JP2019042935A - Method of manufacturing laminate - Google Patents

Abstract

Kind Code: A1 A method for manufacturing a laminated body is provided, which can produce a laminated body in which deformation of the ends is suppressed without using a spacer or a reinforcing plate. A method for producing a laminate comprising a base material and at least one resin layer formed on the base material, the resin layer containing a thermoplastic resin, comprising: A step of vacuum degassing a package in which an object is enclosed in a packaging bag, and a step of heating and pressurizing the vacuum degassed package to produce a laminate, wherein the heating temperature is T1, When the glass transition temperature or melting point of the resin is T2, the Vicat softening temperature of the packaging bag is T3, and the melting temperature of the packaging bag is T4, the respective temperatures T1 to T4 have a relationship of T4>T1≧T2≧T3. A method for manufacturing a laminate that satisfies [Selection drawing] Fig. 1

Description

  The present invention relates to a method of manufacturing a laminate.

  A laminated glass as a laminate is generally melted by heating and pressurizing a package obtained by putting a laminate obtained by laminating a glass plate and a resin layer in a packaging bag such as a heat resistant bag with an autoclave (vacuum evacuation). Bonding is performed by pressure bonding (see, for example, Patent Document 1).

JP, 2016-36998, A

  However, there is a problem that the end of the laminated glass is pressed more strongly than the center and deformed from the vacuum-evacuated (reduced pressure) packaging bag, and the resin is pushed out from the end of the laminated glass.

  In order to solve such problems, (i) frame-shaped spacers are installed in the package to prevent deformation of the end of the laminated glass, or (ii) reinforcing plates are provided on the upper and lower sides in the package, In order to prevent stress concentration on the end of the frame, various measures are taken. However, (i) When the frame-like spacer is installed in the package, the entire pressing pressure is weakened by the height of the frame-like spacer, and there is a problem that bonding failure occurs. In addition, (ii) when reinforcing plates are installed above and below the package, there is a problem that a rigid iron plate is required, or the reinforcing plate and the deformed glass plate are in contact and the glass plate is broken.

  Then, an object of this invention is to provide the manufacturing method of the laminated body which can produce the laminated body by which the deformation | transformation of the edge part was suppressed, without using a spacer or a reinforcement board.

  The present inventors diligently studied to achieve the above object. And this inventor vacuum-degasses the package which sealed the laminated body in the packaging bag softened at the heating temperature at the time of bonding of laminated glass, and heats and pressurizes the vacuum-degassed package, a spacer or The inventors have found that it is possible to produce a laminate in which deformation of the end portion is suppressed without using a reinforcing plate, and the present invention has been completed.

That is, the present invention aims to advantageously solve the above-mentioned problems, and the method for producing a laminate of the present invention comprises a substrate and at least one resin layer formed on the substrate. And a step of vacuum degassing the package in which the laminate is enclosed in a packaging bag, and the vacuum degassing process. Heating and pressing the package to produce a laminate, the heating temperature being T1, the glass transition temperature or melting point of the thermoplastic resin being T2, the Vicat softening temperature of the packaging bag being T3, the packaging Assuming that the melting temperature of the bag is T4, the respective temperatures T1 to T4 satisfy the relationship of T4> T1 ≧ T2 ≧ T3. Thus, if the respective temperatures T1 to T4 satisfy the relationship of T4> T1 ≧ T2 ≧ T3, it is possible to produce a laminate in which the deformation of the end portion is suppressed without using a spacer or a reinforcing plate. it can.
In the present invention, “laminate” means “a laminate provided with a substrate and a resin layer, and before heating and pressing (for example, before autoclaving)”. "Packaging bag" means "a bag for enclosing the laminate", "package" means "the laminate in a packaging bag", and the laminate is "heated and pressed" Means the one taken out from the packaging bag in the packaged body.
In the present invention, "temperature T1 of heating" means the maximum temperature from the start to the end of bonding, and "glass transition temperature or melting point T2 of thermoplastic resin" refers to a plurality of resin layers. When including a thermoplastic resin, it means the glass transition temperature or melting point of the thermoplastic resin having the highest glass transition temperature or melting point, and when the thermoplastic resin has a plurality of glass transition temperatures or melting points, The highest glass transition temperature or melting point means "Vicat softening temperature T3 of the packaging bag" means the Vicat softening temperature of the material of the innermost layer of the packaging bag, when the packaging bag is composed of multiple layers. The melting temperature T4 means the melting temperature of the material of the innermost layer of the packaging bag, when the packaging bag is composed of a plurality of layers.

  Here, in the method for producing a laminate of the present invention, the temperatures T1 to T4 are 90 ° C. ≦ T1 <140 ° C., 90 ° C. ≦ T2 <125 ° C., 90 ° C. ≦ T3 <120 ° C., and 90 <T4. It is preferable to satisfy ≦ 140 ° C. If the temperature of each of T1 to T4 satisfies 90 ° C. ≦ T1 <140 ° C., 90 ° C. ≦ T2 <125 ° C., 90 ° C. ≦ T3 <120 ° C., and 90 <T4 ≦ 140 ° C., the deformation of the end is further increased. It can be well suppressed.

  Here, in the method of manufacturing a laminate of the present invention, the base preferably includes an electronic device. If the substrate includes an electronic device, a laminate with less end deflection can be obtained, and degradation and breakage of the embedded electronic device can be prevented.

  Here, in the method for producing a laminate of the present invention, the packaging bag preferably includes one or more layers made of a polyethylene resin. If the said packaging bag contains one or more layers which consist of polyethylene-type resin, the laminated body by which the deformation | transformation of the edge part was suppressed can be reliably produced, without using a spacer or a reinforcement board.

  Here, the method for producing a laminate of the present invention is not limited to the thermoplastic resin, but is preferably a hydrogenated block copolymer from the viewpoint of light resistance and flexibility. If the thermoplastic resin is a hydrogenated block copolymer, the flexibility of the resulting laminate can be improved.

  According to the method for manufacturing a laminate of the present invention, it is possible to produce a laminate in which deformation of the end portion is suppressed without using a spacer or a reinforcing plate.

FIG. 7 is a drawing for explaining the manufacturing method of the laminate of Example 1; FIG. 7 is a drawing for explaining the manufacturing method of the laminate of Example 2;

  Hereinafter, embodiments of the present invention will be described in detail.

(Method of manufacturing laminate)
The method for producing a laminate of the present invention comprises producing a laminate comprising a substrate and at least one resin layer formed on the substrate, wherein the resin layer comprises a thermoplastic resin. The method includes vacuum degassing a package in which the laminate is enclosed in a packaging bag, and heating and pressing the vacuum degassed package to produce a laminate.

<Laminate>
The configuration of the laminate only needs to include the base and at least one resin layer formed on the base; for example, (i) a two-layer structure of the base and the resin layer may be used. (Ii) It may be a structure having at least one resin layer between the substrates, optionally having an additional substrate, and (iii) a structure having a substrate between the resin layers.
Moreover, a laminated body is generally manufactured by bonding together the resin sheet which comprises a resin layer, and a base material.

<Base material>
The substrate used in the laminate of the present invention is not particularly limited as long as functional problems such as melting, deformation, breakage and decomposition do not occur with respect to the heating temperature, and there are no limitations, for example, electronic devices, glass plates , Metal plates, heat-resistant resin plates, heat-resistant resin films and the like. The heat-resistant resin plate and the heat-resistant resin film do not contain a thermoplastic resin.
Here, it is preferable that the base material includes the electronic device from the viewpoint of being able to obtain a laminate in which the electronic device is embedded in the resin layer with less deflection at the end while preventing deterioration and breakage of the electronic device. It is more preferable to provide a resin layer and an electronic device between glass plates.

The thickness of the substrate used in the laminate of the present invention is not particularly limited, but is preferably 0.05 mm or more from the viewpoint of the strength of the laminate and the embedding property of the electronic device, 0.1 mm or more Is more preferably 0.3 mm or more.
When two or more substrates are used in the laminate of the present invention, the thickness of each substrate may be the same or different (for example, the thickness of one of the substrates is 10 mm, and the thickness of the other substrate may be 1 mm).

<< Electronic Device >>
Specific examples of the electronic device include an LED mounting tape, an organic EL element, a liquid crystal element, an electronic paper, a film speaker, a sensor such as an optical sensor, and the like. The electronic device may have a substrate such as a flexible substrate such as polycarbonate, polyethylene terephthalate, polyethylene naphthalate or alicyclic olefin polymer, or a glass substrate such as quartz glass, soda lime glass (soda glass), inorganic alkali glass, etc. You may or may not have it. That is, an element such as an LED mounting tape or an organic EL element may be disposed on the substrate, or only an element such as an LED mounting tape or an organic EL element may be provided.
A waterproof flexible light source can be manufactured by using an LED mounting tape as an electronic device.
Moreover, a waterproof and antifouling display can be produced by using an organic EL element as an electronic device.
Furthermore, a waterproof sensor can be manufactured by using an optical sensor as an electronic device.

<< Glass plate >>
There is no restriction | limiting in particular as a glass plate, For example, well-known inorganic glass plates, such as float plate glass, polished plate glass, template glass, netted plate glass, heat ray absorption plate glass, etc. are mentioned. These may be used alone or in combination of two or more.
These glass plates have transparency and may be either colorless or colored.
There is no restriction | limiting in particular as a shape of a glass plate, A flat form may be sufficient and curved-surface shape may be sufficient.
Moreover, there is no restriction | limiting in particular as a material of the glass used for a glass plate, For example, aluminosilicate acid glass, alumino borosilicate glass, uranium glass, potassium glass, silicate glass, crystallized glass, germanium glass, quartz glass, soda Lime glass (soda glass), lead glass, barium borosilicate glass, borosilicate glass, etc. are mentioned.

<Resin layer>
The number of resin layers is not particularly limited as long as it is one or more, but is preferably two or more from the viewpoint of the embedding property of the electronic device.
That is, the resin layer is a single layer resin sheet or a stacked body obtained by stacking a plurality of resin sheets.

The thickness of the resin layer is not particularly limited, and is preferably 0.05 mm or more, more preferably 0.1 mm or more, and particularly preferably 0.3 mm or more. By setting the thickness of the resin layer within the above-mentioned preferable range, the handling property is excellent and the thickness can be easily adjusted.
When the laminate has an electronic device, the thickness of the resin layer is preferably 1.0 or more times the thickness of the electronic device from the viewpoint of electronic device protection.
The resin layer may have a non-uniform thickness structure in a minute range, provided with a concavo-convex pattern, an embossed shape, a level difference, a groove shape, etc. on the surface of the resin sheet.

  There is no restriction | limiting in particular as a method to produce a resin layer, For example, a melt extrusion molding method, an inflation molding method, a calendar molding method, etc. are mentioned. Among these, the melt extrusion molding method is preferable from the viewpoint of easiness in shaping the embossed shape on the surface of the resin layer.

  The surface of the resin layer may be flat, embossed, or the like. Moreover, in order to prevent blocking of resin layers, a release film can also be accumulated and stored on the single side | surface of a resin layer.

  The resin layer contains at least a thermoplastic resin and optionally contains an additive. When the resin layer contains a thermoplastic resin, the flexibility of the laminate can be improved. Furthermore, when the resin layer contains a thermoplastic resin, the base material can be taken out of the resin layer by heating, and the base material can be easily recycled.

<< Thermoplastic resin >>
As thermoplastic resins, block copolymers prepared from aromatic vinyl compounds and conjugated diene compounds and their hydrides; block copolymers prepared from aromatic vinyl compounds and isobutene or isobutene derivatives and their hydrides; polyethylene , Polypropylene, poly-1-butene, poly-4-methylpentene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 4-methylpentene copolymer, ethylene / 1-octene copolymer Ethylene, 1-butene, 1-octene copolymer, ethylene, propylene, dicyclopentadiene copolymer, ethylene, propylene, 5-ethylidene-2-norbornene copolymer, ethylene, propylene, 5-vinyl-2- Norbornene copolymer, ethylene, 1-butene, Polyolefin resins such as cyclopentadiene copolymer, ethylene / 1-butene / 5-ethylidene-2-norbornene copolymer, ethylene / 1-butene / vinyl norbornene copolymer; ethylene / norbornene copolymer, ethylene / tetra Cyclododecene copolymer, ring-opened metathesis polymer of norbornene derivative hydrogenated, cycloolefin polymer such as cyclohexadiene polymer; ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / acrylic acid Olefin / (meth) acrylic acid ester copolymers such as ethylene / (meth) acrylic acid ester copolymers such as methyl copolymer and ethylene / ethyl acrylate copolymer; ethylene / unsaturated carboxylic acid random copolymer Obtained by reacting a compound with a metal compound Onomer resins; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexanedimethylene terephthalate, etc .; bisphenol A, 4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis ( 4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) phenylethane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2, 2-bis (3,5-dimeth -4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'- Bisphenols such as dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl oxide, 9,9-bis (4-hydroxyphenyl) fluorene and carbonyl chloride Polycarbonate resins obtained by the reaction of carbonyl compounds; Styrene resins such as polystyrene, styrene / methyl methacrylate copolymer, styrene / acrylonitrile copolymer; polymethyl methacrylate, methyl polyacrylate, methyl methacrylate / glycidyl methacrylate (Meth) acrylic acid ester (co) polymers, such as methyl methacrylate / tricyclodecyl methacrylate copolymer; ethylene / vinyl acetate copolymer; polyvinyl chloride, polyvinylidene chloride, poly fluoride Halogen-containing resins such as vinyl, polyvinylidene fluoride and ethylene / tetrafluoroethylene copolymer; polyurethane resins; aromatic resins such as polyetheretherketone, polysulfone, polyethersulfone, polyarylate and polyetherimide; Polyamide-based resins such as nylon 6, nylon 66, nylon 11, nylon 12, nylon 6T; modified thermoplastic resins obtained by introducing an alkoxysilyl group or an acid anhydride group into these thermoplastic resins;
Among these, (i) block copolymers produced from aromatic vinyl compounds and conjugated diene compounds and hydrides thereof are preferable, and (ii) polymers containing structural units derived from aromatic vinyl compounds as main components A hydrogenated block copolymer [C] comprising a block [A] and a polymer block [B] containing a structural unit derived from a chain conjugated diene compound as a main component (D) is more preferable, and (iii) a polymer block [A] containing as a main component a structural unit derived from an aromatic vinyl compound and a structural unit derived from a chain conjugated diene compound as a main component 90% or more of carbon-carbon unsaturated bonds in the main chain and side chains of the block copolymer [C] comprising the polymer block [B] More preferred is a block copolymer hydride [D] formed by hydrogenating 90% or more of carbon-carbon unsaturated bonds in the aromatic ring, and (iv) a heavy component containing a structural unit derived from an aromatic vinyl compound as a main component Block copolymer hydride formed by hydrogenating a block copolymer [C] comprising a united block [A] and a polymer block [B] containing a structural unit derived from a chain conjugated diene compound as a main component It is particularly preferable to use a modified block copolymer hydride [E] obtained by introducing an alkoxysilyl group into [D] as a main component, and (v) containing a structural unit derived from an aromatic vinyl compound as a main component Main component of a block copolymer [C] comprising a polymer block [A] and a polymer block [B] containing a structural unit derived from a chain conjugated diene compound as a main component And an alkoxysilyl group is introduced into a block copolymer hydride [D] formed by hydrogenating 90% or more of carbon-carbon unsaturated bonds in side chains and 90% or more of carbon-carbon unsaturated bonds in aromatic rings Most preferably, the modified block copolymer hydride [E] is obtained as a main component.
The thermoplastic resin is preferably dissolved in a solvent. If the thermoplastic resin in the resin layer is dissolved in the solvent, the base material such as the electronic device can be taken out of the resin layer, and the electronic device can be easily recycled.
In the present invention, the “polymer block [A] containing as a main component a structural unit derived from an aromatic vinyl compound” is a “polymer containing more than 50% by mass of a structural unit derived from an aromatic vinyl compound” “Polymer block [B] having block [A]” and containing “a structural unit derived from a chain conjugated diene compound as a main component” represents “50% by mass of structural units derived from a chain conjugated diene compound” Super-containing polymer block [B] "is meant.

-Modified block copolymer hydride [E]-
The modified block copolymer hydride [E] is a polymer in which an alkoxysilyl group is introduced into a block copolymer hydride [D] which is a precursor.

--Block copolymer hydride [D]--
The specific block copolymer hydride [D] used in the present invention is a polymer formed by hydrogenating the precursor block copolymer [C], and more specifically, a structure derived from an aromatic vinyl compound Block copolymer [C] which is a polymer having a polymer block [A] containing a unit as a main component and a polymer block [B] containing a structural unit derived from a chain conjugated diene compound as a main component Is a polymer formed by hydrogenation of
The block copolymer hydride [D] is preferably 90% or more, more preferably 97% or more, particularly preferably 99% or more of the carbon-carbon unsaturated bonds in the main chain and the side chains, and preferably aromatically hydrogenated. Preferably 90% or more, more preferably 97% or more, particularly preferably 99% or more of carbon-carbon unsaturated bonds of the ring are hydrogenated. Here, "hydrogenation of carbon-carbon unsaturated bond in main chain and side chain" means "hydrogenation of double bond derived from chain conjugated diene compound in block copolymer [C]""Hydrogenation of carbon-carbon unsaturated bond in aromatic ring" means "hydrogenation of double bond derived from aromatic ring in block copolymer [C]".
The higher the degree of hydrogenation, which indicates the degree of hydrogenation, the better the light resistance, heat resistance and transparency of the resin layer.
The hydrogenation rate of block copolymer hydride [D] can be calculated | required by the method etc. which measure < ¹ > H-NMR of block copolymer [C] and block copolymer hydride [D].

  The hydrogenation method and reaction mode of carbon-carbon unsaturated bond are not particularly limited and may be carried out according to known methods, but there is little polymer chain cleavage reaction in that the hydrogenation rate can be improved. The hydrogenation process is preferred. Examples of the hydrogenation method with less polymer chain cleavage reaction include the methods described in WO 2011/096389, WO 2012/043708, and the like.

  After completion of the hydrogenation reaction, after removing the hydrogenation catalyst and / or the polymerization catalyst from the reaction solution, the block copolymer hydride [D] can be recovered from the obtained solution. The form of the recovered block copolymer hydride [D] is not particularly limited, but is preferably in the form of pellets and subjected to a subsequent reaction for introducing an alkoxysilyl group.

The molecular weight of the block copolymer hydride [D] is not particularly limited, but it is measured by gel permeation chromatography (GPC) using THF as a solvent from the viewpoint of the heat resistance and mechanical strength of the resin layer. The weight average molecular weight (Mw) in terms of polystyrene conversion to be carried out is preferably 35,000 or more, more preferably 38,000 or more, particularly preferably 40,000 or more, and 200,000 or less. It is preferably 150,000 or less, more preferably 100,000 or less.
The molecular weight distribution (Mw / Mn) of the block copolymer hydride [D] is not particularly limited, but is preferably 3 or less, and 2 or less from the viewpoint of heat resistance and mechanical strength of the resin layer. Is more preferably 1.5 or less.

---Block copolymer [C]---
The block copolymer [C] contains, as a main component, one or more polymer blocks [A] containing a structural unit derived from an aromatic vinyl compound as a main component, and a structural unit derived from a chain conjugated diene compound Although it is a polymer having one or more polymer blocks [B] to be contained, it is preferably a polymer comprising two or more polymer blocks [A] and one or more polymer blocks [B].
The number of polymer blocks [A] in the block copolymer [C] is preferably 3 or less, and more preferably 2 or less.
The number of polymer blocks [B] in the block copolymer [C] is preferably 2 or less, more preferably 1.
A block copolymer obtained by hydrogenating the block copolymer [C] by setting the number of the polymer block [A] and the polymer block [B] in the block copolymer [C] respectively within the above ranges In the combined hydride [D], a hydrogenated polymer block derived from the polymer block [A] (hereinafter sometimes referred to as “hydrogenated polymer block [A _h ]”) and a polymer block [B] derived The glass transition temperature on the high temperature side based on the hydrogenated polymer block [A _h ] (hereinafter sometimes referred to as “Tg ₂ ”) by preventing the phase separation with the hydrogenated polymer block from becoming unclear. Can be prevented, and in turn, the heat resistance of the resulting resin layer can be prevented from decreasing.
As the glass transition temperature Tg ₂ of the high-temperature side of the block copolymer hydride (D) is not particularly limited, preferably 90 ° C. to 125 ° C..

  The form of the block of the block copolymer [C] is not particularly limited and may be a chain block or a radial block, but from the viewpoint of mechanical strength, it is a chain block Is preferred. Here, a particularly preferable form of the block copolymer [C] is a triblock copolymer ([A]-[B]-[A] in which the polymer block [A] is bonded to both ends of the polymer block [B]. ]).

The weight fraction of the total amount of polymer block [A] in block copolymer [C] is wA, and the weight fraction of the total amount of polymer block [B] in block copolymer [C] is wB. Sometimes, the ratio wA: wB between wA and wB is preferably 30:70 to 60:40, more preferably 35:65 to 55:45, and 40:60 to 50:50. Is particularly preferred.
By setting the mass fraction of wA to 60% or less, it is possible to prevent the decrease in the flexibility (flexibility) of the obtained resin layer. On the other hand, the heat resistance of the resin layer can be prevented from decreasing by setting the mass fraction of wA to 30% or more.

The molecular weight of the block copolymer [C] is not particularly limited, but from the viewpoint of heat resistance and mechanical strength of the resin layer, the weight average molecular weight in terms of polystyrene measured by GPC using tetrahydrofuran (THF) as a solvent ( Mw) is preferably 35,000 or more, more preferably 38,000 or more, particularly preferably 40,000 or more, and preferably 200,000 or less, 150,000 or less Is more preferably, and particularly preferably 100,000 or less.
The molecular weight distribution (Mw / Mn) of the block copolymer [C] is not particularly limited, but is preferably 3 or less, and 2 or less from the viewpoint of heat resistance and mechanical strength of the resin layer. Is more preferable, and 1.5 or less is particularly preferable.

  The method for producing the block copolymer [C] is not particularly limited, and, for example, the methods described in WO 2003/018656, WO 2011/096389, etc. can be adopted.

[Polymer block [A]]
Polymer block [A] is a polymer block which has as a main component structural unit [a] derived from an aromatic vinyl compound. The content of the structural unit [a] in the polymer block [A] is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 99% by mass or more.
It can prevent that the heat resistance of the resin layer obtained falls that content of a structural unit (a) in polymer block [A] is 90 mass% or more.

Polymer block [A] may contain components other than structural unit [a]. Other components include structural unit [b] derived from a chain conjugated diene compound described later and / or structural unit [j] derived from other vinyl compounds. The total content of the structural unit [b] derived from the chain conjugated diene compound and the structural unit [j] derived from the other vinyl compound in the polymer block [A] is preferably 10% by mass or less, The content is more preferably 5% by mass or less, and particularly preferably 1% by mass or less.
When the polymer block [A] contains a structural unit [b] other than the structural unit [a] and / or a structural unit [j], the polymer block [A] usually contains structural units [a] and [b]. And [j] are irregularly repeated.
When the total content of the structural unit [b] and the structural unit [j] in the polymer block [A] is 10% by mass or less, it is possible to prevent the heat resistance of the obtained resin layer from being lowered.
When the block copolymer [C] has a plurality of polymer blocks [A], the polymer blocks [A] may be identical to or different from each other.

[[Aromatic vinyl compound]]
As an aromatic vinyl compound, for example, styrene; α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butyl "Styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent" such as styrene and 5-t-butyl-2-methylstyrene; "alkoxy having 1 to 6 carbon atoms as a substituent" such as 4-methoxystyrene Styrenes having "; styrenes having an aryl group as a substituent" such as 4-phenylstyrene; vinyl naphthalenes such as 1-vinylnaphthalene, 2-vinylnaphthalene and the like; You may use these individually by 1 type or in combination of 2 or more types.
Among these, from the viewpoint of low hygroscopicity, “aromatic vinyl compounds having no polar group” such as styrene and “styrenes having an alkyl group having 1 to 6 carbon atoms as a substituent” are preferable, and further industrially Styrene is more preferred because of easy availability.

[[Other vinyl compounds]]
Other vinyl compounds include vinyl compounds other than aromatic vinyl compounds and chain conjugated diene compounds, such as chain vinyl compounds, cyclic vinyl compounds, unsaturated cyclic acid anhydrides, unsaturated imide compounds, etc. . These compounds may have a substituent such as a nitrile group, an alkoxycarbonyl group, a hydroxycarbonyl group or a halogen atom. Moreover, you may use these individually by 1 type or in combination of 2 or more types.
Among these, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-eicosene from the viewpoint of low hygroscopicity , C2-C20 linear vinyl compounds such as 4-methyl-1-pentene and 4,6-dimethyl-1-heptene (linear olefins); cyclic vinyls having 5 to 20 carbon atoms such as vinylcyclohexane and norbornene Compounds (cyclic olefins); cyclic diene compounds such as 1,3-cyclohexadiene and norbornadiene; and the like, which do not contain a polar group are preferable.

[Polymer block [B]]
Polymer block [B] is a polymer block which has as a main component structural unit [b] originating in a chain | strand-shaped conjugated diene compound. The content of the structural unit [b] in the polymer block [B] is preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
When the content of the structural unit [b] in the polymer block [B] is 70% by mass or more, the obtained resin layer is preferable because it has flexibility (flexibility).

Polymer block [B] may contain components other than structural unit [b]. Other components include the structural unit [a] derived from the above-mentioned aromatic vinyl compound and / or the structural unit [j] derived from the above-mentioned other vinyl compound. The total content of structural units [a] derived from aromatic vinyl compounds and structural units [j] derived from other vinyl compounds in polymer block [B] is preferably 30% by mass or less, and 20 It is more preferable that it is mass% or less, and it is especially preferable that it is 10 mass% or less.
When the polymer block [B] contains a structural unit [a] other than the structural unit [b] and / or a structural unit [j], the polymer block [B] is usually a structural unit [a], [b] It is preferable to have a portion formed by repeating [j] irregularly.
When the total content of the structural unit [a] and the structural unit [j] in the polymer block [B] is 30% by mass or less, the flexibility (flexibility) of the resulting resin layer is prevented from being impaired can do.
When the block copolymer [C] has a plurality of polymer blocks [B], the polymer blocks [B] may be identical to one another or may be different from one another.

  The polymer block [B] is a structural unit in which a part of the structural unit [b] derived from the chain conjugated diene compound is polymerized by 1,2-linkage and / or 3,4-linkage (1,2- and And / or the remaining part of the structural unit [b] having a structural unit derived from 3,4-addition polymerization and derived from a chain conjugated diene compound is a 1,4-bond (a structural unit derived from 1,4-addition polymerization) It may have a structural unit polymerized by

  A polymer block [B] containing a structural unit derived from a chain conjugated diene compound polymerized by 1,2-linkage and / or 3,4-bond is a chain conjugated diene compound, if necessary, an aromatic group Vinyl compounds and other vinyl compounds can be obtained by polymerizing in the presence of a specific compound having an electron donating atom as a randomizing agent. The content of structural units derived from a chain conjugated diene compound polymerized by 1,2- and / or 3,4-linkage can be controlled by the addition amount of the randomizing agent.

  Examples of the compound having an electron donating atom (for example, oxygen (O), nitrogen (N)) include an ether compound, a tertiary amine compound, and a phosphine compound. Among these, an ether compound is preferable from the viewpoint that the molecular weight distribution of the random copolymer block can be reduced and the hydrogenation reaction is hardly inhibited.

  Specific examples of the compound having an electron donor atom include, for example, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl phenyl ether, Propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol diisopropyl ether, propylene glycol dibutyl ether, di (2-tetrahydrofuryl) methane, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, tetramethyl ethylene diamine, and the like can be mentioned. The content of the compound having an electron donating atom is preferably 0.001 parts by mass or more, and more preferably 0.01 parts by mass or more, with respect to 100 parts by mass of the chain conjugated diene compound. The amount is preferably 10 parts by mass or less, and more preferably 1 part by mass or less.

Examples of the chain conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, chloroprene and the like. You may use these individually by 1 type or in combination of 2 or more types.
Among these, from the viewpoint of low hygroscopicity, chain conjugated diene compounds containing no polar group are preferable, and 1,3-butadiene and isoprene are more preferable from the viewpoint of industrial availability.

-Modified block copolymer hydride [E]-
The modified block copolymer hydride [E] is a polymer in which an alkoxysilyl group is introduced to the above-mentioned block copolymer hydride [D].
By introducing an alkoxysilyl group into the block copolymer hydride [D], the modified block copolymer hydride [E] is imparted with sufficient adhesion to a substrate such as an electronic device.

--Alkoxysilyl group--
As the alkoxysilyl group to be introduced, for example, tri (C1-C6 alkoxy) silyl group such as trimethoxysilyl group and triethoxysilyl group; methyldimethoxysilyl group, methyldiethoxysilyl group, ethyldimethoxysilyl group, (C1-C20 alkyl) di (C1-C6 alkoxy) silyl group such as ethyl diethoxy silyl group, propyl dimethoxy silyl group, propyl diethoxy silyl group; phenyl dimethoxy silyl group, phenyl diethoxy silyl group, etc. And (aryl) di (C1-C6 alkoxy) silyl groups; and the like.
In addition, the alkoxysilyl group is bonded to the block copolymer hydride [D] through a divalent organic group such as an alkylene group having 1 to 20 carbon atoms or an alkylene oxycarbonyl alkylene group having 2 to 20 carbon atoms. It may be done.

[Amount of alkoxysilyl group introduced]
There is no restriction | limiting in particular as introduction amount of the alkoxy silyl group with respect to 100 mass parts of block copolymer hydrides [D], It is preferable that it is 0.1 mass part or more, It is more preferable that it is 0.2 mass part or more The amount is preferably 0.3 parts by mass or more, particularly preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less.
The amount of the alkoxysilyl group introduced is 10 parts by mass or less, before the resulting modified block copolymer hydride [E] is melt-formed into a sheet, and then crosslinked with each other. To prevent gelation and deterioration of moldability due to a decrease in fluidity at the time of melting, and when the introduction amount of the alkoxysilyl group is 0.1 parts by mass or more, It is possible to prevent the occurrence of a failure that sufficient adhesion can not be obtained to bond the sheet to the substrate.
The introduction of the alkoxysilyl group can be confirmed by the IR spectrum of the modified block copolymer hydride [E] into which the alkoxysilyl group is introduced. Moreover, the introduction | transduction amount can be computed by the < ¹ > H-NMR spectrum of modified block copolymer hydride [E] in which the alkoxy silyl group was introduce | transduced.

[Method for introducing alkoxysilyl group]
There is no restriction | limiting in particular as a method to introduce | transduce an alkoxy silyl group into block copolymer hydride [D], For example, block copolymer hydride [D] in the presence of an organic peroxide, ethylenic non A method of introducing an alkoxysilyl group by reacting (grafting reaction) a saturated silane compound, more specifically, consisting of a block copolymer hydride [D], an ethylenically unsaturated silane compound and an organic peroxide The mixture may be kneaded in a molten state in a twin-screw kneader for a desired time, and the like.

  The ethylenically unsaturated silane compound used in the above-mentioned introduction method may be a compound capable of causing an alkoxysilyl group to be introduced into the block copolymer hydride [D] by grafting reaction with the block copolymer hydride [D]. There is no particular limitation, and for example, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, dimethoxymethylvinylsilane, diethoxymethylvinylsilane, p-styryltrimethoxysilane, 3-acryloxypropyl Trimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl ester Distearate silane, 3-acryloxypropyltrimethoxysilane, and the like. These may be used alone or in combination of two or more.

  The organic peroxide used for the grafting reaction is not particularly limited, but one having a half-life temperature of 170 ° C. or more and 190 ° C. or less is preferable, for example, t-butylcumyl peroxide, dicumyl peroxide, Di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, 1,4-bis (2-t-butylperoxyisopropyl) ) Benzene, etc. are preferably mentioned. These may be used alone or in combination of two or more.

The kneading temperature by the twin-screw kneader is not particularly limited, but is preferably 180 ° C. or more, more preferably 185 ° C. or more, particularly preferably 190 ° C. or more, and 220 ° C. or less Preferably, the temperature is 210 ° C. or less, and more preferably 200 ° C. or less.
The heating and kneading time is not particularly limited, but is preferably 0.1 minutes or more, more preferably 0.2 minutes or more, and particularly preferably 0.3 minutes or more. It is preferably for less than or equal to minutes, more preferably for less than or equal to 5 minutes, and particularly preferably for less than or equal to 2 minutes.
Continuous kneading and extrusion can be performed efficiently by setting the heating and kneading temperature and the heating and kneading time (residence time) within the above-mentioned preferable ranges.

  The form of the resulting modified block copolymer hydride (E) is not particularly limited, but in general, it is preferable to form it in the form of a pellet and use it for subsequent forming processing and blending of additives.

  As the molecular weight of the modified block copolymer hydride [E], since the molecular weight of the alkoxysilyl group to be introduced is usually small, it is substantially the same as the molecular weight of the block copolymer hydride [D] used as the raw material. does not change. However, in order to cause the ethylenically unsaturated silane compound to react (grafting reaction) with the block copolymer hydride [D] in the presence of the organic peroxide, the crosslinking reaction and the cleavage reaction of the polymer co-occur, The value of the molecular weight distribution of the modified block copolymer hydride [E] is increased.

The molecular weight of the modified block copolymer hydride [E] is not particularly limited, but from the viewpoint of the heat resistance and mechanical strength of the resin layer, the weight average molecular weight in terms of polystyrene measured by GPC using THF as a solvent (Mw), 35,000 or more is preferable, 38,000 or more is more preferable, 40,000 or more is particularly preferable, 200,000 or less is preferable, 150,000 or less is more preferable, 100,000 or less is particularly preferable .
The molecular weight distribution (Mw / Mn) of the modified block copolymer hydride [E] is not particularly limited, but is 3.5 or less from the viewpoint of the heat resistance and mechanical strength of the resin layer. It is preferably 2.5 or less, more preferably 2.0 or less.

-Glass transition temperature Tg, melting point-
The glass transition temperature Tg or melting point of the thermoplastic resin, that is, T2 is preferably 90 ° C. or higher, preferably 95 ° C. or higher, from the viewpoint of heat resistance to heat generation of the electronic device when the substrate is the electronic device. Is more preferably 100.degree. C. or more, particularly preferably less than 125.degree. C., more preferably 115.degree. C. or less, and preferably 110.degree. C. or less, from the viewpoint of recovery of the substrate. Is particularly preferred.
In addition, "glass transition temperature Tg" has a frequency of 1 Hz, for example, using a viscoelasticity measuring apparatus (product name "ARES", manufactured by TA Instruments Japan Ltd.) based on JIS-K7244-2 method. Dynamic viscoelastic properties are measured at a temperature rising rate of 5 ° C./min in the range of −100 ° C. to + 150 ° C., and can be calculated from the peak top temperature of the loss tangent tan δ.
The “melting point” is measured, for example, by differential scanning calorimetry DSC based on JIS K7121.

<< Additives >>
Examples of the additive added to the resin layer include a tackifier, an ultraviolet absorber, an infrared absorber, an antioxidant, an antiblocking agent, a light stabilizer, and the like. These may be used alone or in combination of two or more.

  As a method of blending the additive with the thermoplastic resin, a commonly used known method can be applied, and for example, (i) pellets of the thermoplastic resin and the additive are mixed with a mixer such as tumbler, ribbon blender, Henschel type mixer, etc. (2) A method of forming pellets by melt mixing and extruding using a continuous melt-kneader such as a twin-screw extruder, and (ii) a thermoplastic resin provided with a side feeder The method of making it pellet by melt-kneading and extruding while continuously adding various additives from a side feeder with a twin-screw extruder can be mentioned. By these methods, it is possible to produce an additive uniformly dispersed in a thermoplastic resin.

<<< Tackifier >>>
By blending a tackifier, tackiness and adhesiveness can be imparted.
Specific examples of the tackifier include, for example, low molecular weight products such as polyisobutylene, polybutene, poly-1-octene, ethylene-α-olefin copolymer and the hydrides thereof; polyisoprene, polyisoprene-butadiene copolymer And low molecular weight substances such as H and the like, and hydrides thereof. These may be used alone or in combination of two or more.
Among these, low molecular weight polyisobutylene hydride and low molecular weight polyisoprene hydride are preferable in that they maintain transparency and light resistance and are excellent in the filling effect.

  The addition amount of the tackifier can be appropriately selected according to the required adhesiveness, but from the viewpoint of ease of handling of the resin layer, 30 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin Is preferable, and it is more preferable to make it 20 parts by weight or less.

<<< UV absorber >>>
By blending a UV absorber into the resin layer, it is possible to shield UV rays more.
Specific examples of the ultraviolet absorber include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, triazine compounds, and the like.

<<< Infrared absorber >>>
By blending an infrared absorber, it is possible to shield infrared rays.
Specific examples of the infrared absorber include tin oxide, aluminum-doped tin oxide, indium-doped tin oxide, antimony-doped tin oxide, zinc oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide, tin-doped zinc oxide, Metal oxide fine particles such as silicon-doped zinc oxide, titanium oxide, niobium-doped titanium oxide, tungsten oxide, sodium-doped tungsten oxide, cesium-doped tungsten oxide, thallium-doped tungsten oxide, rubidium-doped tungsten oxide, indium oxide, tin-doped indium oxide; Compounds, naphthalocyanine compounds, ammonium compounds, diimonium compounds, polymethine compounds, diphenylmethane compounds, anthraquinone compounds, pentadiene compounds, azomethine compounds , Near infrared absorbing dye, such as lanthanum hexaboride; and the like.

<<< Antioxidant >>>
Processability etc. can be improved by mix | blending antioxidant.
Specific examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, and the like.

<<< Antiblocking agent >>>
By blending the antiblocking agent, it is possible to prevent blocking of the pellet mainly composed of the thermoplastic resin.
Specific examples of antiblocking agents include lithium stearate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, barium stearate, calcium laurate, zinc laurate and barium laurate And zinc myristate, calcium ricinoleate, zinc ricinoleate, barium ricinoleate, zinc behenate, sodium montanate, magnesium 12-hydroxystearate, calcium 12-hydroxystearate, zinc 12-hydroxystearate, and the like.

<<< Light stabilizer >>>
The durability can be enhanced by blending a light stabilizer.
Specific examples of the light stabilizer include hindered amine light stabilizers.

  As the addition amount of the ultraviolet absorber, infrared absorber, antioxidant, antiblocking agent, light stabilizer and the like, the total addition amount of these additives is 0.001 mass with respect to 100 mass parts of the thermoplastic resin It is preferably at least parts, more preferably at least 0.01 parts by weight, particularly preferably at least 0.05 parts by weight, preferably at most 5 parts by weight, and at most 4 parts by weight Is more preferable, and 3 parts by mass or less is particularly preferable.

<Vacuum degassing process>
The vacuum degassing step is a step of vacuum degassing the package in which the laminate is enclosed in a packaging bag.

<< Packaging bag >>
The packaging bag is not particularly limited as long as the Vicat softening temperature and the melting temperature satisfy the predetermined relationship described later, but it is preferable to include one or more layers made of polyethylene resin, and the innermost layer is made of polyethylene resin. It is more preferable to

<<< Vicat softening temperature >>>
The Vicat softening temperature T3 is not particularly limited, but it is preferably 90 ° C. or higher and 100 ° C. or higher from the viewpoint of suppressing the thermal contraction of the packaging bag when heating and melting the thermoplastic resin. Is more preferably 110 ° C. or more, and from the viewpoint of preventing the heating temperature from being excessively high, it is preferably less than 120 ° C., more preferably 118 ° C. or less, and 115 ° C. or less Being particularly preferred.

"Vicat softening temperature" can be measured using a Toyo Seiki HDT (heat distortion tester) apparatus based on JIS K7206A method. In this measurement method, a test load of 10 N is applied to a plastic test piece, the heat transfer medium is heated at a heating rate of 50 ° C./hour, and the heat transfer medium when the needle-like indenter penetrates 1 mm from the surface of the test piece To measure the temperature of Here, the resin that has reached the "Vicat softening temperature" is easily deformed. That is, when the packaging bag reaches the Vicat softening temperature, the stress accompanying the deformation such as thermal contraction and elongation of the packaging bag becomes extremely small.
Here, the Vicat softening temperature of a packaging bag means the Vicat softening temperature of the material of the innermost layer of a packaging bag, when a packaging bag consists of a several layer.

<<< melting temperature >>>
The melting temperature T4 is not particularly limited, but is preferably 140 ° C. or less, more preferably 135 ° C. or less from the viewpoint of reducing thermal damage to a substrate such as an electronic device at the time of heat processing. It is particularly preferable that the temperature is 130 ° C. or less, and from the viewpoint of maintaining the vacuum degassing state of the packaging bag, the temperature is preferably over 90 ° C., more preferably 110 ° C. or more, and 125 ° C. or more Particularly preferred.

The “melting temperature” can be measured as the melting point using a differential scanning calorimeter (DSC) (DSC 6200, manufactured by Hitachi High-Tech Science Co., Ltd.). The resin that has reached the melting temperature becomes liquid and can not maintain the shape of the packaging bag. Therefore, the state of the packaging bag which has reached the melting temperature is distinctly different from the state in which the packaging bag which has reached the Vicat softening temperature retains its shape.
Here, the melting temperature of a packaging bag means the melting temperature of the material of the innermost layer of a packaging bag, when a packaging bag consists of a several layer.

<<< Polyethylene resin >>>
Examples of polyethylene resins include high density polyethylene resins, medium density polyethylene resins, low density polyethylene resins, linear low density polyethylene resins, linear low density polyethylene resins having long chain branching, and , Mixtures thereof, and the like.

<Heating and pressing process>
The heating and pressurizing step is a step of heating and pressurizing the vacuum degassed package to produce a laminate. Here, it is preferable that heating and pressurization be the autoclave process performed with an autoclave apparatus.
Assuming that the heating temperature is T1, the glass transition temperature or melting point of the thermoplastic resin is T2, the Vicat softening temperature of the packaging bag is T3, and the melting temperature of the packaging bag is T4, each temperature of T1 to T4 is T4> T1. The relationship of TT2 ≧ T3 is satisfied.
That is, for example, a heat-resistant bag (packaging bag) is made of a polyethylene film having a Vicat softening temperature (T3) of 95 ° C and a melting temperature (T4) of 130 ° C, and a resin layer with a glass transition temperature Tg or melting point (T2) of 105 ° C. The temperature is maintained at 110 ° C. in an autoclave by heating at a heating temperature (T1) of 110 ° C., and the Vicat softening temperature (T3) of the heat-resistant bag (packaging bag) is 95 ° C. or less during heating. When the lamination temperature (heating temperature (T1) 110 ° C.) is reached, the Vicat softening temperature (T3) of the packaging bag exceeds 95 ° C., and no stress is applied to the end. In addition, the bonding temperature (heating temperature (T1) 110 ° C) is the melting temperature (T4) 130 ° C or less of the heat-resistant bag (packaging bag), and is higher than the glass transition temperature Tg or melting point (T2) 105 ° C of the resin layer. Because of the high price, the heat-resistant bag (packaging bag) is not melted down, and the lamination is finished well.

  The heating temperature T1 is not particularly limited, but is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 110 ° C. or higher, from the viewpoint of adhesion, particularly preferably thermal degradation. From the viewpoint of prevention and bag dissolution prevention, the temperature is preferably less than 140 ° C., more preferably 130 ° C. or less, and particularly preferably 125 ° C. or less.

  EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the following description, “%” and “parts” representing amounts are based on mass unless otherwise specified. The measurement or evaluation in this example was performed by the following method.

(1) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
The molecular weight of the block copolymer [C] and the block copolymer hydride [D] was measured at 40 ° C. using tetrahydrofuran (THF) as an eluent to calculate a standard polystyrene conversion value. In addition, as a measuring apparatus, the gel permeation chromatography (GPC) apparatus (HLC8320GPC, the Tosoh company make) was used.

(2) Hydrogenation ratio The hydrogenation ratio of the main chain, side chain and aromatic ring of block copolymer hydride [D] is ¹ H of block copolymer [C] and block copolymer hydride [D]. -Calculated by measuring NMR.

(3) Ratio of wA to wB (wA: wB)
The mass fraction of the total amount of the polymer block [A] in the whole block copolymer [C] is wA, and the mass fraction of the total amount of the polymer block [B] in the whole block copolymer [C] is wB As for “ratio of wA to wB (wA: wB)”, the aromatic vinyl compound used for polymerization of each polymer block in the process of producing the block copolymer [C], chain state Each polymer according to the number of parts of the conjugated diene compound and other vinyl compounds and the polymerization conversion ratio of the used monomer to the polymer at each polymerization block termination stage measured using gas chromatography (GC) The mass fraction of the block was calculated.

Production Example 1
<Production of Si-HSIS sheet>
400 parts of dehydrated cyclohexane, 10 parts of dehydrated styrene, and 0.475 parts of dibutyl ether were charged into a reactor equipped with a stirrer and sufficiently purged with nitrogen. While stirring the entire volume at 60 ° C, 0.91 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 is continuously added to the reactor over 40 minutes to advance the polymerization reaction, and after the addition, the whole volume is kept at 60 ° C. for 20 minutes. Was stirred. The reaction solution was measured by gas chromatography (GC), and the polymerization conversion ratio at this point was 99.5%.
Next, 50 parts of dehydrated isoprene was continuously added over 130 minutes to the reaction solution, and stirring was continued for 30 minutes after the addition was completed. At this time, the reaction solution was analyzed by GC, and as a result, the polymerization conversion was 99.5%.
After that, 25 parts of dehydrated styrene was further added continuously over 70 minutes to the reaction solution, and after completion of the addition, the mixture was stirred for 60 minutes as it was. At this time, the reaction solution was analyzed by GC, and as a result, the polymerization conversion was approximately 100%.

  Here, 0.5 part of isopropyl alcohol was added to the reaction liquid to stop the reaction, and a polymer solution was obtained. The block copolymer [C1] contained in the polymer solution is a triblock copolymer of the [A]-[B]-[A] type, and has a weight average molecular weight (Mw) of 45,200 and a molecular weight distribution ( Mw / Mn) was 1.03 and wA: wB = 50: 50.

Next, the above polymer solution is transferred to a pressure resistant reactor equipped with a stirrer, and a diatomaceous earth supported nickel catalyst (product name "E22U", nickel supported amount 60% as a hydrogenation catalyst, manufactured by JGC Catalysts Chemical Co., Ltd.) 4.0 parts and 100 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, and while stirring the solution, hydrogen was supplied, and a hydrogenation reaction was performed 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 [D1] contained in the reaction solution obtained by the hydrogenation reaction was 47,800, and the molecular weight distribution (Mw / Mn) was 1.04.

After completion of the hydrogenation reaction, the reaction solution is filtered to remove the hydrogenation catalyst, and then the obtained solution is treated with pentaerythritol tetrakis [3- (3,5-di-t-butyl) as a phenolic antioxidant. -4-Hydroxyphenyl) propionate] 2.0 parts of a xylene solution in which 0.1 part of (product name "AO60" manufactured by ADEKA Corporation) was dissolved was added and dissolved.
Subsequently, the above solution was subjected to removal of cyclohexane, xylene and other volatile components from the solution at a temperature of 260 ° C. and a pressure of 0.001 MPa or less using a cylindrical concentrator dryer (product name “Contro”, manufactured by Hitachi, Ltd.) did. The molten polymer was extruded from the die in the form of a strand, cooled, and cut by a pelletizer to obtain 94 parts of a pellet consisting of a block copolymer hydride [D1].
The obtained pellet-like block copolymer hydride [D1] has a weight-average molecular weight (Mw) of 47,600, a molecular weight distribution (Mw / Mn) of 1.04, and a hydrogenation ratio of “main chain and side chain And "aromatic" was almost 100%.

  2.0 parts of vinyltrimethoxysilane and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane relative to 100 parts of the pellet of the obtained block copolymer hydride [D1] 0.2 parts (product name "Perhexa (registered trademark) 25B, manufactured by NOF Corporation) was added. This mixture was kneaded at a resin temperature of 200 ° C. and a residence time of 60 to 70 seconds using a twin-screw extruder (product name “TEM 37B”, manufactured by Toshiba Machine Co., Ltd.). The obtained kneaded product was extruded in a strand shape, air-cooled, and then cut by a pelletizer to obtain 97 parts of a pellet of modified block copolymer hydride [E1] having an alkoxysilyl group.

  After dissolving 10 parts of the modified block copolymer hydride [E1] pellet in 100 parts of cyclohexane, the solution obtained is poured into 400 parts of dehydrated methanol to coagulate the modified block copolymer hydride [E1]. I did. The coagulated material was vacuum dried at 25 ° C. to obtain 9.0 parts of a purified modified block copolymer hydride [E1].

In the FT-IR spectrum of the modified block copolymer hydride [E1], new absorption bands derived from Si-OCH ₃ group at 1090 cm ^-1 and Si-CH ₂ groups at 825 cm ^-1 and 739 cm ^-1 , It was observed at a position different from the absorption bands (1075 cm ⁻¹ , 808 cm ⁻¹ , and 766 cm ⁻¹ ) derived from Si—OCH ₃ group and Si—CH group of vinyltrimethoxysilane.
Moreover, when the ¹ H-NMR spectrum (in deuterated chloroform) of the modified block copolymer hydride [E1] was measured, a peak based on a proton of a methoxy group was observed at 3.6 ppm. From the peak area ratio, it was confirmed that 1.9 parts of vinyltrimethoxysilane was bonded to 100 parts of the block copolymer hydride [D1]. The glass transition temperature or melting point T2 of the modified block copolymer hydride [E1] was 121 ° C.

In a pellet of 100 parts of the modified block copolymer hydride [E1] obtained above, (2- (5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-p, which is a UV absorber, was added. -0.2 parts of cresol (manufactured by Sumitomo Chemical Co., Ltd., product name "SUMISORB (registered trademark) 300), and hydrogenated polyisobutene polymer (product name" Polybutene 10 SH "manufactured by NOF Corporation) which is a tackifier. T-die type film melt extruder (T-die width: 400 mm) having a twin-screw kneader (TEM 37B, manufactured by Toshiba Machine Co., Ltd.) equipped with a screw having a diameter of 37 mm and uniformly mixed. Resin temperature 200 ° C., T-die temperature 180 using an extrusion sheet forming machine equipped with a cast roll (with an embossed pattern) and a sheet take-up device. , It was extruded at a cast roll temperature 40 ° C. conditions, the modified block copolymer hydrides [E1] to obtain a Si-HSIS sheet mainly (thickness 760 .mu.m).
The Si-HSIS sheet transferred the embossed pattern by pressing one side of the extruded sheet against the embossing roll with a nip roll. The obtained Si-HSIS sheet was wound and collected on a roll.
The glass transition temperature or melting point T2 of the Si-HSIS sheet containing modified block copolymer hydride [E1] as a main component was 105 ° C.

Example 1
Two soda lime glasses 22 cm long x 16 cm wide and 2.1 mm thick are prepared, and 22 cm long x 16 cm wide and 760 μm thick Si-HSIS sheet (thermoplastic resin (Si-HSIS sheet (modified block copolymer) Six glass transition temperatures Tg: 105 ° C. of a mixed resin of hydride [E1] and polyisobutene polymer hydride were prepared. Next, four Si-HSIS sheets were aligned with their ends aligned, and the same size as that of the liquid crystal panel (manufactured by LG, LP097QX1 9.7 _{′ ′} 2048 × 1536) was hollowed out to prepare a frame-shaped sheet. Next, as shown in FIG. 1, one Si-HSIS sheet 20 having a thickness of 760 μm is placed on soda lime glass 10, and then frame-shaped sheet 30 is superimposed on Si-HSIS sheet 20. The liquid crystal panel 40 was placed in the frame mold 30 a of the frame mold sheet 30. Furthermore, one Si-HSIS sheet 50 having a thickness of 760 μm is stacked, and finally, soda lime glass 60 is stacked, and temporary fixing is performed with a heat-resistant adhesive tape so as not to cause displacement. Was produced. The flat cable 70 for joining the liquid crystal panel 40 to the power supply and the controller was taken out from between the frame-shaped sheets 30.
Next, a linear load density polyethylene film ("LL-XHT", made by Futamura Chemical Co., Ltd., Vicat softening temperature T3: 95 ° C, melting temperature T4: 130 ° C) 60 μm thickness is cut into a size of 300 mm × 300 mm, impulse Using a sealer, three sides were sealed at a seal width of 10 mm to produce a packaging bag X. The temporarily fixed laminate 1 (laminated product) was placed in the packaging bag X, and was installed at the center of the packaging bag X.
Thereafter, vacuum packaging was performed using a small vacuum packaging device (Nippon Packaging Machinery Co., Ltd., “T-100”) with a sealing time of 4 seconds and a degassing time of 30 seconds. Then, take out the vacuum-packed packaging bag X, and while raising the temperature in the tank from room temperature to a heating temperature T1: 110 ° C., using a small-sized autoclave (“Tande Lion” manufactured by Hanyuda Iron Works Ltd.) The holding pressure is 0.1 MPa, and after the temperature in the tank reaches the heating temperature T1: 110 ° C., the holding pressure is 0.3 MPa, and the holding time is 20 minutes, and heat and pressure welding is performed. 1 was produced. After the holding time passed, the temperature in the tank was cooled to 60 ° C. while keeping the pressure at 0.3 MPa, and after cooling, the pressure was reduced and the laminate 1-1 was taken out. A liquid crystal controller was attached to the flat cable 70 of the laminate 1-1 taken out, and it was joined to an HDMI (registered trademark) terminal of a personal computer to observe a display image state. Moreover, thickness was measured in the center and the long side edge part of the laminated body 1-1, and the difference was computed as deflection amount. The results are shown in Table 1.

(Example 2)
Two soda lime glass pieces 22 cm long x 5 cm wide and 2.1 mm thick are prepared, and a 22 cm long x 5 cm wide and 760 μm thick Si-HSIS sheet (thermoplastic resin (modified block copolymer in Si-HSIS sheet) Six glass transition temperatures Tg: 105 ° C. of a mixed resin of hydride [E1] and polyisobutene polymer hydride were prepared. Next, align the edges of the four Si-HSIS sheets and stack them, and cut out the same size as the LED chip mounting tape (3 mm thick, 8 mm wide, SMD3528 high-brightness type, hereinafter referred to as "LED tape"), frame type A sheet was made. Next, as shown in FIG. 2, one Si-HSIS sheet 20 having a thickness of 760 μm is placed on soda lime glass 10, and then frame-shaped sheet 30 is overlaid on Si-HSIS sheet 20. The LED tape 80 was placed in the frame mold 30 a of the frame sheet 30. Furthermore, one Si-HSIS sheet 50 having a thickness of 760 μm is stacked, and finally, soda lime glass 60 is stacked, and temporary fixing is performed with a heat-resistant adhesive tape so as not to cause displacement. Was produced. The cable 90 for joining the LED tape 80 to the power supply and the controller was taken out from between the frame-shaped sheets 30.
Next, a linear load density polyethylene film ("LL-XHT", made by Futamura Chemical Co., Ltd., Vicat softening temperature T3: 95 ° C, melting temperature T4: 130 ° C) 60 μm thickness is cut into a size of 300 mm × 300 mm, impulse Using a sealer, three sides were sealed at a seal width of 10 mm to produce a packaging bag X. The temporarily fixed laminate 2 (laminated product) was placed in the package X and placed in the center of the package bag X.
Thereafter, vacuum packaging and heat and pressure welding were performed in the same manner as in Example 1 except that the temporarily fixed laminate 2 was used, and a laminate 2-1 was produced and taken out. The controller was attached to the cable 90 of the taken out laminate 2-1, and the light emission state of the LED was observed. In addition, the thickness was measured at the center and the long side end of the laminate 2-1, and the difference was calculated as the amount of deflection. The results are shown in Table 1.

(Example 3)
In Example 1, except for changing the thickness of soda lime glass to 0.7 mm, in the same manner as in Example 1, a temporary tacking laminate 1 and a laminate 3-1 are produced, and a laminate 3-1 I took it out. The liquid crystal controller was attached to the flat cable of the laminated body 3-1 taken out, and it joined to the HDMI terminal of a personal computer, and observed the display image state. Moreover, thickness was measured in the center of the laminated body 3-1, and the long side edge part, and the difference was computed as deflection amount. The results are shown in Table 1.

(Comparative example 1)
In the same manner as in Example 1, a temporarily fixed laminate 1 was produced.
Next, a 60 μm thick cast polypropylene film (Trefhan “ZK100”, manufactured by Toray Film Processing Co., Ltd., Vicat softening temperature T3: 150 ° C., melting temperature T4: 165 ° C.) is cut into a size of 300 mm × 300 mm, and an impulse sealer is obtained. Using the seal width 10 mm, three sides were sealed to produce a packaging bag Z.
Thereafter, in the same manner as in Example 1, a laminate 1-3 was produced and taken out. The liquid crystal controller was attached to the flat cable 70 of the laminate 1-3 taken out, and it was joined to the HDMI terminal of the personal computer, and the display image state was observed. In addition, the thickness was measured at the center and the long side end of the laminate 1-3, and the difference was calculated as the amount of deflection. The results are shown in Table 1.

(Comparative example 2)
In the same manner as in Example 2, a temporarily fixed laminate 2 was produced.
Next, in the same manner as Comparative Example 1, a packaging bag Z was produced.
Thereafter, a laminate 2-3 was produced and taken out in the same manner as in Comparative Example 1 except that the temporary tack laminate 2 was used. A controller was attached to the cable 90 of the laminate 2-3 taken out, and the light emission state of the LED was observed. Further, the thickness was measured at the center and the long side end of the laminate 2-3, and the difference was calculated as the amount of deflection. The results are shown in Table 1.

(Comparative example 3)
In the same manner as in Example 3, a temporarily fixed laminate 1 was produced.
Next, in the same manner as Comparative Example 1, a packaging bag Z was produced.
Thereafter, a laminate 3-3 was produced in the same manner as in Comparative Example 1 except that the temporarily fixed laminate 1 produced in the same manner as in Example 3 was used, and was taken out. The liquid crystal controller was attached to the flat cable 70 of the laminate 3-3 taken out, and then joined to the HDMI terminal of the personal computer, and the state of the displayed image was observed. Moreover, thickness was measured in the center and long-side edge part of the laminated body 3-3, and the difference was computed as deflection amount. The results are shown in Table 1.

(Comparative example 4)
In the same manner as in Example 1, a temporarily fixed laminate 1 was produced.
Next, a 60 μm thickness of Rhodity polyethylene film (“Z323” grade, Ube Maruzen Polyethylene Co., Ltd., Vicat softening temperature T3: 112 ° C., melting temperature T4: 135 ° C.) is cut into a size of 300 mm × 300 mm, and an impulse sealer is obtained. Using the seal width 10 mm, three sides were sealed to produce a packaging bag Y.
Thereafter, a laminate 1-2 was prepared and taken out in the same manner as in Comparative Example 1 except that the temporarily fixed laminate 1 was put in the packaging bag Y. The liquid crystal controller was attached to the flat cable 70 of the laminated body 1-2 taken out, and it joined to the HDMI terminal of a personal computer, and observed the display image state. Moreover, thickness was measured in the center of the laminated body 1-2, and a long side edge part, and the difference was computed as deflection amount. The results are shown in Table 1.

  From Table 1, in the method of manufacturing the laminate of Examples 1 to 3 in which the respective temperatures T1 to T4 satisfy the relationship of T4> T1 ≧ T2 ≧ T3, the respective temperatures T1 to T4 are T4>. Compared with the manufacturing method of the laminate of Comparative Examples 1 to 4 in which the relationship of T1 ≧ T2 ≧ T3 is not satisfied, the deformation of the end is suppressed and the electronic device is damaged without using the spacer and the reinforcing plate. It turns out that lamination of a laminated body can be performed without soda lime glass breaking without.

  According to the method for manufacturing a laminate of the present invention, it is possible to produce a laminate in which deformation of the end portion is suppressed without using a spacer or a reinforcing plate.

1 Temporary tacked laminate (laminate)
2 Temporary tacked laminate (laminate)
10 soda lime glass 20 Si-HSIS sheet 30 frame type sheet 30a frame type 40 liquid crystal panel 50 Si HSIS sheet 60 soda lime glass 70 flat cable 80 LED tape 90 cable

Claims (5)

What is claimed is: 1. A method for producing a laminate, comprising: a base material; and at least one resin layer formed on the base material, wherein the resin layer comprises a thermoplastic resin.
Vacuum degassing the package in which the laminate is enclosed in a packaging bag;
Heating and pressing the vacuum degassed package to produce a laminate;
Assuming that the heating temperature is T1, the glass transition temperature or melting point of the thermoplastic resin is T2, the Vicat softening temperature of the packaging bag is T3, and the melting temperature of the packaging bag is T4, the respective temperatures T1 to T4 are And T4> T1 を 満 た す T2 ≧ T3.   The lamination according to claim 1, wherein the temperature of each of T1 to T4 satisfies 90 ° C ≦ T1 <140 ° C, 90 ° C ≦ T2 <125 ° C, 90 ° C ≦ T3 <120 ° C, and 90 <T4 ≦ 140 ° C. How to make the body.   The manufacturing method of the laminated body of Claim 1 or 2 in which the said base material contains an electronic device.   The manufacturing method of the laminated body in any one of Claims 1-3 in which the said packaging bag contains one or more layers which consist of polyethylene-type resin.   The method for producing a laminate according to any one of claims 1 to 4, wherein the thermoplastic resin is a hydrogenated block copolymer.

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