress migration and to suppress bleeding of the plasticizer A from the laminate of the present invention.

  In addition, it is good also as an aspect which uses the some plasticizer A together and the total amount of the some plasticizer A satisfy | fills the said range.

  In the laminate of the present invention, the plasticizer B may be contained in the layer (1). Here, the plasticizer B means a plasticizer having an HV (B) of less than 30 when the hydroxyl value is HV (B) mgKOH / g.

  HV (B) is less than 30, preferably less than 10, and more preferably less than 5.

  Examples of the plasticizer B include triethylene glycol di-2-ethylhexanoate (3GO), tetraethylene glycol di-2-ethylhexanoate (4GO), and octaethylene glycol di-2-ethylhexanoate (8GO). Diester compound of monohydric carboxylic acid and dihydric alcohol, or dibutyl adipate, dihexyl adipate, di (2- (2-butoxy) ethoxy) ethyl adipate (DBEEA), di (2-butoxyethyl) adipate, adipine Examples thereof include adipic acid esters such as dinonyl acid, or diester compounds of divalent carboxylic acid and monohydric alcohol such as dioctyl phthalate and di (2-ethylhexyl) sebacate. The plasticizer B is a diester compound of a monovalent carboxylic acid and a dihydric alcohol as described above and / or a divalent carboxylic acid and a monohydric alcohol because of its compatibility with polyvinyl acetal and excellent plasticizing effect on the polyvinyl acetal. The diester compound is preferably triethylene glycol di-2-ethylhexanoate.

  The number average molecular weight of the plasticizer B is preferably 200 or more, more preferably 310 or more, still more preferably 360 or more, still more preferably 380 or more, and particularly preferably 400 or more. Preferably, it is 420 or more. The number average molecular weight of the plasticizer B is preferably 2000 or less, more preferably 1200 or less, still more preferably 900 or less, and particularly preferably 750 or less. If the number average molecular weight of the plasticizer B is less than 200, the plasticizer B tends to volatilize or the plasticizer B tends to move to another layer when the laminate is stored for a long period of time. . On the other hand, when the number average molecular weight of the plasticizer B exceeds 2000, the strength and transparency of the laminate are lowered, and the plasticizing effect on the polymer compound tends to be lowered.

  Especially, from a viewpoint of suppressing volatilization of the plasticizer B from a laminated body, it is preferable that 5-100 mass% of the plasticizer B is a compound with a number average molecular weight 310 or more, and 5-100 mass% is a number average molecular weight. More preferably, the compound is 360 or more, more preferably 5 to 100% by mass is a compound having a number average molecular weight of 380 or more, and 5 to 100% by mass is particularly preferably a compound having a number average molecular weight of 400 or more. . Further, 30 to 100% by mass of the plasticizer B is more preferably a compound having a number average molecular weight of 360 or more, more preferably 50 to 100% by mass is a compound having a number average molecular weight of 360 or more, and 70 to 100% by mass. % Is particularly preferably a compound having a number average molecular weight of 360 or more, and most preferably 90 to 100% by mass is a compound having 360 or more.

  Among the plasticizers B, compounds having a number average molecular weight of 360 or more include, for example, triethylene glycol di-2-ethylhexanoate (3GO), tetraethylene glycol di-2-ethylhexanoate (4GO), octaethylene glycol di-2 -Ethylhexanoate (8GO), di (2- (2-butoxyethoxy) ethyl) adipate (DBEEA), dinonyl adipate, dioctyl phthalate, di (2-ethylhexyl) sebacate and the like.

  The plasticizer B is preferably a compound having no hydroxyl group. Since the plasticizer B does not have a hydroxyl group, the plasticizer B tends to be difficult to be extracted with water when the laminate of the present invention is in contact with water.

  When the plasticizer B is contained in the layer (1), the content of the plasticizer B is preferably 3 parts by mass or more with respect to 100 parts by mass of the polymer compound (I), and is 5 parts by mass or more. Is more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and most preferably 25 parts by mass or more. The content of the plasticizer B is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and 60 parts by mass or less with respect to 100 parts by mass of the polymer compound (I). Is more preferably 50 parts by mass or less, particularly preferably 45 parts by mass or less, and most preferably 35 parts by mass or less. When the plasticizer B is 3 parts by mass or more with respect to 100 parts by mass of the polymer compound (I), the flexibility of the laminate tends to be improved. Moreover, the intensity | strength and transparency of a laminated body improve that the plasticizer B is 100 mass parts or less with respect to 100 mass parts of thermoplastic resins (I), or the transfer to the other layer of the plasticizer B is suppressed. There is a tendency to do.

  In addition, it is good also as an aspect which uses the some plasticizer B together and the total amount of the some plasticizer B satisfy | fills the said range.

  In the laminate of the present invention, the plasticizer A and the plasticizer B may be included in the layer (1). When both the plasticizer A and the plasticizer B are contained in the layer (1), the mass ratio of the plasticizer B to the plasticizer A (the content of the plasticizer B / the content of the plasticizer A) is 0. .05 or more, preferably 0.1 or more, more preferably 0.15 or more, and particularly preferably 0.2 or more. The mass ratio of the plasticizer B to the plasticizer A (the content of the plasticizer B / the content of the plasticizer A) is preferably 20 or less, more preferably 10 or less, and 7 or less. More preferably, it is particularly preferably 5 or less. When the mass ratio of the plasticizer B to the plasticizer A in the layer (the content of the plasticizer B / the content of the plasticizer A) is 0.05 or more, the plasticizing effect by the plasticizer B tends to be easily obtained. It is in. Further, when the mass ratio of the plasticizer B to the plasticizer A in the layer (the content of the plasticizer B / the content of the plasticizer A) is 20 or less, the migration of the plasticizer B to another layer is suppressed. Or bleeding of the plasticizer B from the laminate of the present invention tends to be suppressed.

In the laminate of the present invention, when the total amount of the plasticizer contained in the layer (1) is X _i parts by mass with respect to 100 parts by mass of the polymer compound (I), X _i is 0 or more. Is preferably 10 or more, more preferably 20 or more, and particularly preferably 25 or more. X _i is preferably 120 or less, more preferably 110 or less, further preferably 90 or less, particularly preferably 80 or less, and most preferably 70 or less. When X _i exceeds 120, the laminate of the present invention tends to be self-attached (blocking) or the strength tends to be insufficient.

  The thickness of the layer (1) is preferably 0.01 mm or more, more preferably 0.04 mm or more, further preferably 0.08 mm or more, and particularly preferably 0.1 mm or more. . Further, the thickness of the layer (1) is preferably 0.5 mm or less, more preferably 0.4 mm or less, further preferably 0.35 mm or less, and 0.3 mm or less. Particularly preferred. When the thickness of the layer (1) is 0.01 mm or more, the strength of the laminate of the present invention is improved, or the plasticizer A is layered from the layer (2) when the laminate of the present invention is stored for a long period of time. It tends to easily shift to (1) to suppress a decrease in self-adhesion (blocking) resistance and strength. In addition, when the thickness of the layer (1) is 0.5 mm or less, when the laminated body of the present invention is used as an interlayer film for laminated glass to produce a laminated glass, the layer (1) is sufficiently plasticized. The time for transferring A can be reduced, and the production efficiency of laminated glass can be improved.

[Layer (2)]
The laminate of the present invention has at least one layer (2) containing the polymer compound (II). The polymer compound contained in the layer (2) may be the polymer compound (II) alone or a plurality of polymer compounds.

  The polymer compound (II) is preferably a thermoplastic resin like the polymer compound (I). When the polymer compound (II) is a thermoplastic resin, the same thermoplastic resin as that exemplified for the polymer compound (I) can be used. The polymer compound (II) is preferably a thermoplastic resin having one or more kinds of functional groups selected from a hydroxyl group and an ester group, like the polymer compound (I). As the thermoplastic resin having a hydroxyl group, those similar to the polymer compound (I) are preferably used. Further, as the thermoplastic resin having an ester group, those similar to the polymer compound (I) are preferably used. In addition, as the thermoplastic resin having a hydroxyl group and an ester group, those similar to the polymer compound (I) are preferably used.

  Among these, as the polymer compound (II), it is preferable to use polyvinyl acetal similarly to the polymer compound (I). Hereinafter, when polyvinyl acetal is contained in the layer (2), the polyvinyl acetal contained in the layer (2) is referred to as polyvinyl acetal (2), and the average residual hydroxyl group content of the polyvinyl acetal (2) is H (2), The average residual vinyl ester group amount is VE (2), the average acetalization degree is A (2), and the polymerization degree of the raw material polyvinyl alcohol is P (2).

  Suitable ranges of H (2), VE (2), A (2), and P (2) are preferred ranges of H (1), VE (1), A (1), and P (1), respectively. It is the same. H (2), VE (2), A (2), and P (2) may be the same or different from H (1), VE (1), A (1), and P (1), respectively. It may be.

  In the laminated body of this invention, it is preferable that the plasticizer A is contained in the layer (2). As the plasticizer A, those similar to those exemplified in the layer (1) can be used. In the case where the plasticizer A is contained in the layer (2), suitable conditions and suitable contents of the plasticizer A are the same as those suitable for the plasticizer A shown in the layer (1). is there.

  In the laminate of the present invention, the layer (2) may further contain a plasticizer B. As the plasticizer B, those similar to those exemplified in the layer (1) can be used. In the case where the plasticizer B is contained in the layer (2), suitable conditions and suitable contents of the plasticizer B are the same as those suitable for the plasticizer B shown in the layer (1). is there.

  In the laminate of the present invention, the layer (2) may contain both the plasticizer A and the plasticizer B, and the layer (2) contains both the plasticizer A and the plasticizer B. The preferable range of the mass ratio of the plasticizer B to the plasticizer A (the content of the plasticizer B / the content of the plasticizer A) is the same as the preferable range shown in the layer (1).

In the laminate of the present invention, when the total amount of plasticizers contained in the layer (2) is Y _i parts by mass with respect to 100 parts by mass of the polymer compound (II), Y _i may be 20 or more. It is preferably 25 or more, more preferably 30 or more, particularly preferably 40 or more, and most preferably 50 or more. Y _i is preferably 190 or less, more preferably 150 or less, further preferably 130 or less, still more preferably 100 or less, particularly preferably 90 or less, and 80 Most preferably: When Y _i is less than 20, when the laminate of the present invention is used as an interlayer film for laminated glass, sufficient sound insulation properties tend not to be exhibited. On the other hand, if Y _i exceeds 190, the strength of the laminate of the present invention tends to be insufficient.

  The thickness of the layer (2) is preferably 0.05 mm or more, more preferably 0.2 mm or more, further preferably 0.3 mm or more, and particularly preferably 0.4 mm or more. . Further, the thickness of the layer (2) is preferably 1.5 mm or less, more preferably 1.1 mm or less, further preferably 1.0 mm or less, and 0.8 mm or less. Particularly preferred. When the thickness of the layer (2) is 0.05 mm or more, flexibility and sound insulation can be exhibited when the laminate of the present invention is used as an interlayer film for laminated glass. Further, when the thickness of the layer (2) is 1.5 mm or less, when the laminated body of the present invention is used as an interlayer film for laminated glass to produce a laminated glass, the layer (2) has a laminated glass edge. It tends to suppress overhang and improve the yield of the resulting laminated glass.

[Laminate]
The laminate of the present invention is a laminate comprising a layer (1) and a layer (2) on at least one side of the layer (1), the layer (1) comprising the polymer compound (I), (2) is a laminate containing the polymer compound (II) and satisfies the following formulas (1) to (3).
_{(1): S 2 / S} 1 ≧ 0.2 and / or _S 1 -S ₂ ≦ 1.0
(2): S ₃ / S ₁ ≦ 0.9 and / or S ₁ -S ₃ ≧ 0.2
(3): S ₂ -S ₃ > 0

The laminate of the present invention preferably has three or more layers. When the laminate of the present invention has three or more layers, it is preferable that at least one of the outermost layers has a layered structure in which the layers (1) are present, and both outermost layers have a layered structure in which the layers are (1). It is more preferable. For example, a laminate in which the layer (1), the layer (2), and the layer (1) are laminated in this order is preferable. Moreover, it is good also as a laminated body which laminated | stacked the layer (1), the layer (2), the layer (1), the layer (2), and the layer (1) in this order. When the laminate of the present invention has a layer structure including a plurality of layers (1) or (2), the composition and thickness of the plurality of layers satisfy the provisions of the present invention. They may be the same or different.

In the formula (1), S ₂ / S ₁ ≧ 0.2, S ₂ / S ₁ ≧ 0.4 is preferable, S ₂ / S ₁ ≧ 0.6 is more preferable, S ₂ / S ₁ ≧ 0.7 is more preferable, S ₂ / S ₁ ≧ 0.8 is more preferable, S ₂ / S ₁ ≧ 0.9 is particularly preferable, and S ₂ / Most preferably, S ₁ ≧ 0.95. When S ₂ / S ₁ <0.2, the laminate tends to be self-attached when the laminate is stored for a long period of time.

In the formula (1), S ₁ −S ₂ ≦ 1.0, S ₁ −S ₂ ≦ 0.8 is preferable, S ₁ −S ₂ ≦ 0.6 is more preferable, More preferably, ₁₋ S ₂ ≦ 0.4, particularly preferably S ₁ −S ₂ ≦ 0.2, and most preferably S ₁ −S ₂ ≦ 0.1. When S ₁ -S ₂ > 1.0, the laminate tends to be self-attached when the laminate is stored for a long period of time.

In the laminate of the present invention, as a method of setting S ₂ / S ₁ ≧ 0.2 and / or S ₁ -S ₂ ≦ 1.0, each polymer compound contained in the layer (1) or the layer (2) Examples thereof include a method in which the difference (Y _i -X _i ) in plasticizer content relative to 100 parts by mass is greater than 0, a method in which a plasticizer having a hydroxyl value of 30 mgKOH / g or more and 500 mgKOH / g or less is used. Moreover, you may combine these methods.

In the formula (2), S ₃ / S ₁ ≦ 0.9, preferably S ₃ / S ₁ ≦ 0.7, more preferably S ₃ / S ₁ ≦ 0.5, and S More preferably, ₃ / S ₁ ≦ 0.3, particularly preferably S ₃ / S ₁ ≦ 0.2, and most preferably S ₃ / S ₁ ≦ 0.15. When S ₃ / S ₁ > 0.9, when a laminated glass is produced, the laminate is not sufficiently flexible, and the impact absorbing ability of the laminated glass tends to be reduced.

In formula (2), S ₁ −S ₃ ≧ 0.2, S ₁ −S ₃ ≧ 0.4 is preferable, S ₁ −S ₃ ≧ 0.6 is more preferable, More preferably, ₁₋ S ₃ ≧ 0.8, still more preferably S ₁ −S ₃ ≧ 1.0, still more preferably S ₁ −S ₃ ≧ 1.2, and S ₁ -S ₃ ≧ 1.5 is particularly preferred, and S ₁ -S ₃ ≧ 1.7 is most preferred. When S ₁ -S ₃ <0.2, when a laminated glass is produced, the laminate does not have sufficient flexibility, and the impact absorbing ability of the laminated glass tends to decrease.

In the laminate of the present invention, each of the polymer compounds contained in the layer (1) or the layer (2) may be S ₃ / S ₁ ≦ 0.9 and / or S ₁ -S ₃ ≧ 0.2. Examples include a method in which the difference (Y _i -X _i ) in plasticizer content relative to 100 parts by mass is greater than 0, a method using a plasticizer having a hydroxyl group, an ether bond or an ester bond. Moreover, you may combine these methods. Further, when both the layer (1) and the layer (2) contain polyvinyl acetal, the absolute value | H (1) −H (2) | of the difference in the average residual hydroxyl group amount is 20 mol% or less. , Absolute value of difference in average degree of acetalization | A (1) −A (2) | 20 mol% or less, absolute value of difference in average residual vinyl ester group amount | VE (1) −VE (2 ) | Is 20 mol% or less, the polymerization degree (P (1) and P (2)) of the polyvinyl acetal contained in each layer is 1100 or more, the difference in carbon number of the aldehyde that is the raw material A preferable method is a method in which the absolute value | n−m | is 2 or less.

In the formula (3), S ₂ -S ₃ > 0, S ₂ -S ₃ > 0.2 is preferable, S ₂ -S ₃ > 0.4 is more preferable, and S _2- More preferably, S ₃ > 0.7, particularly preferably S ₂ -S ₃ > 1.0, and most preferably S ₂ -S ₃ > 1.5. When S ₂ −S ₃ ≦ 0, when the laminated glass is produced, the laminate is not sufficiently flexible, and the impact absorbing ability of the laminated glass is lowered.

In the laminate of the present invention, the method of setting S ₂ -S ₃ > 0 includes a difference in plasticizer content (Y _{i with} respect to 100 parts by mass of each polymer compound contained in the layer (1) or the layer (2)). -X _i ) 0 or more, a method using a plasticizer having a hydroxyl value of 30 mgKOH / g or more and 500 mgKOH / g or less, a method using a plasticizer having a hydroxyl group or an ether bond or an ester bond, a hydroxyl value of 30 mgKOH / g The method of setting it as the 3 layer structure which mix | blended the plasticizer of g or more with the inner layer is mentioned. A plurality of these methods may be combined. Further, when both the layer (1) and the layer (2) contain polyvinyl acetal, the absolute value | H (1) −H (2) | of the difference in the average residual hydroxyl group amount is 20 mol% or less. , Absolute value of difference in average degree of acetalization | A (1) −A (2) | 20 mol% or less, absolute value of difference in average residual vinyl ester group amount | VE (1) −VE (2 ) | Is 20 mol% or less, the polymerization degree (P (1) and P (2)) of the polyvinyl acetal contained in each layer is 1100 or more, the carbon number of the aldehyde that is the raw material of the polyvinyl acetal A method of setting the absolute value | n−m | of the difference of 2 to 2 or less is a preferable method.

  In the laminate of the present invention, at least one of the layer (1) and the layer (2) is subjected to a dynamic viscoelasticity test under a frequency of 0.3 Hz in accordance with JIS K7244-4: 1999. The temperature at which the tan δ measured at is maximum is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, further preferably 30 ° C. or higher, and particularly preferably 35 ° C. or higher. Most preferably, it is 40 ° C. or higher. Moreover, it is more preferable that the temperature at which tan δ in the layer (1) is maximum satisfies the above range. In both the layer (1) and the layer (2), if the temperature at which tan δ is maximum is less than 20 ° C., the self-adhesion property near the room temperature of the laminate of the present invention may be increased.

  In at least one of the layers (1) and (2), tan δ measured by performing a dynamic viscoelasticity test under the condition of a frequency of 0.3 Hz in accordance with JIS K7244-4: 1999 is the maximum. Examples of the method for setting the temperature to 20 ° C. or higher include a method of preventing the layer (1) and / or the layer (2) from containing a plasticizer, and reducing the content of the plasticizer.

  Since the laminate of the present invention has good compatibility with the plasticizer A and the plasticizer A is difficult to migrate to other layers, at least one of the polymer compound (I) or the polymer compound (II) is: It is preferably a thermoplastic resin having one or more functional groups selected from a hydroxyl group and an ester group, and both of the polymer compound (I) and the polymer compound (II) are selected from a hydroxyl group and an ester group. A thermoplastic resin having the above functional groups is more preferable.

  In the laminate of the present invention, at least one of the polymer compound (I) or the polymer compound (II) is a polyvinyl acetal from the viewpoint of excellent adhesion to glass, transparency, mechanical strength, and flexibility. It is preferable that the polymer compound (I) and the polymer compound (II) are polyvinyl acetals. When the polymer compound (I) is polyvinyl acetal (1) and the polymer compound (II) is polyvinyl acetal (2), at least one of the polyvinyl acetal (1) or the polyvinyl acetal (2) is as described above. It is preferable to satisfy suitable ranges of the average residual hydroxyl group amount, average residual vinyl ester group amount, average acetalization degree, and polymerization degree.

  In the laminate of the present invention, when the polymer compound (I) is polyvinyl acetal (1) and the polymer compound (II) is polyvinyl acetal (2), the difference in the average residual hydroxyl group amount of each polyvinyl acetal The absolute value | H (1) −H (2) | is preferably 20 mol% or less, more preferably 10 mol% or less, further preferably 5 mol% or less, and more preferably 3 mol%. More preferably, it is more preferably 2 mol% or less, and most preferably 1 mol% or less. When | H (1) -H (2) | exceeds 20 mol%, it becomes difficult to recycle trims and off-spec products generated when producing the laminate of the present invention as a transparent composition. There is a tendency.

  In the laminate of the present invention, when the polymer compound (I) is polyvinyl acetal (1) and the polymer compound (II) is polyvinyl acetal (2), the average residual vinyl ester group amount of each polyvinyl acetal The absolute value of the difference | VE (1) −VE (2) | is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less. It is more preferably at most mol%, particularly preferably at most 2 mol%, most preferably at most 1 mol%. When | VE (1) −VE (2) | exceeds 20 mol%, it becomes difficult to recycle trim or off-spec products generated when producing the laminate of the present invention as a transparent composition. There is a tendency.

  In the laminate of the present invention, when the polymer compound (I) is polyvinyl acetal (1) and the polymer compound (II) is polyvinyl acetal (2), the difference in the average degree of acetalization of each polyvinyl acetal The absolute value | A (1) -A (2) | is preferably 20 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, and 3 mol%. More preferably, it is more preferably 2 mol% or less, and most preferably 1 mol% or less. When | A (1) -A (2) | exceeds 20 mol%, it becomes difficult to recycle trim and off-spec products generated when producing the laminate of the present invention as a transparent composition. There is a tendency.

  In the laminate of the present invention, when the thermoplastic resin (I) is polyvinyl acetal (1) and the thermoplastic resin (II) is polyvinyl acetal (2), the average degree of acetalization A (1) and A ( As for 2), it is preferable that all are 67.0 mol% or more, and it is preferable that it is 85.0 mol% or less. Moreover, it is preferable that both polymerization degree P (1) and P (2) are 1100 or more.

  In the laminate of the present invention, the polymer compound (I) is polyvinyl acetal (1), the polymer compound (II) is polyvinyl acetal (2), and the polyvinyl acetal (1) is an aldehyde having n carbon atoms. Is used as a raw material, and the polyvinyl acetal (2) uses an aldehyde having m carbon atoms as a raw material, the absolute value | n−m | of each carbon number difference is preferably 2 or less, and preferably 1 or less. Is more preferred and 0 is even more preferred. When | n−m | exceeds 2, it tends to be difficult to recycle trims and off-spec products generated when the laminate of the present invention is produced as a transparent composition. If the body is stored for a long time, its characteristics may change.

  In the laminate of the present invention, it is preferable that at least one of the layers (1) or (2) contains at least one plasticizer.

  In the laminate of the present invention, it is preferable that at least one of the layer (1) or the layer (2) contains the above-mentioned plasticizer A, and from the viewpoint of suppressing plasticizer migration during long-term storage, the layer (2 It is more preferable that the above-mentioned plasticizer A is contained in

  Moreover, in the laminated body of this invention, it is preferable from the viewpoint of the softness | flexibility of the laminated body obtained that the above-mentioned plasticizer B is included in at least 1 layer of a layer (1) or a layer (2).

  In the laminate of the present invention, when both the layer (1) and the layer (2) contain the plasticizer A and the plasticizer B, the mass ratio of the plasticizer B to the plasticizer A in the layer (1) (plasticity) The content of the plasticizer B / the content of the plasticizer A) was R1, and the mass ratio of the plasticizer B to the plasticizer A in the layer (2) (the content of the plasticizer B / the content of the plasticizer A) was R2. Sometimes, R1> R2. When R1> R2, for example, when the layer (1) is used as the outer layer and the layer (2) is used as the inner layer, the plasticizer hardly migrates during storage, but the laminate is processed at a temperature exceeding 100 ° C. In this case, the plasticizer A is easily transferred from the inner layer to the outer layer, and safety performance can be exhibited when the laminate is used as an interlayer film for laminated glass. For the same reason, the layer (1) may not include the plasticizer A, and the layer (2) may include the plasticizer A or the plasticizer A and the plasticizer B.

  In the laminate of the present invention, either the layer (1) or the layer (2) includes the plasticizer A and the plasticizer B, and the other layer includes one of the plasticizer A or the plasticizer B. This is a preferred embodiment. In the case of such an embodiment, since the amount of the plasticizer is reduced in the layer containing either the plasticizer A or the plasticizer B, a laminate having excellent handleability during storage is obtained. In the case of the above-described aspect, when the laminate is processed at a temperature exceeding 100 ° C., the plasticizer moves from the layer containing both the plasticizer A and the plasticizer B to the other layer, When the laminate is used as an interlayer film for laminated glass, safety performance can be exhibited.

  In the laminate of the present invention, the ratio of the total amount of the plasticizer contained in the layer (1) and the layer (2) to the total amount of the polymer compound (I) and the polymer compound (II) is When the total amount is 100 parts by mass, the total amount of plasticizers contained in the layer (1) and the layer (2) is preferably 20 parts by mass or more, more preferably 30 parts by mass or more. The amount is more preferably 40 parts by mass or more, particularly preferably 43 parts by mass or more, and most preferably 45 parts by mass or more. Further, when the total amount of the polymer compounds is 100 parts by mass, the total amount of the plasticizers contained in the layer (1) and the layer (2) is preferably 120 parts by mass or less, and 110 parts by mass or less. More preferably, it is more preferably 100 parts by mass or less. When the total amount of the plasticizer is 20 parts by mass or more, sound insulation properties tend to be sufficiently exhibited when the laminate of the present invention is used as an interlayer film for laminated glass. Moreover, it exists in the tendency which can suppress the interlayer shift and bleed of the plasticizer from the laminated body of this invention as it is 120 mass parts or less.

In the laminate of the present invention, X _i parts by the total amount of plasticizer contained in the layer (1) of the polymer compound (I) 100 parts by weight, the polymer compound (II) a layer with respect to 100 parts by weight The total amount of plasticizers contained in (2) is Y _i parts by mass.

Y _i -X _i is preferably 0 <Y _i -X _i , more preferably 10 ≦ Y _i -X _i , further preferably 10 <Y _i -X _i , and 15 ≦ More preferably, Y _i -X _i , still more preferably 20 ≦ Y _i -X _i , particularly preferably 25 ≦ Y _i -X _i , and 30 ≦ Y _i -X _i . It is particularly preferred that 35 ≦ Y _i −X _i is most preferred. When Y _i -X _i is 0 ≧ Y _i -X _i , the strength of the laminate is suitable, but it tends to be self-adhering (blocking).

In the laminate of the present invention, when the layer (1) and the laminate obtained by laminating the layer (2) on at least one side of the layer (1) are stored at 23 ° C. and 50% RH for 5 weeks, the polymer compound (I) X _ii parts by mass of the total amount of plasticizer contained in the layer (1) with respect to 100 parts by mass, and Y the total amount of plasticizer contained in the layer (2) with respect to 100 parts by mass of the polymer compound (II). _ii Mass parts.

X _ii -X _i is preferably X _ii -X _i <20, more preferably X _ii -X _i <15, further preferably X _ii -X _i <10, and X _ii -X _i <5 is particularly preferred. When X _ii −X _i <20, the plasticizer is difficult to migrate even if the laminate is stored for a long period of time, so that the self-adhesion property can be kept low. Y _i -Y _ii is preferably Y _i -Y _ii <20, more preferably Y _i -Y _ii <15, more preferably from _{Y i -Y ii <10, Y} i It is particularly preferred that -Y _ii <5. If Y _i -Y _ii <20, the plasticizer is difficult to migrate even if the laminate is stored for a long period of time, so that the self-adhesion property can be kept low.

When the laminate of the present invention was treated at 140 ° C. for 30 minutes, cooled to 23 ° C. within 1 hour, and stored at 23 ° C. and 50% RH for 5 weeks, 100 parts by mass of the polymer compound (I) to the total amount of plasticizer included in a layer (1) Te and X _iii parts by mass, the total amount of the plasticizer contained in the layer (2) of the polymer compound (II) 100 parts by weight of a Y _iii parts by .

X _iii -X _i is preferably 3 <X _iii -X _i , more preferably 10 <X _iii -X _i , further preferably 15 <X _iii -X _i , 20 < X _iii -X _i is particularly preferred. In the case of 3 <X _iii -X _i , the laminate is processed at a temperature exceeding 100 ° C., so that the plasticizer is quickly transferred from the layer (2) to the layer (1), and the laminate is excellent in flexibility. Can be obtained. Similarly, Y _i -Y _iii is 3 <is preferably Y _i -Y _iii, 5 <more preferably Y _i -Y _iii, further preferably from 10 <Y _i -Y _iii 15 <Y _i -Y _iii is more preferable, and 20 <Y _i -Y _iii is particularly preferable. When 3 <Y _i -Y _iii , the laminate is processed at a temperature exceeding 100 ° C., so that the plasticizer is quickly transferred from the layer (2) to the layer (1), and the laminate is excellent in flexibility. Can be obtained.

X _iii -X _ii is preferably 0 <X _iii -X _ii , more preferably 5 <X _iii -X _ii , further preferably 10 <X _iii -X _ii , 15 < X _iii -X _ii is particularly preferable. In the case of 0 <X _iii -X _ii , when the laminate of the present invention is stored for a long period of time, the layer (( It is preferable in that the plasticizer quickly moves from 2) to the layer (1) and is excellent in balance with the characteristic that a laminate having excellent flexibility can be obtained. Similarly, Y _ii -Y _iii is preferably 0 <Y _ii -Y _iii , more preferably 5 <Y _ii -Y _iii , and further preferably 10 <Y _ii -Y _iii. 15 <Y _ii -Y _iii is particularly preferable. In the case of 0 <Y _ii -Y _iii , from the layer (2) by processing at a temperature exceeding 100 ° C. and the property that the plasticizer hardly migrates when the laminate of the present invention is stored for a long period of time. This is preferable in that the plasticizer quickly moves to the layer (1) to obtain a laminate that is excellent in flexibility and is excellent in balance with the characteristics.

In the laminate of the present invention, when the layer (1) and the laminate obtained by laminating the layer (2) on at least one side of the layer (1) are stored at 23 ° C. and 50% RH for 1 week, the polymer compound (I ) X _iv parts by mass of the total amount of plasticizer contained in the layer (1) with respect to 100 parts by mass, and the total amount of plasticizer contained in the layer (2) with respect to 100 parts by mass of the polymer compound (II). Y _iv Mass parts.

X _iv -X _i is preferably X _iv -X _i <10, more preferably X _iv -X _i <8, further preferably X _iv -X _i <6, and X _iv -X _i <4 is particularly preferred, and X _iv -X _i <2 is most preferred. When X _iv −X _i <10, the plasticizer hardly migrates even when the laminate is stored, so that the self-adhesion property can be kept low. Similarly, Y _i -Y _iv is preferably Y _i -Y _iv <10, more preferably Y _i -Y _iv <8, and further preferably Y _i -Y _iv <6. Y _i −Y _iv <4 is particularly preferable, and Y _i −Y _iv <2 is most preferable. When Y _i −Y _iv <10, the plasticizer is difficult to migrate even if the laminate is stored, and thus the self-adhesion property can be kept low.

X _ii -X _iv is preferably X _ii -X _iv <7, more preferably X _ii -X _iv <5, further preferably X _ii -X _iv <4, and X _ii -X _iv <3 is particularly preferred. When X _ii −X _iv <7, the plasticizer is difficult to migrate even if the laminate is stored for a long period of time, and thus the self-adhesiveness can be kept low. Similarly, Y _iv -Y _ii is preferably Y _iv -Y _ii <3, and more preferably Y _iv -Y _ii <2. When Y _iv -Y _ii <3, the plasticizer is difficult to migrate even if the laminate is stored for a long period of time, so that the self-adhesion property can be kept low.

X _iii -X _iv is preferably 0 <X _iii -X _iv , more preferably 5 <X _iii -X _iv , further preferably 10 <X _iii -X _iv , 15 < X _iii -X _iv is particularly preferable, and 20 <X _iii -X _iv is most preferable. In the case of 0 <X _iii -X _iv , when the laminate of the present invention is stored for a long period of time, the plasticizer hardly migrates, and the laminate is treated at a temperature exceeding 100 ° C. It is preferable in that the plasticizer quickly moves from 2) to the layer (1) and is excellent in balance with the characteristic that a laminate having excellent flexibility can be obtained. Similarly, Y _iv -Y _iii is preferably 0 <Y _iv -Y _iii , more preferably 5 <Y _iv -Y _iii , and further preferably 10 <Y _iv -Y _iii. 15 <Y _iv -Y _iii is particularly preferable, and 20 <Y _iv -Y _iii is most preferable. In the case of 0 <Y _iv -Y _iii , from the layer (2) by processing at a temperature exceeding 100 ° C. and a property that the plasticizer hardly migrates when the laminate of the present invention is stored for a long period of time. This is preferable in that the plasticizer quickly moves to the layer (1) to obtain a laminate that is excellent in flexibility and is excellent in balance with the characteristics.

  In the laminate of the present invention, when the total amount of plasticizers satisfies the above conditions, a laminate that is excellent in handleability when stored for a long period of time and exhibits high flexibility when used as an interlayer film for laminated glass. Can be obtained.

  The laminate of the present invention is less likely to be self-attached (blocking) during storage, has high strength, and is excellent in handleability. On the other hand, by treating the laminate of the present invention at a high temperature and a high pressure with a sufficient heat treatment, for example, an autoclave used in a laminated glass production process, the plasticizer contained in the layer (2) is converted into the layer (1). Therefore, the laminate of the present invention can suitably exhibit the flexibility and sound insulation required for the interlayer film for laminated glass.

  In the laminate of the present invention, the total amount of plasticizers contained in the layer (1) after heat treatment at 50 ° C. for 15 days is preferably larger than the total amount of plasticizers contained in the layer (1) before heat treatment. . When the laminate of the present invention satisfies such regulations, the laminate of the present invention is heat-treated at a high temperature and high pressure by an autoclave used in the laminated glass production process, so that the plastic contained in the layer (2) is obtained. When the agent quickly migrates to the layer (1) and the laminated body after the migration is stored, the plasticizer A that has once migrated to the layer (1) is less likely to migrate again to the layer (2). There is a tendency.

  The laminate of the present invention preferably has a thickness of 0.2 mm or more, more preferably 0.25 mm or more, and further preferably 0.3 mm or more. Further, the thickness is preferably 2.0 mm or less, more preferably 1.3 mm or less, and further preferably 1.0 mm or less. When the thickness of the laminate of the present invention is less than 0.2 mm, the penetration resistance tends to decrease when the laminate of the present invention is used as an interlayer film for laminated glass. Moreover, when the thickness of the laminated body of this invention exceeds 2.0 mm, it exists in the tendency for the weight of the laminated glass using the laminated body of this invention to increase.

  In the laminate of the present invention, the combination of the thicknesses of the layers (1) and (2) is, for example, that the sum of the thicknesses of the layers (1) is smaller than three times the sum of the thicknesses of the layers (2). Is preferably less than 2 times, more preferably less than 1.2 times, particularly preferably less than 0.7 times, and most preferably less than 0.5 times. When the sum of the thicknesses of the layer (1) is 3 times or more of the thickness of the layer (2), the plasticizer tends to move between layers or bleed when the laminate of the present invention is stored, and the present invention. When the laminate is used as an interlayer film for laminated glass, the penetration resistance and sound insulation properties of the obtained laminated glass tend to be impaired.

  The surface of the laminate of the present invention may be flat or may have a concavo-convex structure, but it is preferable that the concavo-convex structure is formed from the viewpoint of improving the bubble-removing property during the production of laminated glass.

  In the layered product of the present invention, conventionally known antioxidants, ultraviolet absorbers and other additives other than the polymer compound and the plasticizer are added to the layer (1) or the layer (2) as long as the effects of the present invention are not impaired. An agent may be further contained.

  When the laminate of the present invention is used by appropriately adjusting the adhesion with glass, such as an interlayer film for laminated glass, an adhesion improver (adhesion modifier) may be further added. As such an adhesion improver, conventionally known adhesion improvers such as alkali metal salts such as sodium acetate, potassium acetate, magnesium acetate and magnesium butyrate, and alkaline earth metal salts can be used. The addition amount of the adhesion improver can be adjusted so that, for example, the Pummel value obtained by the Pummel test becomes a value according to the purpose. When using an adhesive improvement agent, it is preferable to include in a layer (1).

  The total amount of the polymer compound (I) and the plasticizer in the layer (1) is preferably 40% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more. It is more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. When the total amount of the polymer compound (I) and the plasticizer is 40% by mass or more, the object of the present invention can be suitably achieved. The total amount of the polymer compound (II) and the plasticizer in the layer (2) is preferably 40% by mass or more, more preferably 60% by mass or more, and further preferably 80% by mass or more. Preferably, it is more preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more. When the total amount of the polymer compound (II) and the plasticizer is 40% by mass or more, the object of the present invention can be suitably achieved.

  The laminate of the present invention preferably has a moisture content of 0.1% by mass or more, more preferably 0.2% by mass or more. The laminate of the present invention preferably has a moisture content of 1% by mass or less, and more preferably 0.8% by mass or less. When the moisture content satisfies this range, when the laminate of the present invention is used as an interlayer film for laminated glass, the adhesive strength with glass can be set to an appropriate value.

  The laminate of the present invention can be obtained, for example, by molding a mixture obtained by mixing polyvinyl acetal, a plasticizer, and other additives by a conventionally known method into a sheet shape and laminating them. A method of forming into a sheet and a method of laminating can be performed by a conventionally known method.

[Laminated glass]
Especially the laminated body of this invention can be used conveniently as an intermediate film for laminated glasses.

  When the laminate of the present invention is used as an interlayer film for laminated glass, the laminated glass obtained by sandwiching the interlayer film for laminated glass between two sheets of glass and treating at a temperature exceeding 100 ° C. for 10 minutes or more The plasticizer contained in (1) and the layer (2), in particular, the plasticizer A migrates between the layers, and tends to be suitable in terms of obtaining a laminated glass excellent in safety including a flexible interlayer film for laminated glass. It is in.

  When the laminate of the present invention is used as an interlayer film for laminated glass, the glass laminated with the laminate of the present invention is, for example, inorganic glass such as float plate glass, polished plate glass, mold plate glass, meshed plate glass, and heat ray absorbing plate glass. Conventionally known organic glasses such as polymethyl methacrylate and polycarbonate can be used. These may be either colorless or colored. These may be used alone or in combination of two or more. Moreover, it is preferable that the thickness of glass is 100 mm or less normally.

  The laminated body of the present invention is a laminated glass obtained by sandwiching between two glasses and treating at a temperature of 120 ° C. or higher for at least 20 minutes, and the maximum loss coefficient at 20 ° C. and 2000 to 6000 Hz is 0.05. Preferably, it is 0.10 or more, more preferably 0.15 or more, and particularly preferably 0.20 or more. When the maximum value of the loss factor at 20 ° C. and 2000 to 6000 Hz is less than 0.05, the sound insulation near room temperature tends to be lowered.

  In a laminated glass obtained by sandwiching between two glasses and treating at a temperature of 120 ° C. or higher for at least 20 minutes, the maximum loss factor at 20 ° C. and 2000 to 6000 Hz is set to 0.05 or higher. Is a method in which the layer (1) and / or the layer (2) is a laminate containing polyvinyl acetal, and the total amount of the polymer compounds contained in the layer (1) and the layer (2) is 100 parts by mass. And a method in which the total amount of plasticizers contained in the layer (1) and the layer (2) is 20 parts by mass or more.

  Laminated glass obtained by using the laminate of the present invention as an interlayer film for laminated glass also constitutes the present invention. Such a laminated glass can be produced by a conventionally known method. For example, a method using a vacuum laminator device, a method using a vacuum bag, a method using a vacuum ring, a method using a nip roll, and the like can be mentioned. Moreover, after temporary press-bonding by the above-described method, a method of putting in an autoclave and performing a main bonding is also included. When processing by an autoclave, the conditions are preferably heat-treated for 10 to 120 minutes at 100 to 150 ° C. and 1.0 to 1.3 MPa, for example. In particular, when the laminate of the present invention is used as an interlayer film for laminated glass having excellent sound insulation, the laminate of the present invention is sandwiched between two glasses and temporarily bonded, and then 100 to 150 ° C., 1.0 to 1 When a laminated glass is produced by heat treatment in an autoclave at 3 MPa for 10 to 120 minutes, a laminate having a loss factor of 0.15 or more, preferably 0.20 or more at 20 ° C. or 40 ° C. at 2000 to 6000 Hz. Is preferably used. Similarly, it is preferable to use a laminate in which the haze of the laminated glass is 0.01% to 1.0% under the above conditions.

  In the laminate of the present invention, after melt-kneading at 150 ° C. for 5 minutes, the laminated glass is formed into a sheet having a thickness of 0.8 mm and sandwiched between two glasses. The haze is preferably less than 3%, more preferably less than 1%, and even more preferably less than 0.5%. When the haze of the laminated glass exceeds 3%, the transparency of the laminated glass tends to decrease.

As a method for setting the haze of the laminated glass to less than 3%, when the polymer compound (I) is polyvinyl acetal (1) and the polymer compound (II) is polyvinyl acetal (2), | H (1) -H (2) | is a method of 20 mol% or less, | A (1) -A (2) | is a method of 20 mol% or less, | VE (1) -VE (2) | 20 mol% or less, P (1) and P (2) are both 1100 or more, | n−m | is 2 or less, Y _i −X _i is 0 or more, etc. Is mentioned.

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

[Evaluation method]
(Evaluation of physical properties of polymer compounds)
The average degree of acetalization, average residual vinyl ester group amount and average residual hydroxyl group amount of PVB-1 to PVB-4 obtained in Production Examples 1 to 4 were measured according to JIS K6728: 1977.

  The hydroxyl values of PVB-1 to PVB-4 obtained in Production Examples 1 to 4 were measured according to JIS K1557: 2007.

  The ester values of PVB-1 to PVB-4 obtained in Production Examples 1 to 4 were measured according to JIS K 0070: 1992. Table 1 shows the measurement results of the average degree of acetalization, the average residual vinyl ester group amount, the average residual hydroxyl group amount, the hydroxyl value, and the ester value.

(Flexibility evaluation of laminate: measurement of S ₁ , S ₂ and S ₃ )
The laminates produced in this example and the comparative example were cut into a size of 1 cm × 10 cm, and were used at 23 ° C., a distance between chucks of 50 mm, 100 mm / 100 mm using an autograph (manufactured by Shimadzu Corporation, AG-IS) A tensile test was performed at min, and the stress S ₁ MPa at the time of 10% elongation of the laminate in the initial stage of production was measured. In addition, after storing the produced laminate at 23 ° C. for 5 weeks, the laminate was cut into a size of 1 cm × 10 cm and subjected to a tensile test at a rate of 23 ° C., a distance between chucks of 50 mm, and 100 mm / min using an autograph. The stress S ₂ MPa at 10% elongation was measured. Moreover, the produced laminated body was pinched | interposed into two PET films, and it pressed for 10 minutes with the load of 100 kg / cm < ² > under the temperature of 30 degreeC using the press. Further, the outside was sandwiched between two float glasses and treated at 140 ° C. for 30 minutes using an autoclave for laminated glass. The heat-treated laminate was cooled to 23 ° C. in 60 minutes and stored as it was in an atmosphere of 23 ° C. and 50% RH for 5 weeks. The treated laminate is cut to a size of 1 cm × 10 cm, and using an autograph, a tensile test is performed at 23 ° C., a distance between chucks of 50 mm, and 100 mm / min. The stress S ₃ MPa was measured. In addition, it can be said that it is a laminated body which is excellent in a softness | flexibility, so that the stress at the time of 10% elongation is low. Therefore, a laminate having a low stress at 10% elongation is suitable from the viewpoint of developing safety performance when used as an interlayer film for laminated glass.

(Evaluation of self-adhesion of laminates)
The laminated body at the initial stage of production obtained in this example and the comparative example was cut into a size of 10 cm × 3 cm to produce two laminated pieces. The two laminate pieces were stacked, a 6 kg weight was placed thereon, and treated for 24 hours at 23 ° C. and 50% RH. The two laminate pieces after the treatment were subjected to a T-type peel strength test at a speed of 100 mm / min using an autograph. The value obtained by dividing the maximum value of the peeling force by the width (3 cm) of the laminate piece was defined as the self-adhesion force (N / 3 cm). The same test was conducted 5 times in total, and the average value was defined as the average self-adhesion force (N / 3 cm).

  In this example and comparative example, the average self-adhesion force was also measured in the same manner as described above for the laminates stored for 5 weeks under the atmosphere of 23 ° C. and 50% RH.

(Measurement of temperature at which tan δ is maximized)
In the examples and comparative examples, the compositions used for the layer (1) and the layer (2) were respectively 100 kgf / cm at a temperature of 120 ° C. with a hot press machine (SFA-37, manufactured by Shindo Metal Industry Co., Ltd.). The sample was pressed for 10 minutes under a load of ² to prepare a sample having a thickness of 0.8 mm. These were each cut into a width of 3 mm to obtain dynamic viscoelasticity measurement samples. About this measurement sample, a dynamic viscoelastic device (Rheogel-E4000 manufactured by UBM Co., Ltd.) was used according to JIS K7244-4: 1999, and the temperature was increased from −50 ° C. to 120 ° C. at 3 ° C./min. While being heated, the distance between chucks was 20 mm, the frequency was 0.3 Hz, the displacement was 75.9 μm, the automatic static load was 26 g, and the tensile mode was used for analysis.

(Production of laminate kneaded materials, measurement of haze of laminated glass)
The laminates in this example and the comparative example were melt kneaded at 150 ° C. for 5 minutes to prepare a kneaded product. The obtained kneaded material was hot-pressed at a load of 100 kgf / cm ² for 30 minutes at a temperature of 150 ° C. to form a sheet having a thickness of 0.8 mm. The obtained sheet was sandwiched between two float glass sheets having a thickness of 3 mm, temporarily bonded by vacuum back, and then subjected to main bonding at 135 ° C. and 1.2 MPa for 60 minutes in an autoclave to obtain a laminated glass without bubbles. . The haze of the obtained laminated glass was measured based on JIS K 7105: 1981 using a haze meter HZ-1 (manufactured by Suga Test Instruments Co., Ltd.).

(Measurement of the maximum loss factor)
The laminates obtained in this example and comparative example were sandwiched between 50 mm × 300 mm × 3 mm glass, temporarily bonded by vacuum back, then processed by autoclaving at 135 ° C. and 1.2 MPa for 60 minutes for main bonding, A laminated glass having no thickness was obtained. Excitation was performed in the range of 100 to 10000 Hz with a vibrator (EMIC, small vibration generator 512-A) at 20 ° C., and the frequency response function at that time was FFT analyzer (manufactured by Ono Sokki, DS-2100). The maximum loss coefficient at 2000 to 6000 Hz was calculated using servo analysis software (DS-0242, manufactured by Ono Sokki Co., Ltd.). The larger the loss factor, the better the sound insulation performance of the laminated glass.

[Polyvinyl butyral]
(Production Example 1)
A 5 liter glass container equipped with a reflux condenser, thermometer, and squid type stirring blade was charged with 4050 g of ion-exchanged water and 330 g of polyvinyl alcohol (PVA-1: polymerization degree 1700, saponification degree 99 mol%), and the temperature was raised to 95 ° C. Warm to dissolve the polyvinyl alcohol completely. The resulting solution was gradually cooled to 10 ° C. over about 30 minutes with stirring at 160 rpm, 189 g of n-butyraldehyde and 200 mL of 20% aqueous hydrochloric acid were added, and a butyralization reaction was performed for 50 minutes. Thereafter, the temperature was raised to 65 ° C. over 60 minutes, held at 65 ° C. for 120 minutes, and then cooled to room temperature. After washing the obtained resin with ion-exchanged water, sodium hydroxide aqueous solution is added to neutralize the remaining acid, and further washed with excess ion-exchanged water and dried to obtain polyvinyl butyral (PVB-1). It was.

(Production Example 2)
PVB- was prepared in the same manner as in Production Example 1 except that 330 g of polyvinyl alcohol (PVA-2: polymerization degree 1700, saponification degree 92 mol%) was charged instead of PVA-1 and the amount of n-butyraldehyde was changed to 195 g. 2 was obtained.

(Production Example 3)
PVB-3 was obtained in the same manner as in Production Example 1 except that the amount of n-butyraldehyde used was changed to 165 g.

(Production Example 4)
PVB-4 was obtained in the same manner as in Production Example 1 except that the amount of n-butyraldehyde used was changed to 139 g.

[Plasticizer A and Plasticizer B]
Tables 2 and 3 show the plasticizer A and the plasticizer B used in this example and the comparative example, respectively.

Example 1
(Preparation of layer (1))
100 parts by mass of PVB-1 and 25 parts by mass of plasticizer B-1 were prepared and melt-kneaded at 150 ° C. for 5 minutes using a lab plast mill (Toyo Seiki Seisakusho, 20R200). did. The obtained composition was pressed for 10 minutes at a load of 100 kgf / cm ² at a temperature of 150 ° C. using a hot press machine to produce a layer (1) having a thickness of 0.1 mm.

(Preparation of layer (2))
100 parts by mass of PVB-1, 97 parts by mass of plasticizer A-1, and 35 parts by mass of plasticizer B-1 were prepared and melt-kneaded at 150 ° C. for 5 minutes using a lab plast mill. did. The obtained composition was pressed with a heat press at a temperature of 120 ° C. under a load of 100 kgf / cm ² for 10 minutes to produce a layer (2) having a thickness of 0.6 mm.

(Production of laminate)
Layer (1), layer (2), and layer (1) were stacked in this order, and were pressed with a press at a load of 100 kgf / cm ² for 10 minutes at a temperature of 30 ° C. to obtain a laminate. The composition and thickness of layer (1) and layer (2) are shown in Table 4-1.

(Examples 2-27 and Comparative Examples 1-4)
In the same manner as in Example 1, except that the composition and thickness of the layer (1) and layer (2) were as described in Table 4-1 or Table 4-2, Examples 2 to 27 and Comparative Example The laminated body of Examples 1-4 was produced.

For the laminates of Examples 1 to 27 and Comparative Examples 1 to 4, the absolute value of the difference in average residual hydroxyl group amount in each polyvinyl acetal contained in the layer (1) or the layer (2) | H (1) −H ( 2) |, absolute value of difference in average acetalization degree | A (1) -A (2) |, absolute value of difference in average residual vinyl ester group amount | VE (1) -VE (2) |, and raw material And the difference in the plasticizer content (Y _i − with respect to 100 parts by mass of each polymer compound contained in the layer (1) or the layer (2)). X _i ) is shown in Table 5.

Further, the laminates of Examples 1 to 27 and Comparative Examples 1 to 4 were evaluated for S _1, S ₂ and S ₃ of the laminate according to the method described in the evaluation method described above. Table 6 shows the values of the obtained results S ₁ , S ₂ , S ₃ , S ₂ / S ₁ , S ₁ -S ₂ , S ₃ / S ₁ , S ₁ -S ₃ , and S ₂ -S _3. .

  For the laminates of Examples 1-27 and Comparative Examples 1-4, according to the method described in the evaluation method described above, the average self-adhesion force at the initial stage of production of the laminate and the average self-adhesion force of the laminate after storage for 5 weeks from production Evaluation, evaluation of temperature at which tan δ of layer (1) is maximized and temperature at which tan δ of layer (2) is maximized, evaluation of haze when kneaded product of laminated body is used as interlayer film for laminated glass, laminated body The maximum loss coefficient at 2000 to 6000 Hz was evaluated. Table 7 shows the evaluation results.

Claims (14)

A layered product comprising a layer (1) and a layer (2) on at least one side of the layer (1),
The layer (1) contains the polymer compound (I),
The layer (2) contains the polymer compound (II),
The stress at 10% elongation of the laminate at 23 ° C. is S ₁ MPa,
After the laminate is stored at 23 ° C. and 50% RH for 5 weeks, the stress at 10% elongation at 23 ° C. is S ₂ MPa,
The laminate was treated at 140 ° C. for 30 minutes, cooled to 23 ° C. within 1 hour after the treatment, and after cooling, the stress at 10% elongation at 23 ° C. after storage at 23 ° C. and 50% RH for 5 weeks. S ₃ MPa
A laminated body satisfying the following formulas (1) to (3).
_{(1): S 2 / S} 1 ≧ 0.2 and / or _S 1 -S ₂ ≦ 1.0
(2): S ₃ / S ₁ ≦ 0.9 and / or S ₁ -S ₃ ≧ 0.2
(3): S ₂ -S ₃ > 0   The layered product according to claim 1 which has a layered structure which has three or more layers and at least layer (1) is the outermost layer.   The laminate according to claim 1 or 2, wherein at least one layer (1) or layer (2) comprises at least one plasticizer. At least one plasticizer is plasticizer A;
The laminate according to claim 3, wherein HV (A) ≥30 when the hydroxyl value of the plasticizer A is HV (A) mgKOH / g.   In at least one of the layers (1) and (2), tan δ measured by performing a dynamic viscoelasticity test under the condition of a frequency of 0.3 Hz in accordance with JIS K7244-4: 1999 is the maximum. The laminated body in any one of Claims 1-4 whose temperature which becomes 20 degreeC or more.   The laminate according to any one of claims 1 to 5, wherein at least one of the polymer compound (I) or the polymer compound (II) is polyvinyl acetal. The polymer compound (I) is polyvinyl acetal (1), the polymer compound (II) is polyvinyl acetal (2),
When the average residual hydroxyl group amount of the polyvinyl acetal (1) is H (1) and the average residual hydroxyl group amount of the polyvinyl acetal (2) is H (2), | H (1) −H (2) | The layered product according to claim 6 which is below mol%. The total amount of plasticizers contained in the layer (1) with respect to 100 parts by mass of the polymer compound (I) is X _i parts by mass, and contained in the layer (2) with respect to 100 parts by mass of the polymer compound (II). When the total amount of plasticizer is Y _i parts by mass,
0 <Y _i -X _i, laminate according to any one of claims 3-7. In a laminated glass obtained by sandwiching between two glasses and treating at a temperature of 120 ° C. or higher for at least 20 minutes,
The laminate according to any one of claims 1 to 8, wherein a maximum value of a loss coefficient at 20 ° C and 2000 to 6000 Hz is 0.05 or more.   The laminated body in any one of Claims 1-9 whose thickness of a layer (1) is below the thickness of a layer (2). After melting and kneading at 150 ° C. for 5 minutes, when forming a laminated glass sandwiched between two glasses formed into a 0.8 mm thick sheet,
The laminate according to any one of claims 1 to 10, wherein the haze of the laminated glass is less than 3%.   The intermediate film for laminated glasses containing the laminated body in any one of Claims 1-11.   A laminated glass in which the interlayer film for laminated glass according to claim 12 is sandwiched between two glasses. The manufacturing method of the laminated glass obtained by pinching | interposing the intermediate film for laminated glasses of Claim 12 with two sheets of glass, and processing for 10 minutes or more at the temperature exceeding 100 degreeC.