JP2021070269A - Laminate and method for producing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated body capable of suppressing deformation of a sealed material in the laminated body.
SOLUTION:
A sealing layer in which a sealing material is sealed in a resin I containing a block copolymer hydride having no alkoxysilyl group, and an alkoxysilyl arranged adjacent to the front surface and the back surface of the sealing layer, respectively. It is a laminate including two alkoxysilyl group-containing resin layers composed of resin II containing block copolymer hydride having a group. The thickness of the sealing layer is d1, the thickness of the alkoxysilyl group-containing resin layer is d2, d3, the thickness of the sealed product is d6, and the value of d1 / d6 is 1.80 or more, and (d2 + d3) / d1. The value of is 0.01 or more and 1.10 or less.
[Selection diagram] Fig. 1

Description

The present invention relates to a laminate and a method for producing a laminate.

Conventionally, structural units derived from aromatic vinyl compounds have been mainly used for producing encapsulants for solar cell modules, encapsulants for organic electroluminescence (EL) elements, encapsulants for electronic parts, laminated glass polymers, and the like. A polymer obtained by subjecting a block copolymer having a polymer block as a component and a polymer block containing a structural unit derived from a chain conjugated diene compound as a main component to a hydrogenation reaction (block common weight). Combined hydride) is used.

For example, in Patent Document 1, in the method for producing an organic EL element encapsulant, an alkoxysilyl is used as a block copolymer hydride obtained by hydrogenating a block copolymer containing an aromatic vinyl block and a chain-conjugated diene block. A method for manufacturing an organic EL element encapsulant, which comprises adhering and integrating a sheet-shaped encapsulant made of a resin having a base introduced therein, has been proposed.
Further, in Patent Document 2, an ultraviolet absorber is used on one or both sides of a film made of a block copolymer hydride obtained by hydrogenating a block copolymer containing an aromatic vinyl block and a chain-conjugated diene block. A multilayer film in which layers of a resin composition containing a block copolymer hydride having an alkoxysilyl group introduced therein is laminated has been proposed. Further, Patent Document 2 discloses that a multilayer film satisfying such a configuration is useful as an optical film such as a polarizer protective film for a polarizing film.

International Publication No. 2017/159859 International Publication No. 2015/105127

Here, in the laminated body formed by sealing the material to be sealed (hereinafter referred to as "sealed material") inside, the sealed material is contained in the laminated body even when the laminated body is heated. It is required to be able to suppress deformation. However, depending on the method according to the above-mentioned prior art, the deformation of the sealed material in the obtained laminate could not be sufficiently suppressed.

Therefore, an object of the present invention is to provide a laminate capable of suppressing deformation of the sealed material in the laminate, and a method for producing such a laminate.

The present inventors have diligently studied to achieve the above object. As a result, when forming a laminate in which the sealed material is sealed in the resin, a resin containing a predetermined block copolymer hydride having no alkoxysilyl group is adjacent to the sealed material. Further, by arranging a layer made of a resin containing a predetermined block copolymer hydride having an alkoxysilyl group on the outside thereof, it is effective that the sealed material sealed in the laminate is deformed. The present invention has been completed by finding that it can be suppressed.

That is, the present invention aims to advantageously solve the above problems, and the laminate of the present invention is sealed in a resin I containing a block copolymer hydride having no alkoxysilyl group. Two alkoxysilyls consisting of a sealing layer in which a fastener is sealed and a resin II containing a block copolymer hydride having an alkoxysilyl group, which are arranged adjacent to each other on the front surface and the back surface of the sealing layer. A laminate comprising a group-containing resin layer, wherein the block copolymer hydride contained in the resin I contains at least two structural units [a-1] derived from an aromatic vinyl compound as main components. A block copolymer [C] having a polymer block [A-1] and at least one polymer block [B-1] containing a structural unit [b-1] derived from a chain conjugated diene compound as a main component. The block copolymer [D-1] formed by hydrogenating -1], and the block copolymer hydride having the alkoxysilyl group contained in the resin II is a structural unit [a] derived from an aromatic vinyl compound. At least two polymer blocks [A-2] containing at least two polymer blocks [A-2] as main components and at least one polymer block [B-2] containing at least two polymer blocks [b-2] derived from a chain conjugated diene compound as main components. ], And the block polymer [E] formed by introducing an alkoxysilyl group into the block polymer [D-2] formed by hydrogenating the block copolymer [C-2] having the above. Structural unit [a-1] and the structural unit [a-2], the polymer block [A-1] and the polymer block [A-2], the structural unit [b-1] and the structural unit [ b-2], the polymer block [B-1] and the polymer block [B-2], the block copolymer [C-1] and the block copolymer [C-2], and the above. The block copolymer [D-1] and the block copolymer [D-2] may be the same or different from each other, and the thickness of the sealing layer is d1 and the two alkoxysilyls are used. The thickness of one of the group-containing resin layers is d2, the thickness of the other alkoxysilyl group-containing resin layer is d3, the thickness of the encapsulated product is d6, and the values of d1 / d6 are It is characterized in that it is 1.80 or more and the value of (d2 + d3) / d1 is 0.01 or more and 1.10 or less. A laminate having such a structure can suppress deformation of the sealed material in the laminate.

Here, in the laminate of the present invention, the shortest distance from the surface of the sealing layer to the surface of the sealing material is d4, and the shortest distance from the back surface of the sealing layer to the back surface of the sealing material is d5. , D4 / d5 is preferably 0.33 or more and 3.00 or less. If the position in the sealing layer in the thickness direction of the sealing material is within the range satisfying the above conditions, the deformation of the sealing material in the laminated body can be suppressed more satisfactorily.

Further, in the laminate of the present invention, the total amount of the structural unit [a-1] derived from the aromatic vinyl compound in the block copolymer [C-1] is the entire block copolymer [C-1]. The mass fraction of the block copolymer [C-1] is wb-1, and the total amount of the structural unit [b-1] derived from the chain-conjugated diene compound is wb-1. When this is done, the ratio of wa-1 to wb-1 (wa-1: wb-1) is 20:80 to 65:35, and the aromatic in the block copolymer [C-2]. The total amount of the structural unit [a-2] derived from the vinyl compound has a mass fraction of wa-2 in the entire block copolymer [C-2], and the structural unit [b-2] derived from the chain conjugated diene compound. ], The ratio of wa-2 to wb-2 (wa-2: wb-2) is calculated when the mass fraction of the block copolymer [C-2] in the whole is wb-2. , 20:80 to 65:35, and the w-1 and the w-2, and the wb-1 and wb-2 may be the same or different from each other. If the resin constituting the sealing layer and the alkoxysilyl group-containing resin layer has a composition that satisfies the above conditions, the deformation of the sealed product in the laminated body can be further reduced.

Further, in the laminate of the present invention, the thicknesses d2 and d3 of the alkoxysilyl group-containing resin layer are independently any value within the range of 1 μm or more and 400 μm or less, and the thickness d1 of the sealing layer. Is preferably 200 μm or more and 2,000 μm or less. If the structure of the laminated body satisfies such a condition, the deformation of the sealed material in the laminated body can be further reduced.

Further, in the laminated body of the present invention, the thickness d6 of the sealed material is preferably 10 μm or more and 500 μm or less. When the thickness of the sealed material is within the above range, the deformation of the sealed material in the laminated body can be further reduced.

Further, in the laminate of the present invention, the encapsulant is a plate-like body, and the constituent material of the encapsulant is a resin containing a polyethylene terephthalate resin, a polycarbonate resin, a polypropylene resin, a polyethylene resin, or a polyacrylonitrile resin; It preferably contains any of float glass, heat-strengthened glass, or glass containing chemically strengthened glass, a metal containing stainless steel, aluminum, or copper, and a composite composed of a combination thereof. If the encapsulant is a plate-like body and the constituent material of the encapsulant contains a resin, glass, metal, or a composite thereof, the deformation of the encapsulant in the laminate is further reduced. be able to.
In addition, in this specification, a "plate-like body" is a concept including not only a flat plate-like object but also a plate-like object including a shape having irregularities on one or both of the front surface and the back surface.

Further, in the laminate of the present invention, the groups of the two alkoxysilyl group-containing resin layers made of the resin II are arranged adjacent to the surface opposite to the surface adjacent to the sealing layer. Further materials may be provided. A laminate having a base material on both sides can be suitably applied to various uses.

An object of the present invention is to solve the above problems advantageously, and the method for producing a laminate of the present invention comprises sealing a sealed material in a resin I having no alkoxysilyl group. A method for producing a laminate comprising a sealing layer and two alkoxysilyl group-containing resin layers made of alkoxysilyl group-containing resin II arranged adjacent to each other on the front surface and the back surface of the sealing layer. Contains the alkoxysilyl group-containing resin II layer (2-1), the resin I layer (1-1), the encapsulant, the resin I layer (1-2), and the alkoxysilyl group-containing layer (1-2). The step of heating and integrating the laminate in which the layer (2-2) composed of the resin II is laminated in this order is included, and the resin I contains a block copolymer hydride and the block copolymer hydrogen. The compound is mainly composed of at least two polymer blocks [A-1] containing the structural unit [a-1] derived from the aromatic vinyl compound as a main component and the structural unit [b-1] derived from the chain conjugated diene compound. A block copolymer [D-1] formed by hydrogenating a block copolymer [C-1] having at least one polymer block [B-1] as a component, and the alkoxysilyl group-containing resin. II contains a block copolymer hydride having an alkoxysilyl group, and the block copolymer hydride having an alkoxysilyl group has at least a structural unit [a-2] derived from an aromatic vinyl compound as a main component. A block copolymer having two polymer blocks [A-2] and at least one polymer block [B-2] containing a structural unit [b-2] derived from a chain conjugated diene compound as a main component. It is a block copolymer [E] formed by introducing an alkoxysilyl group into a block copolymer [D-2] formed by hydrogenating [C-2], and the structural unit [a-1] and the above. Structural unit [a-2], the polymer block [A-1] and the polymer block [A-2], the structural unit [b-1] and the structural unit [b-2], the polymer block [B-1] and the polymer block [B-2], the block copolymer [C-1] and the block copolymer [C-2], and the block copolymer [D-1]. And the block copolymer [D-2] may be the same or different from each other, and the thickness of the layer (1-1) made of the resin I is (t1-1), and the thickness of the layer (1-1) is higher than that of the resin I. The thickness of the layer (1-2) made of (1-2) is (t1-2), the thickness of the layer (2-1) made of resin II is (t2-1), and the resin I The thickness of the layer (2-2) composed of I is (t2-2), and the thickness of the sealant is St, (t2-1) / (t1-1), and (t2-2) / ( The values of t1-2) are independently within the range of 0.01 or more and 1.10 or less, and the values of St / (t1-1) and St / (t1-2) are independent of each other. Therefore, it is characterized in that it is 1.20 or less. By carrying out a step of heating and integrating a predetermined laminate including a layer satisfying the predetermined composition as described above to form a laminate, deformation of the sealed material in the laminate is small. The laminate can be satisfactorily manufactured.

Here, in the method for producing a laminated body of the present invention, it is preferable that the value of (t1-1) / (t1-2) is 0.33 or more and 3.00 or less. If the relative relationship between the thickness of the layer (1-1) made of resin I and the thickness of the layer (1-2) made of resin I is within the above range, the sealing material in the sealing layer The position in the thickness direction can be controlled within an appropriate range, and the deformation of the sealed material in the obtained laminate can be suppressed more satisfactorily.

According to the present invention, it is possible to provide a laminate capable of suppressing deformation of the sealed material in the laminate, and a method for producing such a laminate.

It is a schematic structure of the laminated body with a base material which concerns on an example of this invention. It is a schematic structure of a laminate that is heated and integrated in the production method according to an example of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. Although drawings may be referred to in the description, the same components are shown with the same reference numerals. First, the laminate of the present invention will be described, and then a method for producing the laminate of the present invention capable of suitably producing such a laminate will be described. The laminate of the present invention can be suitably used, for example, as a window member used for automobiles, ships, railways, and building materials, or as a sealing body having electronic components inside.

(Laminated body)
In the laminate of the present invention, an alkoxy layer in which a sealing material is sealed in a resin I containing a block copolymer hydride and an alkoxy arranged adjacent to the front surface and the back surface of the sealing layer, respectively. It is a laminate including two alkoxysilyl group-containing resin layers made of resin II containing block copolymer hydride having a silyl group. Further, in the laminate of the present invention, at least two polymer blocks [A-] in which the block copolymer hydride contained in the resin I contains the structural unit [a-1] derived from the aromatic vinyl compound as a main component. Block copolymer [C-1] having at least one polymer block [B-1] containing 1] and a structural unit [b-1] derived from a chain conjugated diene compound as a main component is hydrogenated. It is a block copolymer [D-1] composed of. Furthermore, in the laminate of the present invention, the block copolymer hydride having an alkoxysilyl group contained in Resin II contains at least two block copolymer hydrides containing the structural unit [a-2] derived from an aromatic vinyl compound as a main component. A block copolymer [C] having a polymer block [A-2] and at least one polymer block [B-2] containing a structural unit [b-2] derived from a chain conjugated diene compound as a main component. It is a block copolymer [E] formed by introducing an alkoxysilyl group into a block copolymer [D-2] formed by hydrogenating -2]. Then, the structural unit [a-1] and the structural unit [a-2], the polymer block [A-1] and the polymer block [A-2], the structural unit [b-1] and the structural unit [b-2] ], Polymer block [B-1] and polymer block [B-2], block copolymer [C-1] and block copolymer [C-2], and block copolymer [D-1]. ] And the block copolymer [D-2] may be the same or different from each other. Further, the thickness of the sealing layer is d1, the thickness of one of the two alkoxysilyl group-containing resin layers is d2, and the thickness of the other alkoxysilyl group-containing resin layer is d3. The feature is that the value of d1 / d6 is 1.80 or more and the value of (d2 + d3) / d1 is 0.01 or more and 1.10 or less, where d6 is the thickness of the stop.
In the laminated body having a structure satisfying such a condition, the deformation of the sealed material is small. Hereinafter, the structure of the laminated body according to an example of the present invention and each component constituting the laminated body will be described in detail.

<Thickness of each layer in the laminated body>
FIG. 1 shows a schematic configuration of a laminate with a base material according to an example of the present invention. The laminated body 100 with a base material includes the laminated body 10. The laminate 10 includes a sealing layer 1 in which the sealing material 3 is sealed in the resin I, and an alkoxysilyl group-containing resin layer 2 composed of a resin II containing a block copolymer hydride having an alkoxysilyl group. , Equipped with. The laminated body 10 having such a structure includes a base material 11 arranged adjacent to the front surface and the back surface. Here, the thickness of the sealing layer 1 is d1, the thickness of one of the two alkoxysilyl group-containing resin layers (upper in FIG. 1) is d2, and the thickness of the other (lower in FIG. 1) is d2. The thickness of the alkoxysilyl group-containing resin layer 2 on the side) is d3, the thickness of the encapsulated product 3 is d6, the value of d1 / d6 is 1.80 or more, and the value of (d2 + d3) / d1 is 0.01. It is 1.10 or less.

Here, the value of d1 / d6 is preferably 2.45 or more, more preferably 2.50 or more, preferably 5.50 or less, and more preferably 5.00 or less. preferable.
Further, the value of (d2 + d3) / d1 is preferably 1.05 or less, more preferably 0.90 or less, and further preferably 0.50 or less.
If the structure of the laminated body 10 satisfies such a condition, the deformation of the sealed material 3 in the laminated body 10 can be reduced more satisfactorily.

Further, the value of d4 / d5 is 0, where d4 is the shortest distance from the front surface of the sealing layer 1 to the front surface of the sealing material 3, and d5 is the shortest distance from the back surface of the sealing layer 1 to the back surface of the sealing material 3. It is preferably .33 or more, more preferably 0.35 or more, preferably 3.00 or less, more preferably 2.50 or less, and further preferably 2.40 or less. preferable. The value of d4 / d5 is a parameter that can define the position of the sealing material 3 in the sealing layer 1 in the thickness direction. That is, the closer the value of d4 / d5 is to 1, the more the structure is such that the sealing material 3 is arranged near the center in the thickness direction in the sealing layer 1. Then, as long as the value of d4 / d5 is within the range satisfying the condition, the sealing material 3 is not excessively biased toward the upper side or the lower side in the thickness direction in the sealing layer 1. Therefore, the deformation of the sealed material 3 in the laminated body can be suppressed more satisfactorily.

Further, it is preferable that the thicknesses d2 and d3 of the alkoxysilyl group-containing resin layer 2 are independently set to any value within the range of 1 μm or more and 400 μm or less. Further, it is more preferable that the thicknesses d2 and d3 are independently set to any value within the range of 5 μm or more and 100 μm or less.
Furthermore, the thickness d1 of the sealing layer 1 is preferably 200 μm or more, more preferably 600 μm or more, preferably 2,000 μm or less, preferably 1,400 μm or less, 1, It is more preferably 000 μm or less.
The thickness d6 of the sealed product 3 is preferably 10 μm or more and 500 μm or less.
If the structure of the laminated body 10 satisfies such a condition, the deformation of the sealed material 3 in the laminated body 10 can be reduced more satisfactorily.

The sealing material 3 can be a plate-like body. When the encapsulant 3 of the plate-shaped body has a shape having irregularities on one or both of the front surface and the back surface, the maximum distance between the front surface and the back surface corresponds to the thickness d1 of the plate-shaped body.

<Encapsulation layer>
The sealing layer 1 has a structure in which the sealing material 3 is sealed in the resin I containing the block copolymer hydride. Resin I containing block copolymer hydride does not contain block copolymer hydride having an alkoxysilyl group, unlike resin II. Therefore, it is possible to satisfactorily suppress the deformation of the sealed material 3 in the laminated body 10.

<< Resin I >>
Resin I contains a block copolymer hydride having no alkoxysilyl group and may optionally contain an additive.
The block copolymer hydride contained in Resin I is derived from at least two polymer blocks [A-1] having a structural unit [a-1] derived from an aromatic vinyl compound as a main component and a chain conjugated diene compound. Block copolymer [D-1] formed by hydrogenating at least one polymer block [B-1] containing the structural unit [b-1] of the above and a block copolymer [C-1] having the same. ].

Hereinafter, the polymer block [A-1], the polymer block [B-1], the block copolymer [C-1], the block copolymer hydride [D-1], and the additive will be described in detail in this order. To do.

[Polymer block [A-1]]
The polymer block [A-1] is a polymer block containing a structural unit [a-1] derived from an aromatic vinyl compound as a main component. Here, "mainly composed of the structural unit [a-1] derived from the aromatic vinyl compound" means "the structural unit [a-1] derived from the aromatic vinyl compound in the polymer block [A-1]". ] Content is more than 50% by mass. " The content of the structural unit [a-1] derived from the aromatic vinyl compound in the polymer block [A-1] is usually 90% by mass or more, preferably 95% by mass or more, and more preferably 99% by mass or more. is there. When the content of the structural unit [a-1] derived from the aromatic vinyl compound in the polymer block [A-1] is equal to or higher than the above lower limit, the sealing layer 1 has good heat resistance. The polymer block [A-1] may contain a component other than the structural unit [a-1] derived from the aromatic vinyl compound. Other components include structural units [b-1] and / or other structural units derived from chain conjugated diene. The content of the structural unit [b-1] and / or other structural units is usually 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, based on the polymer block [A-1]. Is.

The composition and block length of the structural units in the plurality of polymer blocks [A-1] contained in the block copolymer [C-1] may be the same as long as they satisfy the above range. , May be different.

<Polymer block [B-1]>
The polymer block [B-1] is a polymer block containing a structural unit [b-1] derived from a chain conjugated diene compound as a main component. Here, "mainly composed of the structural unit [b-1] derived from the chain-conjugated diene compound" means "the structural unit [b-1] derived from the chain-conjugated diene compound in the polymer block [B-1]". -1] has a content of more than 50% by mass. " The content of the structural unit [b-1] derived from the chain conjugated diene compound in the polymer block [B-1] is usually 90% by mass or more, preferably 95% by mass or more, and more preferably 99% by mass or more. Is. When the content of the structural unit [b-1] derived from the chain conjugated diene compound in the polymer block [B-1] is equal to or higher than the above lower limit, the sealing layer 1 has good flexibility and impact resistance. .. The polymer block [B-1] may contain a component other than the structural unit [b-1] derived from the chain conjugated diene compound. Examples of other components include structural units [a-1] derived from aromatic vinyl compounds and / or other structural units. The content of the structural unit [a-1] and / or other structural units is usually 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less, based on the polymer block [B-1]. Is.

When the block copolymer [C-1] has a plurality of polymer blocks [B-1], the composition and block length of the structural units in the polymer block [B-1] are the same, but the phases. It may be different.

Here, examples of the aromatic vinyl compound capable of forming the above-mentioned structural unit [a-1] include styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4. Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, such as −diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, etc .; 4-chloro Styrenes having halogen atoms as substituents such as styrene, dichlorostyrene, 4-monofluorostyrene; styrenes having alkoxy groups having 1 to 6 carbon atoms as substituents such as 4-methoxystyrene; 4-phenylstyrene. Etc., styrenes having an aryl group as a substituent; and the like. Among these, aromatic vinyl compounds containing no polar group, such as styrene and styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent, are preferable from the viewpoint of hygroscopicity, and are easily available industrially. , Styrene is particularly preferable.

Examples of the chain-conjugated diene compound capable of forming the above-mentioned structural unit [b-1] include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and 1,3-. Examples include pentadiene. Among these, a chain-conjugated diene compound containing no polar group is preferable from the viewpoint of hygroscopicity, and 1,3-butadiene and isoprene are particularly preferable from the viewpoint of industrial availability.

<Block copolymer [C-1]>
The block copolymer [C-1] is a precursor of the block copolymer hydride [D-1], and is a precursor of at least two polymer blocks [A-1] and at least one polymer block [B-1]. ] And is a polymer containing.

The number of polymer blocks [A-1] in the block copolymer [C-1] is usually 3 or less, preferably 2. The number of polymer blocks [B-1] in the block copolymer [C-1] is usually 2 or less, preferably 1.

The form of the block copolymer [C-1] is not particularly limited and may be a chain type block or a radial type block, but the chain type block is preferable because of its excellent mechanical strength.
The most preferable form of the block copolymer [C-1] is a triblock copolymer ([A-1]-[] in which the polymer block [A-1] is bonded to both ends of the polymer block [B-1]. B-1]-[A-1]).

Here, the mass fraction of the total amount of the structural unit [a-1] derived from the aromatic vinyl compound in the block copolymer [C-1] to the entire block copolymer [C-1] is wa-1. When the mass fraction of the total amount of the structural unit [b-1] derived from the chain conjugated diene compound to the entire block copolymer [C-1] is wb-1, wa-1 and wb- The ratio to 1 (wa: wb) is preferably 20:80 to 65:35, more preferably 30:70 to 60:40, and even more preferably 40:60 to 55:45. If the amount of w-1 is too large, the heat resistance of the sealing layer 1 is high, but the flexibility may be low. On the other hand, when the amount of wa-1 is too small, the flexibility of the sealing layer 1 is increased, but the heat resistance may be lowered. Therefore, by setting the value of wa-1 within an appropriate range, the heat resistance and flexibility of the resin component constituting the sealing layer 1 can be appropriately balanced, and as a result, the inside of the sealing layer 1 It is possible to effectively prevent the sealed material 3 sealed in the above from being deformed by heat.
In addition, wa-1 and wb-1 can be calculated by measuring ^{1 1 H-NMR.}

The molecular weight of the block copolymer [C-1] is a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent, and is usually 35. It is 000 or more, preferably 38,000 or more, more preferably 40,000 or more, usually 200,000 or less, preferably 150,000 or less, and more preferably 100,000 or less. The molecular weight distribution (Mw / Mn) of the block copolymer [C-1] is preferably 3.0 or less, more preferably 2.0 or less, still more preferably 1.6 or less. When Mw and Mw / Mn are within the above ranges, the heat resistance and mechanical strength of the sealing layer 1 are improved. As a result, it is possible to effectively suppress the deformation of the sealed material 3 sealed in the sealing layer 1 due to heat.

The method for producing the block copolymer [C-1] is not particularly limited, and a known method can be adopted. Specifically, as a method for producing the block copolymer [C-1], for example, the method described in International Publication No. 2015/105127 and the like can be mentioned.

<Block Copolymer Hydride [D-1]>
The block copolymer hydride [D-1] selectively hydrogenates only the carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain-conjugated diene compound of the block copolymer [C-1]. The polymer may be a polymer, or the carbon-carbon unsaturated bond of the main chain and side chain derived from the chain-conjugated diene compound of the block copolymer [C-1], and the aromatic ring derived from the aromatic vinyl compound. It may be a polymer obtained by hydrogenating the carbon-carbon unsaturated bond of the above, or it may be a mixture thereof. The method of hydrogenating the unsaturated bond in the block copolymer [C-1], the reaction form, and the like are not particularly limited, and the method may be carried out according to a known method.

Among them, carbon-carbon unsaturated bonds of the main chain and side chains derived from the chain-conjugated diene compound of the block copolymer [C-1] and carbon-carbon unsaturated bonds of the aromatic ring derived from the aromatic vinyl compound are formed. When hydrogenated, the hydrogenation rate is 90% or more, preferably 95% or more, more preferably 99% or more of the total carbon-carbon unsaturated bond. When the hydrogenation rate of the block copolymer hydride [D-1] is at least the above lower limit, the sealing layer 1 is excellent in transparency and heat resistance.

Hydrogenation rate of carbon-carbon unsaturated bond derived from chain conjugated diene compound of block copolymer hydride [D-1], and hydrogenation of carbon-carbon unsaturated bond derived from aromatic vinyl compound. ^{The rate can be determined, for example, by measuring 1} H-NMR of the block copolymer [C-1] and the block copolymer hydride [D-1].

Further, the molecular weight of the block copolymer hydride [D-1] is a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC using THF as a solvent, and is usually 35,000 or more, preferably 38,000 or more. , More preferably 40,000 or more, usually 200,000 or less, preferably 150,000 or less, more preferably 100,000 or less. The molecular weight distribution (Mw / Mn) of the block copolymer hydride [D-1] is preferably 3.0 or less, more preferably 2.0 or less, and particularly preferably 1.6 or less. When Mw and Mw / Mn are within the above ranges, the heat resistance and mechanical strength of the sealing layer 1 are further improved. As a result, it is possible to effectively suppress the deformation of the sealed material 3 sealed in the sealing layer 1 due to heat.

[Additive]
The arbitrary additive that can be blended in the resin I is not particularly limited, and examples thereof include an adhesiveness-imparting agent, an adhesiveness-imparting agent, an ultraviolet absorber, an antioxidant, an antiblocking agent, and a light stabilizer. Be done. These can be used individually by 1 type or in combination of 2 or more types.

<< Sealed material >>
The sealing material 3 sealed in the sealing layer 1 contains a resin containing polyethylene terephthalate resin, polycarbonate resin, polypropylene resin, polyethylene resin, or polyacrylonitrile resin; float glass, heat-reinforced glass, or chemical. It is preferable to include any of glass containing tempered glass, metal containing stainless steel, aluminum, or copper, and a composite obtained by combining these. The composite of the resin and the metal according to the above enumeration may be, for example, a metal vapor deposition of a resin plate, more specifically, an electronic substrate. Then, if the laminate according to the example contains a seal containing resin, glass, metal, or a composite thereof as a constituent material, the deformation of the seal in the laminate is further satisfactorily reduced. be able to.

As described above, the sealed product 3 preferably has a thickness d6 of 10 μm or more and 500 μm or less. More specifically, when the constituent material of the encapsulant 3 is the resin or metal-deposited resin according to the above enumeration, the thickness d6 of the encapsulant 3 can be 20 μm or more and 500 μm or less. Further, when the constituent material of the sealing material 3 is the glass according to the above enumeration, the thickness d6 of the sealing material 3 may be 10 μm or more and 500 μm or less. Furthermore, when the constituent material of the encapsulant 3 is the metal according to the above enumeration, the thickness d6 of the encapsulant 3 can be 10 μm or more and 500 μm or less.

<Alkoxysilyl group-containing resin layer>
The alkoxysilyl group-containing resin layer 2 is a layer made of resin II containing a block copolymer hydride having an alkoxysilyl group, which is arranged adjacent to the front surface and the back surface of the sealing layer 1, respectively. If the laminate has the alkoxysilyl group-containing resin layer 2, the alkoxysilyl group-containing resin layer 2 can satisfactorily adhere to an adherend such as a base material.

<< Resin II >>
Resin II contains a block copolymer hydride having an alkoxysilyl group and may optionally contain additives.
The block copolymer hydride having an alkoxysilyl group contained in Resin II includes at least two polymer blocks [A-2] containing a structural unit [a-2] derived from an aromatic vinyl compound as a main component and a chain. A block co-weight formed by hydrogenating at least one polymer block [B-2] containing a structural unit [b-2] derived from a state-conjugated diene compound and a block copolymer [C-2] having the same. It is a block copolymer [E] formed by introducing an alkoxysilyl group into the coalescence [D-2].
Here, the structural unit [a-2], the polymer block [A-2], the structural unit [b-2], the polymer block [B-2], the block copolymer [C-2], and the block together. Regarding the polymer [D-2], the structural unit [a-1], the polymer block [A-1], the structural unit [b-1], and the polymer described in the above << Resin I >>. Block [B-1], block copolymer [C-1], and the same as block copolymer [D-1] can be preferably adopted. Then, the structural unit [a-1] and the structural unit [a-2], the polymer block [A-1] and the polymer block [A-2], the structural unit [b-1] and the structural unit [b-2] ], Polymer block [B-1] and polymer block [B-2], block copolymer [C-1] and block copolymer [C-2], and block copolymer [D-1]. ] And the block copolymer [D-2] may be the same or different from each other.
Further, the resin II may contain any additive described in the above item << Resin I >>.

Furthermore, the total amount of the structural unit [a-2] derived from the aromatic vinyl compound in the block copolymer [C-2] wa-2 the mass fraction of the entire block copolymer [C-2]. , Wa-2 and wb-2, where wb-2 is the mass fraction of the total amount of the structural unit [b-2] derived from the chain-conjugated diene compound to the entire block copolymer [C-2]. The ratio (wa-2: wb-2) to and from is preferably 20:80 to 65:35, more preferably 30:70 to 60:40, and 40:60 to 55:45. Is even more preferable.
Then, the values wa-1 and wb-1 which are the mass fractions for the block copolymer [C-1] and the values wa-2 and wb which are the mass fractions for the block copolymer [C-2]. With -2, wa-1 and wa-2, and wb-1 and wb-2 may be the same or different from each other.

[Block copolymer [E]]
The block copolymer [E] is a polymer obtained by introducing an alkoxysilyl group into the block copolymer [D-2] which is a hydride. When the block copolymer [E] has an alkoxysilyl group, the alkoxysilyl group-containing resin layer 2 can be satisfactorily adhered to an adherend such as a base material.

Here, the method for introducing an alkoxysilyl group into the block copolymer [D-2] which is a hydride is not particularly limited. For example, by reacting the above-mentioned block copolymer [D-2] which is a hydride with an ethylenically unsaturated silane compound in the presence of an organic peroxide, the block copolymer [D-2] which is a hydride is allowed to react. -2] can be introduced with an alkoxysilyl group.

Examples of the alkoxysilyl group include a tri (1 to 6 alkoxy) silyl group such as a trimethoxysilyl group and a triethoxysilyl group; a methyldimethoxysilyl group, a methyldiethoxysilyl group, an ethyldimethoxysilyl group, and an ethyldiethoxysilyl group. Group, propyldimethoxysilyl group, propyldiethoxysilyl group, etc., (1 to 20 alkyl carbon number) di (1 to 6 alkoxy carbon number) silyl group; phenyldimethoxysilyl group, phenyldiethoxysilyl group, etc., (aryl) ) Di (alkoxy with 1 to 6 carbon atoms) silyl group; and the like. Of these, a trimethoxysilyl group is particularly preferable from the viewpoint of further improving the adhesive strength of the alkoxysilyl group-containing resin layer 2 to the substrate. Further, the alkoxysilyl group is bonded to the block copolymer hydride via a divalent organic group such as an alkylene group having 1 to 20 carbon atoms or an alkyleneoxycarbonylalkylene group having 2 to 20 carbon atoms. Is also good.

The amount of the alkoxysilyl group introduced into the block copolymer [D-2], which is a hydride, is usually 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the block copolymer hydride. It is preferably 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less. The introduction of the alkoxysilyl group can be confirmed by the IR spectrum. In addition, the amount introduced ^{can be calculated from 1 1} H-NMR spectrum.

The ethylenically unsaturated silane compound to be used is not particularly limited as long as it is graft-polymerized with a block copolymer hydride and an alkoxysilyl group is introduced into the block copolymer hydride. Examples of the ethylenically unsaturated silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, and 3-acrylic. Loxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-acryloxypropyltrimethoxysilane, and the like are preferably used.
These ethylenically unsaturated silane compounds may be used alone or in combination of two or more.

The amount of the ethylenically unsaturated silane compound used is usually 0.1 parts by mass or more and 10 parts by mass or less, preferably 0.2 parts by mass, based on 100 parts by mass of the block copolymer [D-2] which is a hydride. It is 5 parts by mass or more, more preferably 0.3 parts by mass or more, preferably 5 parts by mass or less, and more preferably 3 parts by mass or less.

As the organic peroxide, one having a half-life temperature of 170 ° C. or higher and 190 ° C. or lower for 1 minute is preferably used. For example, t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, Di (2-t-butylperoxyisopropyl) benzene and the like are preferably used.
These organic peroxides may be used individually or in combination of two or more.
The amount of the organic peroxide used is usually 0.05 parts by mass or more and 2 parts by mass or less, preferably 0.08 parts by mass or more, and more preferably 0 parts by mass with respect to 100 parts by mass of the block copolymer hydride. It is 1 part by mass or more, preferably 1 part by mass or less, and more preferably 0.5 part by mass or less.

The method for reacting the block copolymer hydride and the ethylenically unsaturated silane compound in the presence of an organic peroxide is not particularly limited. For example, an alkoxysilyl group can be introduced into the block copolymer hydride by kneading at a desired temperature for a desired time with a twin-screw kneader. Specifically, in the introduction of the alkoxysilyl group into the block copolymer hydride, the block copolymer hydride, the ethylenically unsaturated silane compound and the organic peroxide are continuously added while appropriately adjusting the temperature and the residence time. It may be kneaded and extruded.

<Base material>
The base material as an adherend arranged adjacent to the surface opposite to the surface adjacent to the sealing layer 1 of the alkoxysilyl group-containing resin layer 2 described above depends on the type of the desired laminated body. It may be selected as appropriate, and is not particularly limited. For example, the main materials constituting the base material are resin materials such as thermoplastic resin and thermosetting resin, glass, copper, iron, stainless steel, aluminum, gold, silver, platinum, SiO ₂ , SiN, Al ₂ O. _{Examples include 3rd} grade inorganic materials. Further, as the constituent material of the base material, components other than the resin material and the inorganic material can also be used. Further, a resin material and an inorganic material can be used in combination for producing the base material. Furthermore, the substrate may be surface treated according to a known method.

The shape of the base material is not particularly limited, and may be determined according to the desired application. For example, when the base material is in the form of a sheet or a plate, the thickness thereof is not particularly limited, but is preferably 0.02 mm or more and 10 mm or less. Further, the thickness of the sheet-shaped or plate-shaped base material may be uniform or non-uniform.

(Manufacturing method of laminated body)
In the method for producing a laminate of the present invention, a sealing layer in which a sealing material is sealed in a resin I having no alkoxysilyl group and a sealing layer are arranged adjacent to each other on the front surface and the back surface of the sealing layer. This is a method for producing a laminate comprising two alkoxysilyl group-containing resin layers made of an alkoxysilyl group-containing resin II. Then, as shown in FIG. 2, the production method of the present invention comprises a layer made of an alkoxysilyl group-containing resin II (2-1), a layer made of a resin I (1-1), a sealant 3, and a resin I. It is characterized by including a step (heating step) of heating and integrating a laminate formed by laminating a layer made of (1-2) and a layer made of an alkoxysilyl group-containing resin II (2-2) in this order. To do. Then, the thickness of the layer (1-1) made of resin I is (t1-1), the thickness of the layer (1-2) made of resin I is (t1-2), and the thickness of the layer made of resin II (2-1). (T2-1), the thickness of the layer (2-2) made of resin II is (t2-2), and the thickness of the encapsulated product is St, (t2-1) / (t1-1). The values of (t2-2) / (t1-2) are independently within the range of 0.01 or more and 1.10 or less, and St / (t1-1) and St / ( The value of t1-2) is 1.20 or less independently of each other. Since the production method of the present invention includes a step of heating and integrating the laminate satisfying the structural conditions, it is possible to satisfactorily produce the laminate with less deformation of the sealed material in the laminate. .. Further, optionally, the heating step may be performed after both sides of the laminate are sandwiched between the base materials.

<Layer made of resin I>
The layer made of resin I used in the production method of the present invention can be produced according to a known method such as a melt extrusion molding method using the resin described in the item << Resin I >> of (laminated body). it can.

Further, from the viewpoint of further satisfactorily reducing the deformation of the sealed material in the laminated body, the values of (t2-1) / (t1-1) and (t2-2) / (t1-2) are set, respectively. Independently, it is preferably 1.0 or less.
Furthermore, from the viewpoint of further satisfactorily reducing the deformation of the sealed material in the laminated body, the values of St / (t1-1) and St / (t1-2) are independently set to 1.0 or less. It is preferable to have.
Then, from the viewpoint of further satisfactorily reducing the deformation of the sealed material in the laminated body, the thicknesses (t1-1) (t1-2) of the layer made of the resin I are (t1-1) / (t1-2). The value of is preferably 0.40 or more, more preferably 0.45 or more, preferably 3.00 or less, more preferably 2.50 or less, and 1.50 or less. It is more preferable to have.
Further, the thickness (t1-1) (t1-2) of the layer made of the resin I is preferably 100 μm or more, more preferably 300 μm or more, and 1,000 μm or less, respectively. Is preferable, and it is more preferably 700 μm or less. When the thickness (t1-1) (t1-2) of the layer made of the resin I is within the above range, the deformation of the sealed material in the laminated body can be reduced more satisfactorily.

<Layer made of resin II>
The layer made of resin II used in the manufacturing method of the present invention is manufactured by using the resin described in the item << Resin II >> of (laminate) according to the same known method as the layer made of resin I. can do. The thickness (t2-1) (t2-2) of the layer made of Resin II is preferably 1 μm or more, more preferably 5 μm or more, and preferably 400 μm or less, respectively. , 100 μm or less is more preferable. When the thickness (t2-1) (t2-2) of the layer made of Resin II is within the above range, the deformation of the sealed material in the laminated body can be reduced more satisfactorily.

Each layer may be manufactured as a multilayer sheet including a layer made of resin I and a layer made of resin II. The method for producing the multilayer sheet is not particularly limited, and a known method can be adopted (see, for example, International Publication No. 2015/105127).

<Interrelationship between the thickness of the layer made of resin I and the thickness of the layer made of resin II>
Further, from the viewpoint of further satisfactorily reducing the deformation of the sealed material in the laminated body, the thickness of the layer made of resin I (t1-1) (t1-2) and the thickness of the layer made of resin II (t2-1). ) (T2-2), it is preferable that the following mutual relationships are satisfied.
Furthermore, from the viewpoint of further satisfactorily reducing the deformation of the sealed material in the laminated body, the value of {(t2-1) + (t2-2)} / {(t1-1) + (t1-2)} Is preferably 0.01 or more, preferably 1.10 or less, more preferably 1.05 or less, further preferably 0.90 or less, and 0.50 or less. Is even more preferable.

<Enclosed material>
As the encapsulant used in the production method of the present invention, the encapsulant described in the item of (laminated body) can be preferably used.

<Interrelationship between the thickness of the encapsulant and the thickness of the layer made of resin I>
Then, in the production method of the present invention, the following mutual relationship is satisfied between the thickness St of the sealing material and {thickness (t1-1) (t1-2) of the layer made of resin I. Is preferable.
The value of {(t1-1) + (t1-2)} / St is preferably 1.80 or more, preferably 2.45 or more, and more preferably 2.50 or more. It is preferably 5.50 or less, and more preferably 5.00 or less. If the value of {(t1-1) + (t1-2)} / St satisfies such a range, the deformation of the sealed product in the laminated body can be further reduced.

<Base material>
As the base material that can be arbitrarily used in the production method of the present invention, the base material described in the item of (laminated body) can be preferably used. By carrying out a step of heating and integrating the laminate after both sides of the laminate are sandwiched between the base materials, the sealed material is sealed in the sealing layer, and the sealing layer is formed of an alkoxysilyl group. Adhesion to the substrate via two alkoxysilyl group-containing resin layers made of the containing resin II can be carried out in one step.

<Method of heating and integrating>
The production method of the present invention includes a step of heating and integrating the laminate having the above-mentioned structure. The heat-bonding method is preferable as the heating and integrating method adopted in this step.
The heat crimping method is not particularly limited, and for example, a laminate having the above-mentioned structure is placed in a flexible bag (hereinafter, may be referred to as a "bag") to degas the air in the bag. While heat-crimping to form a bonded body; the laminate obtained in the same manner as above is put in a bag, the air in the bag is degassed, and then heat-crimped and pasted in an oven or an autoclave. Method of combining to form a laminate; Method of heat-pressing the laminate with a heat press device to form a laminate; Heat-pressing the laminate using a pressurizer such as a vacuum laminator, a vacuum press, or a roll laminator. And the like can be used.

The temperature (adhesion temperature) at the time of heating and integrating is not particularly limited and can be appropriately set according to the types of resin I and resin II to be used.

Further, when the laminate is put in a bag, the air in the bag is degassed, and then heat-pressed by heating, the pressure in the bag is preferably less than 0 Mpa. Furthermore, the heating time for heat-pressing is not particularly limited, and may be, for example, 10 minutes or more and 60 minutes or less.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. Unless otherwise specified, "parts" and "%" are based on mass. The pressure is a gauge pressure unless otherwise specified.

In Examples and Comparative Examples, the deformation suppressing ability of the sealed material was evaluated as follows. Laminated glass formed by encapsulating a 100 mm × 80 mm encapsulant produced in Examples and Comparative Examples was observed vertically from the glass surface, and the lengths of the long side and the short side of the encapsulant were measured. Using the measured values, the value of initial dimension: (long side + short side) / 2 was calculated.
The laminated glass prepared in Examples and Comparative Examples was placed in an oven and heated at 85 ° C. for 100 hours to perform a heat resistance test. The laminated glass after the heat resistance test was observed vertically from the glass surface, and the lengths of the long side and the short side of the sealed material were measured. Using the measured values, the value of the dimensions after the heat resistance test: (long side + short side) / 2 was calculated.
Then, the value of the dimensional change rate (%) by the heat resistance test is calculated according to the formula: | Initial dimension-Dimension after heat resistance test | / Initial dimension x 100, and the deformation of the sealed product of the laminated body is calculated according to the following criteria. The suppressive ability was evaluated.
A: Dimensional change rate is within 5% B: Dimensional change rate is more than 5% and 10% or less C: Dimensional change rate is more than 10%

In Examples and Comparative Examples, various attributes were measured or calculated according to the following methods.
(1) Weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
The molecular weights of the block copolymer and the block copolymer hydride were measured at 38 ° C. as a standard polystyrene-equivalent value by GPC using THF as an eluent. As a measuring device, HLC8320GPC manufactured by Tosoh Corporation was used.
(2) Hydrogenation rate The hydrogenation rate of the main chain, side chain and aromatic ring of the block copolymer hydride ^{was calculated by measuring 1} H-NMR of the block copolymer and the block copolymer hydride.
(3) Mass fraction The block copolymers prepared in Examples and Comparative Examples ^{were measured by 1} H-NMR, and the total amount of the structural unit [a] derived from the aromatic vinyl compound in the block copolymer was the same as that of the block copolymer. The mass ratio wa in the entire polymer and the mass ratio wb in which the total amount of the structural unit [b] derived from the chain conjugated diene compound accounts for the entire block copolymer are obtained, and the ratio of wa to wb (wa: wb) is obtained. ) Was obtained.

(Example 1)
<Preparation of resin I>
Resin I containing a block copolymer hydride having no alkoxysilyl group was prepared according to the following.
<< Preparation of block copolymer >>
400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene and 0.475 parts of dibutyl ether were placed in a reactor equipped with a stirrer in which the inside was sufficiently nitrogen-substituted. While stirring the whole volume at 60 ° C., 0.88 parts of n-butyllithium (15% cyclohexane solution) was added to initiate polymerization. Subsequently, while stirring the whole volume at 60 ° C., 15 parts of dehydrated styrene was continuously added into the reactor for 40 minutes to proceed with the polymerization reaction, and after the addition was completed, the whole volume was further stirred at 60 ° C. for 20 minutes. .. When the reaction solution was measured by gas chromatography (GC), the polymerization conversion rate at this point was 99.5%.
Next, 50.0 parts of dehydrated isoprene was continuously added to the reaction solution for 130 minutes, and stirring was continued for 30 minutes as it was after the addition was completed. At this point, as a result of analyzing the reaction solution by GC, the polymerization conversion rate was 99.5%.
Then, 25.0 parts of dehydrated styrene was continuously added to the reaction solution for 70 minutes, and after the addition was completed, the mixture was stirred as it was for 60 minutes. At this point, as a result of analyzing the reaction solution by GC, the polymerization conversion rate was almost 100%.

Here, by adding 0.5 part of isopropyl alcohol to terminate the reaction, a polymer solution containing the [A]-[B]-[A] type block copolymer [C-1] was obtained. The weight average molecular weight (Mw) of the block copolymer [C-1] is 47,200, the molecular weight distribution (Mw / Mn) is 1.34, and the mass fraction ratio (wa: wb) of wa and wb is 50. : It was 50.

<Block Copolymer Hydride [D-1]>
Next, the above polymer solution was transferred to a pressure resistant reactor equipped with a stirrer, and used as a hydrogenation catalyst, a diatomaceous earth-supported nickel catalyst (product name "E22U", nickel-supported amount 60%, manufactured by JGC Catalysts and Chemicals, Inc.). ,) 4.0 parts and 30 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, hydrogen was further supplied while stirring the solution, and a hydrogenation reaction was carried out at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours.
The weight average molecular weight (Mw) of the block copolymer hydride [D-1] contained in the reaction solution obtained by the hydrogenation reaction was 49,000, and the molecular weight distribution (Mw / Mn) was 1.36.

After completion of the hydrogenation reaction, the reaction solution is filtered to remove the hydrogenation catalyst, and then pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl)], which is a phenolic antioxidant. Propionate] (product name "Songnox (registered trademark) 1010", manufactured by Matsubara Sangyo Co., Ltd.) was dissolved by adding 2.0 parts of a xylene solution in which 0.1 part was dissolved.
Next, cyclohexane, xylene and other volatile components were removed from the above solution using a cylindrical concentrated dryer (product name "Contro", manufactured by Hitachi, Ltd.) at a temperature of 260 ° C. and a pressure of 0.001 MPa or less. The molten polymer was extruded from a die into strands, cooled, and then 95 parts of block copolymer hydride [D-1] pellets (that is, resin I pellets) were prepared by a pelletizer.
The obtained pellet-shaped block copolymer hydride [D-1] has a weight average molecular weight (Mw) of 49,500, a molecular weight distribution (Mw / Mn) of 1.40, and a main chain derived from a chain-conjugated diene. The hydrogenation rate of the carbon-carbon unsaturated bond in the side chain and the hydrogenation rate of the carbon-carbon unsaturated bond derived from the aromatic ring of the aromatic vinyl compound are both approximately 100% (99% or more). there were.

<Preparation of resin II>
2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (product name) with respect to 100 parts of resin I pellets obtained by the same operation as above. "Perhexa (registered trademark) 25B", manufactured by NOF CORPORATION), 0.1 part was added. The mixture is kneaded using a twin-screw extruder at a kneading temperature of 230 ° C. and a kneading time of 70 to 90 seconds, extruded into strands, air-cooled, and then cut with a pelletizer to block copolymer hydride [D-2. ], An alkoxysilyl group was introduced to obtain 96 parts of block copolymer [E] pellets (that is, resin II pellets).

After dissolving 10 parts of the obtained block copolymer [E] pellet in 100 parts of cyclohexane, the block copolymer [E] was coagulated by pouring it into 400 parts of dehydrated methanol, and the coagulated product was collected by filtration. The filtrate was vacuum dried at 25 ° C. to isolate 9.0 parts of crumb of block copolymer [E].
Measurement of the crumb of the FT-IR spectrum of the block copolymer [E], Si-OCH ₃ group in 1090 cm ^-1, a new absorption band derived from Si-CH ₂ group to 825cm ^-1 and 739cm ^-1 is , It was observed at a position different from the absorption bands (1075 cm ^-1 , 808 cm ^-1 and 766 cm ^-1 _{) derived from 3} Si-OCH _{groups and 2} Si-CH groups of vinyltrimethoxysilane.
^{Further, when the 1} H-NMR spectrum (in deuterated chloroform) of the block copolymer [E] was measured, a peak based on the proton of a methoxy group was observed at 3.6 ppm, and the block copolymer hydride was observed from the peak area ratio. [D-2] It was confirmed that 1.8 parts of vinyltrimethoxysilane was bound to 100 parts.

<Manufacturing of a multilayer sheet containing a layer made of resin I and a layer made of resin II>
2- (5-Chloro-2H-benzotriazole-2-yl) -6- (1,1-) as an ultraviolet absorber for 100 parts each of the pellets of the resin I and the resin II obtained as described above. 0.8 parts of dimethylethyl) -4-methyl (manufactured by BASF Japan, product name "Tinuvin (registered trademark) 326") was blended, and the obtained mixture was mixed with a coextruded multilayer T-die having a feed block and a single shaft. An extruder was used to produce a two-layer sheet in which a layer made of resin I and a layer made of resin II were laminated. In the production of the two-layer sheet, the molding conditions were changed to obtain two types of two-layer sheets. One of the two types of two-layer sheets is a sheet 1 in which a layer (1-1) made of resin I having a thickness of 340 μm and a layer (2-1) made of resin II having a thickness of 5 μm are laminated. The other was the sheet 2 in which a layer (1-2) made of resin I having a thickness of 650 μm and a layer (2-2) made of resin II having a thickness of 5 μm were laminated. Table 2 shows the thickness of each layer constituting the sheet used.

<Manufacturing of laminate>
Using a plate-shaped body (thickness d6: 300 μm, length 100 mm × width 80 mm) made of polyethylene terephthalate (PET) as a sealing material, a laminate in which the sealing material is sealed in the sealing layer is prepared according to the following. Manufactured.
Specifically, first, in order from the bottom, the lower glass base material (thickness: 2 mm), the sheet 2 (arranged so that the layer (1-2) made of resin I is on the upper side), and the encapsulant ( PET), sheet 1 (arranged so that the layer (2-1) made of resin II is on the upper side), and the upper glass base material (thickness: 2 mm) were laminated to obtain a laminate.
The obtained laminate was placed in a vacuum bag and depressurized by a pump (−0.08 MPa). A vacuum bag containing the laminate was placed in an oven and heated at 120 ° C. for 30 minutes to obtain a laminate. The vacuum bag containing the laminate was cooled to room temperature (25 ° C.), and then the laminate was removed from the vacuum bag. The obtained laminates are, in order from the top, an upper glass base material (thickness: 2 mm), an upper alkoxysilyl group-containing resin layer (thickness: 5 μm), a sealing layer (thickness: 990 μm), and a lower alkoxysilyl group-containing resin. It was provided with a layer (thickness: 5 μm) and a lower glass base material (thickness: 2 mm). Further, by observing the cross section of the laminate, the shortest distance d4 from the surface of the sealing layer to the surface of the sealing material and the shortest distance d5 from the back surface of the sealing layer to the back surface of the sealing material are measured. , D4 / d5 values were calculated. The results are shown in Table 1. Furthermore, the deformation suppressing ability of the obtained laminate was evaluated according to the above. The results are shown in Table 1.

(Examples 2 to 3)
In manufacturing the sheet 1 and the sheet 2, various sheets were obtained by performing the same operation as in the first embodiment except that the conditions at the time of manufacturing the multilayer sheet were changed so that the thickness of each sheet was as shown in Table 2. It was. Further, as the sealing material, a plate-like body (length 100 mm × width 80 mm) made of PET having each thickness shown in Table 1 was used. Except for these points, a laminate was produced in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The results are shown in Table 1.

In Table 1, "AS group" indicates "alkoxysilyl group".

From the above-mentioned results, it can be seen that the laminates according to Examples 1 to 4 satisfying the predetermined structure were excellent in the ability to suppress deformation of the sealed material when the laminate was heat-tested.
On the other hand, it can be seen that the laminates according to Comparative Examples 1 to 3 that do not satisfy the predetermined structure were inferior in the ability to suppress deformation of the sealed product when the laminate was heated and tested.

According to the production method of the present invention, it is possible to provide a laminate capable of suppressing deformation of the sealed material in the laminate, and a method for producing such a laminate.

1 Encapsulation layer 1-1, 1-2 Layer composed of resin I 2 Alkoxysilyl group-containing resin layer 2-1,2-2 Alkoxysilyl group-containing resin II layer 3 Encapsulation 10 Laminated product 11 Base material 100 Laminate with base material d1 Thickness of sealing layer d2, d3 Thickness of alkoxysilyl group-containing resin layer d4 Shortest distance from the surface of the sealing layer to the surface of the encapsulation d5 From the back surface of the encapsulation layer to the back surface of the encapsulant Shortest distance to d6, st Thickness of encapsulated material t1-1, t1-2 Thickness of layer made of resin I t2-1, t2-2 Thickness of layer made of alkoxysilyl group-containing resin II

Claims (9)

A sealing layer in which a sealing material is sealed in a resin I containing a block copolymer hydride having no alkoxysilyl group, and
Two alkoxysilyl group-containing resin layers composed of resin II containing block copolymer hydride having an alkoxysilyl group, which are arranged adjacent to each other on the front surface and the back surface of the sealing layer, and
It is a laminated body including
The block copolymer hydride contained in the resin I is composed of at least two polymer blocks [A-1] containing a structural unit [a-1] derived from an aromatic vinyl compound as a main component and a chain-conjugated diene. A block copolymer [D] formed by hydrogenating at least one polymer block [B-1] containing a compound-derived structural unit [b-1] as a main component and a block copolymer [C-1] having the same. -1]
The block copolymer hydride having an alkoxysilyl group contained in the resin II includes at least two polymer blocks [A-2] containing a structural unit [a-2] derived from an aromatic vinyl compound as a main component. , A block formed by hydrogenating a block copolymer [C-2] having at least one polymer block [B-2] containing a structural unit [b-2] derived from a chain conjugated diene compound as a main component. It is a block copolymer [E] formed by introducing an alkoxysilyl group into the copolymer [D-2].
The structural unit [a-1] and the structural unit [a-2], the polymer block [A-1] and the polymer block [A-2], the structural unit [b-1] and the structural unit. [B-2], the polymer block [B-1] and the polymer block [B-2], the block copolymer [C-1] and the block copolymer [C-2], and The block copolymer [D-1] and the block copolymer [D-2] may be the same or different from each other.
The thickness of the sealing layer is d1, the thickness of one of the two alkoxysilyl group-containing resin layers is d2, and the thickness of the other alkoxysilyl group-containing resin layer is d3. A laminate in which the value of d1 / d6 is 1.80 or more and the value of (d2 + d3) / d1 is 0.01 or more and 1.10 or less, where d6 is the thickness of the sealed material. The value of d4 / d5 is 0.33, where d4 is the shortest distance from the surface of the sealing layer to the surface of the sealing material, and d5 is the shortest distance from the back surface of the sealing layer to the back surface of the sealing material. The laminate according to claim 1, which is 3.00 or less. The mass fraction of the total amount of the structural unit [a-1] derived from the aromatic vinyl compound in the block copolymer [C-1] to the entire block copolymer [C-1] is wa-1. , Wa-1 and wb, where wb-1 is the mass fraction of the total amount of the structural unit [b-1] derived from the chain-conjugated diene compound to the entire block copolymer [C-1]. The ratio to -1 (wa-1: wb-1) is 20:80 to 65:35.
The total amount of the structural unit [a-2] derived from the aromatic vinyl compound in the block copolymer [C-2] is the mass fraction of the entire block copolymer [C-2] wa-2. , Wa-2 and wb, where wb-2 is the mass fraction of the total amount of the structural unit [b-2] derived from the chain-conjugated diene compound to the entire block copolymer [C-2]. The ratio to -2 (wa-2: wb-2) is 20:80 to 65:35.
The w-1 and the w-2, and the wb-1 and wb-2 may be the same or different from each other.
The laminate according to claim 1 or 2. The thicknesses d2 and d3 of the alkoxysilyl group-containing resin layer are independently any value within the range of 1 μm or more and 400 μm or less.
The thickness d1 of the sealing layer is 200 μm or more and 2,000 μm or less.
The laminate according to any one of claims 1 to 3. The laminate according to any one of claims 1 to 4, wherein the thickness d6 of the sealed product is 10 μm or more and 500 μm or less. The encapsulant is a plate-like body, and the constituent material of the encapsulant is a resin containing a polyethylene terephthalate resin, a polycarbonate resin, a polypropylene resin, a polyethylene resin, or a polyacrylonitrile resin; float glass, heat-reinforced glass, or chemical. The laminate according to any one of claims 1 to 5, which comprises glass containing tempered glass, a metal containing stainless steel, aluminum, or copper, and a composite obtained by combining these. Claims 1 to further include a base material of the two alkoxysilyl group-containing resin layers made of the resin II, which are arranged adjacent to the surface of the two alkoxysilyl group-containing resin layers opposite to the surface adjacent to the sealing layer. The laminate according to any one of 6. Two sheets composed of a sealing layer in which an encapsulant is sealed in a resin I having no alkoxysilyl group, and an alkoxysilyl group-containing resin II arranged adjacent to the front surface and the back surface of the sealing layer, respectively. A method for producing a laminate comprising an alkoxysilyl group-containing resin layer.
The layer made of the alkoxysilyl group-containing resin II (2-1), the layer made of the resin I (1-1), the encapsulant, the layer made of the resin I (1-2), and the alkoxysilyl group. The step of heating and integrating the laminate in which the layer (2-2) composed of the contained resin II is laminated in this order is included.
The resin I contains a block copolymer hydride, and the block copolymer hydride contains at least two polymer blocks [A-] containing a structural unit [a-1] derived from an aromatic vinyl compound as a main component. Block copolymer [C-1] having at least one polymer block [B-1] containing 1] and a structural unit [b-1] derived from a chain conjugated diene compound as a main component is hydrogenated. It is a block copolymer [D-1] composed of
The alkoxysilyl group-containing resin II contains a block copolymer hydride having an alkoxysilyl group, and the block copolymer hydride having an alkoxysilyl group is a structural unit derived from an aromatic vinyl compound [a-2]. At least two polymer blocks [A-2] containing the main component, and at least one polymer block [B-2] containing the structural unit [b-2] derived from the chain conjugated diene compound as the main component. It is a block copolymer [E] formed by introducing an alkoxysilyl group into a block copolymer [D-2] formed by hydrogenating a block copolymer [C-2] having the above.
The structural unit [a-1] and the structural unit [a-2], the polymer block [A-1] and the polymer block [A-2], the structural unit [b-1] and the structural unit. [B-2], the polymer block [B-1] and the polymer block [B-2], the block copolymer [C-1] and the block copolymer [C-2], and The block copolymer [D-1] and the block copolymer [D-2] may be the same or different from each other.
The thickness of the layer made of resin I (1-1) is (t1-1), the thickness of the layer made of resin I (1-2) is (t1-2), and the thickness of the layer made of resin II (2-1). ) Is (t2-1), the thickness of the layer (2-2) made of the resin II is (t2-2), and the thickness of the sealed product is St, (t2-1) / (t1-). The values of 1) and (t2-2) / (t1-2) are independently within the range of 0.01 or more and 1.10 or less, and St / (t1-1) and The values of St / (t1-2) are independently 1.20 or less.
Method for manufacturing a laminate. The method for producing a laminate according to claim 8, wherein the value of (t1-1) / (t1-2) is 0.33 or more and 3.00 or less.

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