WO2017047632A1 - Corps stratifié - Google Patents

Corps stratifié Download PDF

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Publication number
WO2017047632A1
WO2017047632A1 PCT/JP2016/077088 JP2016077088W WO2017047632A1 WO 2017047632 A1 WO2017047632 A1 WO 2017047632A1 JP 2016077088 W JP2016077088 W JP 2016077088W WO 2017047632 A1 WO2017047632 A1 WO 2017047632A1
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WO
WIPO (PCT)
Prior art keywords
layer
resin
fiber
laminate
group
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Application number
PCT/JP2016/077088
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English (en)
Japanese (ja)
Inventor
寛一 砂川
速雄 伏見
豪 盤指
Original Assignee
王子ホールディングス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Priority claimed from JP2015223845A external-priority patent/JP6641912B2/ja
Priority claimed from JP2016008854A external-priority patent/JP6620567B2/ja
Priority claimed from JP2016038360A external-priority patent/JP6701807B2/ja
Application filed by 王子ホールディングス株式会社 filed Critical 王子ホールディングス株式会社
Priority to US15/760,898 priority Critical patent/US11065850B2/en
Priority to EP16846503.7A priority patent/EP3351374B1/fr
Priority to KR1020187010239A priority patent/KR102196197B1/ko
Priority to CN201680054470.3A priority patent/CN108136714B/zh
Publication of WO2017047632A1 publication Critical patent/WO2017047632A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments

Definitions

  • the present invention relates to a laminate containing fine fibrous cellulose.
  • fibrous cellulose having a fiber diameter of 10 ⁇ m or more and 50 ⁇ m or less in particular, fibrous cellulose (pulp) derived from wood has been widely used mainly as a paper product so far.
  • fibrous cellulose fine fibrous cellulose having a fiber diameter of 1 ⁇ m or less is also known.
  • the resin substrate is reinforced with fibers.
  • fine fibrous cellulose has attracted attention because it can reinforce the resin base material while ensuring transparency.
  • a non-woven fabric cellulose non-woven fabric
  • polycarbonate a non-woven fabric composed of fine fibrous cellulose
  • Patent Document 1 proposes that a cellulose non-woven fabric and a polycarbonate sheet that have previously contained a primer treatment solution such as an acrylic primer are heat-fused to form a laminate.
  • a sheet for example, Patent Documents 2 and 3 obtained by dispersing and curing fine fibrous cellulose in a resin composition containing an acrylic monomer or the like, or a porous fine fiber Sheets obtained by impregnating a cellulose composition-containing sheet with a resin composition containing an acrylic monomer or the like (for example, Patent Documents 4 and 5) are known. Further, as composites, for example, those described in Patent Documents 6 to 9 are known.
  • the present invention has the following configuration.
  • a laminate including a fiber layer formed of cellulose fibers having a fiber width of 1000 nm or less, a resin layer, and an adhesive layer provided between the fiber layer and the resin layer.
  • the adhesive layer includes a functional group (A) that forms a covalent bond with the (meth) acryloyl group, and further hydrolyzes the functional group (B) and the functional group (B) that form a covalent bond with the hydroxyl group.
  • the laminate according to [1] including at least one selected from a group, wherein the resin layer includes a polymer of an acrylic monomer.
  • the functional group (A) is at least two selected from a (meth) acryloyl group and a group represented by H 2 C ⁇ CR 2 —CH (—OH) —. (Wherein R 2 represents a hydrogen atom or a methyl group).
  • R 2 represents a hydrogen atom or a methyl group.
  • the functional group (B) is at least one selected from an isocyanate group, a carbodiimide group, an epoxy group, an alkoxysilyl group, a silanol group, and an oxazoline group.
  • the adhesive layer includes a polymer having a functional group (A) and a compound having a functional group (B).
  • the resin layer includes a first layer disposed on the adhesive layer side and a second layer disposed on one surface side of the first layer and on the opposite side of the adhesive layer.
  • the first layer includes an acrylic resin
  • the second layer includes a polycarbonate resin according to [9] or [10].
  • the first layer includes an epoxy (meth) acrylate resin.
  • the urethane (meth) acrylate resin contained in the adhesive layer includes a urethane unit and an acrylic unit, the content (% by mass) of the urethane unit is P, and the content (% by mass) of the acrylic unit is Q.
  • P / Q is 0.1 or more and 0.9 or less.
  • the adhesive layer is composed of (meth) acrylic acid ester polymer, ⁇ -olefin copolymer, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyurethane, styrene-butadiene copolymer, polyvinyl chloride, epoxy resin.
  • the ratio of the total thickness of the resin layer to the total thickness of the fiber layer is 10 or more [1] to [20]
  • a plurality of fiber layers are laminated on at least one surface side of the resin layer, and the plurality of fiber layers are joined to each other only through the adhesive layer or directly [1] to [29].
  • the number of peels in the 100 masses of the fiber layer when a cross cut test according to JIS K 5400 is performed is 10 or less.
  • the present invention may be an invention relating to the following manufacturing method.
  • the functional group (A) is at least one selected from a (meth) acryloyl group or a group represented by H 2 C ⁇ CR 2 —CH (—OH) —.
  • the method for producing a laminate according to (however, R 2 represents a hydrogen atom or a methyl group).
  • the functional group (B) is at least one selected from an isocyanate group, a carbodiimide group, an epoxy group, an alkoxysilyl group, a silanol group, and an oxazoline group. Production method.
  • the composition containing the functional group (A) and the functional group (B) includes a resin having a functional group (A) and a hydroxyl group, and a compound having at least two functional groups (B).
  • the resin layer has a first layer disposed on the adhesive layer side and a second layer disposed on one surface side of the first layer and on the opposite side of the adhesive layer.
  • the first layer includes an epoxy (meth) acrylate resin
  • the second layer includes a polycarbonate resin
  • the resin layer is formed by applying an epoxy (meth) acrylate-containing composition on the second layer.
  • the resin layer includes a first layer disposed on the adhesive layer side, and a second layer disposed on one surface side of the first layer and on the opposite side of the adhesive layer.
  • the first layer contains an alkyl (meth) acrylate resin
  • the second layer contains a polycarbonate resin
  • the resin layer is formed by coextrusion of the first layer and the second layer [40].
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • (meth) acrylate means that both “acrylate” and “methacrylate” are included.
  • the laminate of the present invention includes a fiber layer formed of cellulose fibers having a fiber width of 1000 nm or less, a resin layer, and an adhesive layer provided between the fiber layer and the resin layer.
  • the number of fiber layers and resin layers constituting the laminate is not limited to one layer, and may be two or more layers.
  • an adhesive layer may be provided between the fiber layers.
  • the adhesive layer that joins the fiber layers may be the same as or different from the adhesive layer that joins the resin layer and the fiber layer.
  • the fiber layers may be directly in contact with each other and bonded, the fiber layers are preferably bonded via an adhesive layer from the viewpoint of improving the adhesive force between the fiber layers.
  • a multi-layer papermaking method can be given as a method of directly joining the fiber layers.
  • an adhesive layer is provided between at least one resin layer and at least one fiber layer.
  • a plurality of fiber layers may be laminated on at least one surface side of the resin layer constituting the laminate of the present invention.
  • the plurality of fiber layers may be joined to each other only through the adhesive layer, or may be joined directly.
  • another resin layer may be sandwiched between the plurality of fiber layers.
  • an adhesive layer is preferably interposed between the fiber layer and the other resin layer, but may not be interposed.
  • Examples of the laminated structure of the laminate of the present invention include FIGS. 1 to 3 and FIGS. 5 to 7.
  • 1A includes a first resin layer 1A (1), a first adhesive layer 2A (2), a fiber layer 3, a second adhesive layer 2B (2), and a second resin layer 1B (1). It has a laminated structure that is laminated in order.
  • 2 has a laminated structure in which a resin layer 1, an adhesive layer 2, and a fiber layer 3 are laminated in this order.
  • 3C includes a first fiber layer 3A (3), a first adhesive layer 2A (2), a second fiber layer 3B (3), a second adhesive layer 2B (2), a resin layer 1,
  • the third adhesive layer 2C (2), the third fiber layer 3C (3), the fourth adhesive layer 2D (2), and the fourth fiber layer 3D (3) are stacked in this order.
  • the fiber layers are uniformly laminated on each of one side (front surface side) and the other side (back surface side) of the resin layer.
  • fiber layers of 1 to 3 layers, and further 4 to 10 layers are laminated on the surface side of the resin layer, and the fiber layer on the surface side is laminated on the back surface side of the resin layer.
  • stacked is mentioned. If the total thickness of the fiber layers provided on the front side of the resin layer is equal to the total thickness of the fiber layers provided on the back side, the mechanical strength of the front and back sides of the laminate is determined. Balance is adjusted evenly. As a result, the mechanical strength of the laminate can be improved in a balanced manner. Furthermore, it is possible to prevent warping during production of the laminate, use, and deterioration over time.
  • the balance is adjusted as described above, and the above effects can be obtained.
  • the number of fiber layers is preferably the same on the front surface side and the back surface side of the resin layer in order to adjust the balance with higher accuracy.
  • the resin layer is laminated
  • the laminated structure it is possible to prevent the fiber layer from absorbing moisture or receiving external contamination.
  • at least one of the uppermost surface and the lowermost surface constituting the outermost layer of the laminate of the present invention is a resin layer.
  • the outermost layer is a resin layer, the water resistance, chemical resistance, weather resistance, etc. of the laminate are more reliably ensured.
  • the thickness from the front surface to the back surface is 2T, and the thickness from either one of the front surface or the back surface to the center (intermediate from one surface to the other surface) is T, the thickness from one surface to the other
  • the ratio of the thickness of the fiber layer existing in the region up to T ⁇ 0.2 is preferably 30% or more and 100% or less, more preferably 50% or more and 100% or less, relative to the thickness (100%) of the entire region, 70 % To 100% is more preferable.
  • the flexural modulus of the laminate according to the present invention can be further increased, and the linear expansion coefficient can be further decreased.
  • the reason for paying attention to the region from one surface to a thickness of 0.2 T is that when the ratio of the fiber layer in the vicinity of the surface of the laminate (near the surface layer) is high, at least of the flexural modulus and the linear expansion coefficient of the laminate This is because one can be improved.
  • the front surface and the back surface are substantially parallel. If they are not substantially parallel, an arbitrary three points that are not arranged on one straight line are determined on one surface, and an average value of the results obtained for the ratios at the three points is calculated. If this average value is within the above range, the laminate including a plane defined by at least three points has excellent physical properties similar to those described above.
  • the relative thickness relationship between adjacent layers is preferably resin layer> fiber layer ⁇ adhesive layer. With this relationship, the fiber layer reinforces the resin layer, and the mechanical properties of the resin layer can be further improved.
  • the ratio of the thickness of the fiber layer and the resin layer bonded to the fiber layer through the adhesive layer is preferably 1.5 or more, and preferably 10 or more. More preferably, 20 or more is more preferable, and 30 or more is particularly preferable. By setting the ratio of the thickness of the resin layer to the thickness of the fiber layer in the above range, the mechanical strength of the laminate is further improved.
  • the upper limit of the thickness ratio is not particularly limited, and is set as appropriate according to the application, and may be, for example, 50 to 100 or more.
  • the ratio of the total thickness of the resin layer to the total thickness of the fiber layer (the total thickness of the resin layer / the thickness of the fiber layer) Is preferably 1.5 or more, more preferably 10 or more, further preferably 20 or more, and particularly preferably 30 or more.
  • the upper limit of the thickness ratio is not particularly limited, and is set as appropriate according to the application, and may be, for example, 50 to 100 or more.
  • the total thickness of the fiber layers provided in the laminate is the thickness of the one fiber layer.
  • the thickness of the laminate is not particularly limited. For example, it is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, further preferably 200 ⁇ m or more, preferably 0.5 mm or more, and more preferably 1 mm or more. 2 mm or more is more preferable. Moreover, it is preferable that the thickness of a laminated body is 20 mm or less. By setting the thickness of the laminate to the above lower limit value or more, it becomes easy to apply the laminate of the present invention to applications where glass has been conventionally applied.
  • the total light transmittance of the laminate is not particularly limited, and is preferably 60% or more, more preferably 65% or more, and still more preferably 70% or more.
  • the total light transmittance of the laminate may be 85% or more, 87% or more, or 90% or more.
  • the total light transmittance of the laminated body is a value measured with a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-150) in accordance with JIS K 7361.
  • the haze of the laminate is not particularly limited, and is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less. Further, the haze of the laminate may be 5% or less. The lower the haze, the easier it is to apply the laminate of the present invention to applications where conventionally transparent glass has been applied.
  • haze is a value measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-150) according to JIS K 7136.
  • a 1st aspect is related with the laminated body which has a fiber layer, an adhesive bond layer, and a resin layer in this order.
  • the fiber layer contains fine fibrous cellulose having a fiber width of 1000 nm or less.
  • the adhesive layer includes a functional group (A) that forms a covalent bond with a (meth) acryloyl group, and further selected from a functional group (B) that forms a covalent bond with a hydroxyl group and a hydrolyzable group of the functional group (B).
  • the resin layer includes an acrylic monomer polymer. In the first aspect, it is possible to obtain a laminate having high transparency and sufficient strength and capable of exhibiting excellent interlayer adhesion even in a harsh environment.
  • the laminate in the first aspect has excellent transparency and strength because it has a fiber layer containing fine fibrous cellulose, an adhesive layer containing a specific functional group, and a resin layer containing a polymer of an acrylic monomer. Yes. Furthermore, in the laminated body in a 1st aspect, durability is favorable. Here, that the durability is good means that the adhesion between the layers of the laminate is excellent, and that good adhesion is exhibited even under severe conditions such as high temperature and high humidity conditions. This is included in the composition in which the functional group (B) contained in the composition forming the adhesive layer is covalently bonded to the hydroxyl group of the fine fibrous cellulose contained in the fiber layer to form the adhesive layer.
  • Functional group (A) forms a covalent bond with the acryloyl group contained in the resin layer, and further, the hydroxyl group and functional group (B) contained in the composition forming the adhesive layer form a covalent bond. This is considered to be achieved. That is, it is considered that adhesion between the layers of the laminate is strengthened by forming a series of cross-linked structures that connect the fiber layer and the resin layer in the adhesive layer.
  • the laminate in the first aspect may be a three-layer laminate containing at least one fiber layer, an adhesive layer, and a resin layer. It may be a laminate of more than one layer.
  • the laminate in the first aspect may be a laminate 10 having a combination of the adhesive layer 2 and the resin layer 1 on both sides of the fiber layer 3. It may be a layered product.
  • the laminated body in a 1st aspect may be a laminated body which has a combination of an adhesive bond layer and a fiber layer on both surfaces of a resin layer, respectively.
  • the resin layer can function as a layer for coating the surface of the fiber layer.
  • a fiber layer may have a function which reinforces a resin layer, and a fiber layer can function as a reinforcement layer.
  • each layer can exhibit various functions depending on the application and configuration.
  • it is preferable that the thickness of each layer is suitably selected according to a use or a structure.
  • the thickness of the resin layer is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 5 ⁇ m or more.
  • the resin layer functions as a layer that coats the surface of the fiber layer, it may be a thin film. Further, the thickness of the resin layer is preferably 10 mm or less, and more preferably 5 mm or less.
  • the resin layer preferably has a certain thickness.
  • the thickness of the fiber layer is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, and further preferably 5 ⁇ m or more.
  • the thickness of the fiber layer is preferably 1 mm or less, and more preferably 100 ⁇ m or less.
  • the thickness of the adhesive layer is preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 1 ⁇ m or more.
  • the thickness of the adhesive layer is preferably 100 ⁇ m or less, and more preferably 50 ⁇ m or less.
  • the above-described laminate is excellent in adhesion between the layers, and the fiber layer is firmly bonded to the resin layer via the adhesive layer.
  • the number of peels in the fiber layer 100 mass is preferably 10 or less, more preferably 5 or less, and 3 or less. Is more preferable.
  • the adhesive evaluation method based on JIS K 5400 is specifically as follows.
  • the laminate in the first aspect is also characterized in that the adhesion between each layer does not deteriorate even under severe conditions such as high temperature and high humidity conditions. Even when the laminate is placed in a high temperature and high humidity condition for a long time, the fiber layer is firmly bonded to the resin layer via the adhesive layer. Specifically, the number of peels in the 100 masses of the fiber layer when the cross cut test according to JIS K 5400 is performed after placing the laminate under conditions of a temperature of 85 ° C. and a relative humidity of 85% for 240 hours is 20 Is preferably 10 or less, more preferably 10 or less, still more preferably 5 or less, and particularly preferably 3 or less.
  • the tensile elastic modulus of the laminate in the first embodiment is preferably 5 GPa or more, more preferably 7 GPa or more, and further preferably 9 GPa or more.
  • the tensile elastic modulus of the laminate is a value measured according to JIS P 8113, and is a tensile elastic modulus at a temperature of 23 ° C. and a relative humidity of 50%.
  • Tensile Tester CODE SE-064 manufactured by L & W, Inc. can be used as a tensile tester.
  • the total light transmittance of the laminate in the first embodiment is preferably 85% or more, more preferably 87% or more, and further preferably 90% or more.
  • the total light transmittance of the laminate is a value measured with a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS K 7361.
  • the haze value of the laminate in the first aspect is preferably 20% or less, more preferably 15% or less, and even more preferably 10% or less.
  • the haze value of the laminate is a value measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-150) in accordance with JIS K 7136.
  • the laminate in the first aspect includes at least a functional group (A) and a resin having a hydroxyl group and a functional group (B) on at least one surface of a fiber layer containing fine fibrous cellulose having a fiber width of 1000 nm or less. It was manufactured by forming a resin layer by applying a resin composition containing an acrylic monomer on the adhesive layer after forming an adhesive layer by applying a composition containing two compounds. It is preferable. That is, in the laminate of the first aspect, it is preferable that the adhesive layer is a coating adhesive layer, and the resin layer is also a coating resin layer.
  • a coating adhesive layer is a layer obtained by apply
  • a coating resin layer is a layer obtained by apply
  • a series of cross-linked structures that connect the fiber layer and the resin layer are formed in the adhesive layer. For this reason, it becomes possible to improve the interlayer adhesiveness in a laminated body more effectively.
  • a 2nd aspect is related with the laminated body which has the fiber layer containing the fine fibrous cellulose whose fiber width is 1000 nm or less, the adhesive bond layer containing a urethane (meth) acrylate resin, and the resin layer in this order. Since the laminate in the second aspect has the above-described configuration, the laminate has excellent adhesion between the fiber layer containing fibrous cellulose having a fiber width of 1000 nm or less and the resin layer. Moreover, the laminated body of this invention can exhibit the outstanding adhesiveness also at the time of bending stress provision.
  • the laminated body of the present invention may have at least one fiber layer 2, adhesive layer 4 and resin layer 6, but may have two or more fiber layers 2, and adhesive layer 4 May have two or more layers, and may have two or more resin layers 6.
  • FIG. 1 shows a laminate 10 having two resin layers 1 and two adhesive layers 2.
  • the two resin layers 1 may be provided on both surfaces of the fiber layer 3.
  • the adhesive layer 2 is provided on both surfaces of the fiber layer 2, and the resin layer 1 is laminated via the adhesive layer 2.
  • the fiber layer 3 may be a fiber layer having a multilayer configuration.
  • the total thickness of the laminate of the present invention is not particularly limited, but is preferably 50 ⁇ m or more, more preferably 100 ⁇ m or more, and further preferably 200 ⁇ m or more. Moreover, it is preferable that the whole thickness of a laminated body is 20 mm or less. The thickness of the laminate is preferably adjusted as appropriate according to the application.
  • the thickness of the fiber layer of the laminate is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, and further preferably 20 ⁇ m or more.
  • the thickness of the fiber layer is It is preferably 500 ⁇ m or less, more preferably 200 ⁇ m or less, More preferably, it is 100 ⁇ m or less.
  • the thickness of the fiber layer constituting the laminate is measured by cutting a cross section of the laminate with an ultramicrotome UC-7 (manufactured by JEOL), and observing the cross section with an electron microscope, a magnifier, or visually. Value.
  • the total thickness of the fiber layers is preferably within the above range.
  • the thickness of the adhesive layer of the laminate is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and further preferably 2 ⁇ m or more.
  • the thickness of the adhesive layer is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the thickness of the adhesive layer constituting the laminate is measured by cutting out a cross section of the laminate with an ultramicrotome UC-7 (manufactured by JEOL), and observing the cross section with an electron microscope, a magnifying glass, or visually. Is the value to be When the laminated body contains a plurality of adhesive layers, the total thickness of the adhesive layers is preferably within the above range.
  • the thickness of the resin layer of the laminate is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, further preferably 50 ⁇ m or more, still more preferably 100 ⁇ m or more, and 200 ⁇ m or more. It is particularly preferred.
  • the thickness of the resin layer is preferably 15000 ⁇ m or less, more preferably 5000 ⁇ m or less, and even more preferably 500 ⁇ m or less.
  • the thickness of the resin layer constituting the laminate is measured by cutting a section of the laminate with an ultramicrotome UC-7 (manufactured by JEOL), and observing the section with an electron microscope, a magnifying glass, or visually. Value.
  • the total resin layer thickness is preferably within the above range.
  • the thickness of the resin layer is preferably 30% or more, more preferably 100% or more of the thickness of the fiber layer.
  • the ratio of the total thickness of the resin layer to the total thickness of the fiber layer (the total thickness of the resin layer / the thickness of the fiber layer) Is preferably 0.5 or more.
  • the total light transmittance of the laminate is preferably 60% or more, more preferably 65% or more, still more preferably 70% or more, and particularly preferably 85% or more.
  • the total light transmittance is a value measured according to JIS K 7361 using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-150).
  • the haze of the laminate is preferably 20% or less, more preferably 15% or less, further preferably 10% or less, and particularly preferably 5% or less.
  • haze is a value measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-150) according to JIS K 7136.
  • the tensile elastic modulus of the laminate at 23 ° C. and 50% relative humidity is preferably 2.5 GPa or more, more preferably 5.0 GPa or more, and further preferably 10 GPa or more. Further, the tensile elastic modulus at 23 ° C. and 50% relative humidity of the laminate is preferably 30 GPa or less, more preferably 25 GPa or less, and further preferably 20 GPa or less.
  • the tensile elastic modulus of the laminate is a value measured in accordance with JIS P 8113.
  • the fiber layer is a layer formed of cellulose fibers having a fiber width of 1000 nm or less.
  • the fiber layer is a dense layer in which cellulose fibers are physically entangled and chemically crosslinked.
  • the fiber width of the cellulose fiber is 1000 nm or less, the fiber layer can be a transparent layer that easily transmits visible light.
  • the content of fine fibrous cellulose contained in the fiber layer is preferably 50% by mass or more, preferably 60% by mass or more, and 70% by mass or more with respect to the total mass of the fiber layer. Is more preferable, and it is further more preferable that it is 80 mass% or more.
  • the content of fine fibrous cellulose contained in the fiber layer is preferably 100% by mass or less, more preferably 95% by mass or less, and 90% by mass or less, with respect to the total mass of the fiber layer. More preferably.
  • content of each fiber layer in a laminated body may be mutually the same, and may differ.
  • the physical entanglement and chemical cross-linking of cellulose fibers are sufficiently formed, so that the strength of the fiber layer can be sufficiently increased.
  • an optional component can be held between cellulose fibers while maintaining the strength of the fiber layer.
  • the thickness of one layer of the fiber layer is, for example, preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, further preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more. Particularly preferred is 30 ⁇ m or more.
  • the thickness of one layer of the fiber layer is preferably 1 mm or less, more preferably 500 ⁇ m or less, further preferably 300 ⁇ m or less, further preferably 200 ⁇ m or less, and 100 ⁇ m or less. Is particularly preferred. When the thickness of one layer of the fiber layer is not less than the above lower limit value, the effect of reinforcing the strength of the laminate by the fiber layer is enhanced.
  • the thickness of one layer of the fiber layer is not more than the above upper limit value, a fiber layer having a uniform thickness is easily formed at the time of production, and it is easy to suppress the occurrence of partial unevenness in the strength of the laminate.
  • the thickness of one layer of the fiber layer constituting the laminate is a value measured by cutting a cross section of the laminate with an ultramicrotome UC-7 (manufactured by JEOL) and observing the cross section with an electron microscope. It is.
  • the thickness of each fiber layer is preferably independently 10 ⁇ m or more, more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more.
  • the thicknesses of the fiber layers may be the same or different. When the thickness of each fiber layer is 10 ⁇ m or more, the reinforcing effect of the resin layer by each fiber layer can be reliably obtained.
  • the total thickness of each fiber layer is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more, and even more preferably 100 ⁇ m or more. By being 20 micrometers or more, the reinforcement effect of the resin layer by the whole fiber layer is further improved.
  • the density of each fiber layer in the laminate is preferably independently 1.0 g / cm 3 or more, more preferably 1.2 g / cm 3 or more, and 1.4 g / cm 3 or more. More preferably.
  • the density in each fiber layer is preferably independently 2.0 g / cm 3 or less, more preferably 1.7 g / cm 3 or less, that is 1.65 g / cm 3 or less More preferably, it is more preferably 1.6 g / cm 3 or less.
  • the density of each fiber layer in the laminate may be the same or different. When the density of the fiber layer is equal to or higher than the lower limit, the effect of reinforcing the strength of the laminate by the fiber layer is further enhanced.
  • the adhesiveness of a fiber layer and an adhesive bond layer improves more as the density of a fiber layer is below the said upper limit.
  • the density of the fiber layer has a correlation with the smoothness of the surface of the fiber layer, and when the density increases, the surface of the fiber layer tends to be smooth.
  • the density of the fiber layer is not more than the above upper limit value, it is considered that moderate roughness remains on the surface of the fiber layer, the adhesive layer is easily anchored on the surface, and the adhesion is improved.
  • the density of one layer of the fiber layer constituting the laminate is a value calculated based on the basis weight and thickness of one layer of the fiber layer constituting the laminate in accordance with JIS standard P8118: 2014. .
  • the basis weight of one fiber layer can be calculated according to JIS standard P8124: 2011 after cutting so that only the fiber layer of the laminate remains with an ultramicrotome UC-7 (manufactured by JEOL).
  • the density of each fiber layer is a density containing arbitrary components other than a cellulose fiber.
  • the present invention is also characterized in that the fiber layer is a non-porous layer.
  • the fiber layer is a non-porous, which means that the overall density of the fiber layer is 1.0 g / cm 3 or more. If the density of the entire fiber layer is 1.0 g / cm 3 or more, it means that the porosity contained in the fiber layer is suppressed to a predetermined value or less, and is distinguished from a porous sheet or layer. .
  • the non-porous fiber layer is also characterized by a porosity of 15% by volume or less. The porosity of a fiber layer here is calculated
  • Porosity (volume%) [1 ⁇ B / (M ⁇ A ⁇ t)] ⁇ 100
  • A is the area (cm 2 ) of the fiber layer
  • t is the thickness (cm) of the fiber layer
  • B is the mass (g) of the fiber layer
  • M is the density of cellulose.
  • Each fiber layer in the laminate may independently contain an optional component other than cellulose fibers.
  • the optional component a substance capable of improving the strength, density, chemical resistance, etc. of the fiber layer is preferable, and examples thereof include hydrophilic oxygen-containing organic compounds (excluding the cellulose fiber).
  • the kind and content of the optional component contained in each fiber layer in the laminate may be the same or different.
  • the oxygen-containing organic compound is preferably non-fibrous, and such non-fibrous oxygen-containing organic compound does not contain fine fibrous cellulose or thermoplastic resin fibers.
  • the oxygen-containing organic compound is preferably a hydrophilic organic compound.
  • the hydrophilic oxygen-containing organic compound can improve the strength, density and chemical resistance of the fiber layer.
  • the hydrophilic oxygen-containing organic compound preferably has, for example, an SP value of 9.0 or more.
  • the hydrophilic oxygen-containing organic compound is preferably one in which 1 g or more of the oxygen-containing organic compound is dissolved in, for example, 100 ml of ion exchange water.
  • oxygen-containing organic compound examples include polyethylene glycol, polyethylene oxide, casein, dextrin, starch, modified starch, polyvinyl alcohol, modified polyvinyl alcohol (such as acetoacetylated polyvinyl alcohol), polyvinyl pyrrolidone, polyvinyl methyl ether, and polyacrylates.
  • Hydrophilic polymers such as polyacrylamide, alkyl acrylate copolymer, urethane copolymer, cellulose derivatives (hydroxyethyl cellulose, carboxyethyl cellulose, carboxymethyl cellulose, etc.); hydrophilic low molecules such as glycerin, sorbitol, ethylene glycol, etc. Is mentioned.
  • polyethylene glycol, polyethylene oxide, glycerin, and sorbitol are preferable from the viewpoint of improving the strength, density, chemical resistance, and the like of the fiber layer, and more preferably at least one selected from polyethylene glycol and polyethylene oxide.
  • it is polyethyleneglycol.
  • the oxygen-containing organic compound is preferably an organic compound polymer having a molecular weight of 50,000 to 8,000,000.
  • the molecular weight of the oxygen-containing organic compound is preferably 100,000 to 5,000,000, but may be a low molecule having a molecular weight of less than 1,000, for example.
  • the content of the oxygen-containing organic compound contained in the fiber layer is preferably 1 part by mass or more and 40 parts by mass or less, with respect to 100 parts by mass of the fine fibrous cellulose contained in the fiber layer. More preferably, the amount is 15 parts by mass or more and 25 parts by mass or less.
  • the content of the oxygen-containing organic compound is at least the above lower limit, the strength, density, chemical resistance, etc. of the fiber layer can be further improved. Further, when the content of the oxygen-containing organic compound is not more than the above upper limit value, the physical entanglement between the cellulose fibers and the structure by chemical crosslinking are sufficiently maintained, and the strength of the fiber layer is sufficiently maintained.
  • the content of the oxygen-containing organic compound is within the above range, the balance of the content of the oxygen-containing organic compound with respect to the fine fibrous cellulose is improved, and the strength, density, chemical resistance, etc. of the fiber layer are further improved. Can be made.
  • the total mass of fine fibrous cellulose and oxygen-containing organic compound with respect to the total mass of the single fiber layer is preferably 90% by mass or more, more preferably 95 to 100% by mass.
  • the total mass is preferably 90% by mass or more, more preferably 95 to 100% by mass.
  • the fiber layer may contain organic ions as an optional component.
  • organic ions include tetraalkylammonium ions and tetraalkylphosphonium ions.
  • tetraalkylammonium ions include tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, tetraheptylammonium ion, tributylmethylammonium ion, and lauryltrimethyl.
  • Examples include ammonium ion, cetyltrimethylammonium ion, stearyltrimethylammonium ion, octyldimethylethylammonium ion, lauryldimethylethylammonium ion, didecyldimethylammonium ion, lauryldimethylbenzylammonium ion, and tributylbenzylammonium ion.
  • tetraalkylphosphonium ions examples include tetramethylphosphonium ions, tetraethylphosphonium ions, tetrapropylphosphonium ions, tetrabutylphosphonium ions, and lauryltrimethylphosphonium ions.
  • examples of the tetrapropylonium ion and the tetrabutylonium ion include tetra n-propylonium ion and tetra n-butylonium ion, respectively.
  • the total light transmittance of one layer of the fiber layer is preferably 70% or more, more preferably 80% or more, and further preferably 90% or more.
  • the total light transmission of one layer of the fiber layer constituting the laminate The rate was cut with an ultramicrotome UC-7 (manufactured by JEOL) so that only the fiber layer of the laminate remained, and in accordance with JIS standard K7361: 1997, a haze meter ("HM-150" manufactured by Murakami Color Research Laboratory Co., Ltd.) ).
  • the haze (cloudiness) of one layer of the fiber layer is preferably 2.0% or less, more preferably 1.5% or less, and further preferably 1.0% or less.
  • the haze of one layer of the fiber layer constituting the laminate is cut so that only the fiber layer of the laminate remains with an ultramicrotome UC-7 (manufactured by JEOL), in accordance with JIS standard K7136: 2000, It is a value measured using a haze meter (“HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd.).
  • the cellulose fiber constituting the fiber layer is a fine cellulose fiber having an average fiber width of 1000 nm or less (hereinafter sometimes referred to as fine fibrous cellulose).
  • the fine fibrous cellulose is preferably an aggregate of cellulose molecules having an I-type (parallel chain) crystal structure.
  • the average fiber width of the cellulose fibers constituting the fiber layer of the laminate is cut out of the cross section of the laminate with an ultramicrotome UC-7 (manufactured by JEOL) to expose the fiber layer.
  • the average value obtained by observing and measuring the width of at least 20 cellulose fibers by image analysis processing is obtained.
  • “width” means the distance from one end to the other end of the cellulose fiber, which is the shorter one.
  • ⁇ Fine fibrous cellulose> Although it does not specifically limit as a fibrous cellulose raw material for obtaining a fine fibrous cellulose, It is preferable to use a pulp from the point of being easy to acquire and cheap.
  • the pulp include wood pulp, non-wood pulp, and deinked pulp.
  • wood pulp include hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), sulfite pulp (SP), dissolved pulp (DP), soda pulp (AP), unbleached kraft pulp (UKP), oxygen bleached craft Chemical pulps such as pulp (OKP) are listed.
  • semi-chemical pulps such as semi-chemical pulp (SCP) and chemi-ground wood pulp (CGP), mechanical pulps such as ground wood pulp (GP), thermomechanical pulp (TMP, BCTMP) and the like can be mentioned, but are not particularly limited.
  • Non-wood pulp includes cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw and bagasse, cellulose isolated from sea squirts and seaweed, chitin, chitosan, etc., but is not particularly limited.
  • the deinking pulp includes deinking pulp made from waste paper, but is not particularly limited. The pulp of this embodiment may be used alone or in combination of two or more.
  • wood pulp containing cellulose and deinked pulp are preferable in terms of availability.
  • chemical pulp has a large cellulose ratio, so the yield of fine fibrous cellulose during fiber refinement (defibration) is high, and the degradation of cellulose in the pulp is small, and the fineness of long fibers with a large axial ratio is high. It is preferable at the point from which fibrous cellulose is obtained.
  • kraft pulp and sulfite pulp are most preferably selected. Sheets containing long fibrous fine fibrous cellulose having a large axial ratio tend to provide high strength.
  • the average fiber width of the cellulose fibers is 1000 nm or less.
  • the fine fibrous cellulose is, for example, monofilamentous cellulose having a fiber width of 1000 nm or less.
  • the average fiber width is preferably 1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more.
  • the average fiber width is preferably 200 nm or less, more preferably 100 nm or less, further preferably 50 nm or less, still more preferably 25 nm or less, and particularly preferably 10 nm or less.
  • the average fiber width is 1 nm or more, it is possible to suppress dissolution in water as cellulose molecules, so that physical properties (strength, rigidity, dimensional stability) as fine fibers can be easily expressed.
  • An average fiber width of 200 nm or less is preferable because it is sufficiently smaller than the wavelength of visible light, so that refraction of visible light hardly occurs at the interface with the adhesive layer and transparency is improved.
  • the average fiber width of the cellulose fibers is within the above range, it is not necessary for all cellulose fibers to be within the above fiber width range, and some cellulose fibers may have a fiber width that exceeds the upper limit or less than the lower limit. It may be. That is, thick fibers and thin fibers may be mixed.
  • the measurement of the average fiber width of the fine fibrous cellulose by electron microscope observation is performed as follows.
  • An aqueous suspension of fine fibrous cellulose having a concentration of 0.05% by mass or more and 0.1% by mass or less is prepared, and the suspension is cast on a carbon film-coated grid subjected to a hydrophilic treatment to prepare a sample for TEM observation. To do.
  • an SEM image of the surface cast on glass may be observed.
  • Observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times, or 50000 times depending on the width of the constituent fibers.
  • the sample, observation conditions, and magnification are adjusted to satisfy the following conditions.
  • One straight line X is drawn at an arbitrary location in the observation image, and 20 or more fibers intersect the straight line X.
  • a straight line Y perpendicular to the straight line is drawn in the same image, and 20 or more fibers intersect the straight line Y.
  • the average fiber width (sometimes simply referred to as “fiber width”) of fine fibrous cellulose is an average value of the fiber widths read in this way.
  • the average fiber length of the cellulose fibers is preferably 100 nm or more, more preferably 1 ⁇ m or more, and further preferably 10 ⁇ m or more. Further, the average fiber length of the cellulose fibers is preferably 2.0 mm or less, more preferably 1.0 mm or less, further preferably 800 ⁇ m or less, further preferably 600 ⁇ m or less, and 500 ⁇ m. It is particularly preferred that By making the fiber length within the above range, the destruction of the crystalline region of the fine fibrous cellulose can be suppressed, and the slurry viscosity of the fine fibrous cellulose can be made an appropriate range.
  • the average fiber length of the cellulose fibers is not less than the above lower limit value, the cellulose fibers are easily entangled with each other, and the strength of the fiber layer is further improved.
  • the average fiber length of the cellulose fibers is not more than the above upper limit value, the mechanical strength of the individual cellulose fibers is increased, and the strength of the fiber layer is further improved.
  • the average fiber length of the cellulose fibers constituting the fiber layer of the laminate was cut out of the cross-section of the laminate with an ultramicrotome UC-7 (manufactured by JEOL) to expose the fiber layer, and the fiber layer was observed with an electron microscope.
  • the average value obtained by observing and measuring the length of at least 20 cellulose fibers by image analysis processing is obtained. Specifically, it can be obtained by image analysis using TEM, SEM, or AFM.
  • the axial ratio (major axis / minor axis) of the cellulose fiber is obtained as a value obtained by dividing the above-described average fiber length by the average fiber width. That is, “major axis” means average fiber length, and “minor axis” means average fiber width.
  • the axial ratio of the cellulose fibers is preferably in the range of 20 to 10,000. When the axial ratio is 20 or more, entanglement between cellulose fibers constituting the fiber layer is increased, so that the strength of the fiber layer is improved, and when the axial ratio is 10,000 or less, the density of the fiber layer is increased. The strength of the fiber layer is further improved. In addition, when the axial ratio is in the range of 20 to 10,000, when the cellulose fiber dispersion is paper-formed when forming the fiber layer, the drainage can be kept high.
  • the fine fibrous cellulose preferably has an I-type crystal structure.
  • the proportion of the I-type crystal structure in the fine fibrous cellulose is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more.
  • the ratio of the crystal parts contained in the fine fibrous cellulose is not particularly limited in the present invention, but it is preferable to use cellulose having a crystallinity obtained by X-ray diffraction of 60% or more.
  • the degree of crystallinity is preferably 65% or more, more preferably 70% or more. In this case, further excellent performance can be expected in terms of heat resistance and low linear thermal expansion.
  • the degree of crystallinity is obtained by measuring an X-ray diffraction profile and determining the crystallinity by an ordinary method (Seagal et al., Textile Research Journal, 29, 786, 1959).
  • the cellulose fiber forming the fiber layer may be chemically modified to substitute a hydroxyl group in cellulose with another substituent (functional group).
  • Chemical modification is performed by a known method.
  • the substituent introduced into cellulose by chemical modification include, for example, an acyl group such as a phosphate group, an acetyl group, an acryloyl group, a methacryloyl group, a propionyl group, and a propioyl group, an isocyanate group such as a 2-methacryloyloxyethylisocyanoyl group, Examples thereof include alkyl groups such as methyl group, ethyl group, propyl group, 2-propyl group, butyl group, 2-butyl group and tert-butyl group, and aryl groups such as benzoyl group and naphthoyl group.
  • the substituent is preferably an anionic group.
  • the anionic group include a phosphate group or a substituent derived from a phosphate group (sometimes simply referred to as a phosphate group), a carboxyl group or a substituent derived from a carboxyl group (sometimes simply referred to as a carboxyl group), And at least one selected from a sulfone group or a substituent derived from a sulfone group (sometimes simply referred to as a sulfone group), and at least one selected from a phosphate group and a carboxyl group It is more preferable that it is a phosphate group.
  • the proportion of chemically modified hydroxyl groups (chemical modification rate) out of all hydroxyl groups in cellulose is not particularly limited, and is preferably adjusted as appropriate in the range of, for example, 0.1 mmol / g to 5.0 mmol / g. It is preferable to adjust appropriately in the range of 1 mmol / g to 3.5 mmol / g. Usually, when it is 0.1 mmol / g or more, an effect by chemical modification (for example, an effect of preventing coloring by heating) is easily obtained. Since the crystallinity of a cellulose fiber is fully maintained as it is 5.0 mmol / g or less, the linear expansion coefficient of a fiber layer and a laminated body can be made smaller. Further, when the ratio of the chemically modified hydroxyl group is set to 0.1 mmol / g to 3.5 mmol / g, the fine fibrous cellulose is easily made ultrafine due to the electrostatic repulsion effect.
  • Measurement of the amount of introduced cellulose fiber substituents is carried out by the following method.
  • a fiber-containing slurry containing about 0.04 g of cellulose fiber in an absolutely dry mass is prepared and diluted to about 50 g using ion-exchanged water. While stirring this solution, the change in the value of electrical conductivity when a 0.01N sodium hydroxide aqueous solution was added dropwise was measured, and the amount of 0.01N sodium hydroxide aqueous solution added when the value was minimal Is the dropping amount at the titration end point.
  • V A dripping amount (ml) of 0.01N sodium hydroxide aqueous solution
  • W cellulose fiber (g) contained in the fiber-containing slurry.
  • the chemical modification rate can also be determined by an analysis method such as weight increase rate, elemental analysis, neutralization titration methods other than those described above, FT-IR, proton NMR and the like.
  • the fine fibrous cellulose is preferably one having a phosphate group or a substituent derived from a phosphate group.
  • the phosphoric acid group is a divalent functional group equivalent to the phosphoric acid obtained by removing the hydroxyl group. Specifically, it is a group represented by —PO 3 H 2 .
  • Substituents derived from phosphoric acid groups include substituents such as groups obtained by polycondensation of phosphoric acid groups, salts of phosphoric acid groups, and phosphoric acid ester groups. It may be a group.
  • the phosphate group or the substituent derived from the phosphate group may be a substituent represented by the following formula (1).
  • R represents a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group.
  • ⁇ is a monovalent or higher cation composed of an organic substance or an inorganic substance.
  • the method of chemical treatment of the cellulose raw material is not particularly limited as long as it is a method capable of obtaining fine fibers.
  • Examples of chemical treatment include acid treatment, ozone treatment, TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl radical) oxidation treatment, enzyme treatment, and covalent bonding with functional groups in cellulose or fiber raw materials. Treatment with a compound capable of forming.
  • the fine fibrous cellulose is hydrolyzed with sulfuric acid, hydrochloric acid, or the like.
  • Those produced by high-concentration acid treatment are almost decomposed in non-crystalline regions and have short fibers (also called cellulose nanocrystals), which are also included in fine fibrous cellulose.
  • a method described in JP 2010-254726 A can be exemplified, but it is not particularly limited. Specifically, after the fiber is treated with ozone, it is dispersed in water, and the resulting aqueous suspension of the fiber is pulverized.
  • TEMPO oxidation As an example of TEMPO oxidation, the method described in Saito T & al. Homogeneous suspensions of individualized microfibrils from TEMPO-catalyzed o oxidation of native cellulose. Biomacromolecules 2006, 7 (6), 6871687-91 can be mentioned. Specifically, after the fiber is subjected to TEMPO oxidation treatment, it is dispersed in water, and the aqueous suspension of the obtained fiber is pulverized.
  • the method described in WO2013 / 176033 can be mentioned, but is not particularly limited.
  • the fiber raw material is treated with an enzyme at least under a condition where the ratio of the enzyme EG activity to the CBHI activity is 0.06 or more.
  • the fine fibrous cellulose preferably has an anionic substituent.
  • the anionic group is preferably at least one selected from a phosphate group, a carboxyl group, and a sulfone group, more preferably at least one selected from a phosphate group and a carboxyl group, Particularly preferred is an acid group.
  • the amount of the anionic substituent introduced is not particularly limited, but is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, per 1 g (mass) of fine fibrous cellulose. / G or more is more preferable, and 0.5 mmol / g or more is particularly preferable.
  • the amount of anionic substituent introduced is preferably 3.5 mmol / g or less, more preferably 3.0 mmol / g or less, further preferably 2.5 mmol / g or less. Particularly preferred is 0 mmol / g or less.
  • the fine fibrous cellulose preferably has a phosphate group or a substituent derived from the phosphate group.
  • a fiber raw material containing cellulose is reacted with at least one selected from a compound having a phosphate group and a salt thereof (hereinafter referred to as “phosphorylation reagent” or “compound A”).
  • phosphorylation reagent may be mixed in a powder or aqueous solution with a dry or wet fiber raw material.
  • a phosphorylating reagent powder or an aqueous solution may be added to the fiber raw material slurry.
  • the phosphoric acid group introduction step can be performed by reacting a fiber raw material containing cellulose with at least one selected from a phosphoric acid group-containing compound and a salt thereof (phosphorylation reagent or compound A). This reaction may be carried out in the presence of at least one selected from urea and derivatives thereof (hereinafter referred to as “compound B”).
  • An example of a method for causing compound A to act on the fiber raw material in the presence of compound B is a method of mixing powder or an aqueous solution of compound A and compound B with a dry or wet fiber raw material.
  • Another example is a method in which powders and aqueous solutions of Compound A and Compound B are added to the fiber raw material slurry.
  • a method of adding an aqueous solution of Compound A and Compound B to a dry fiber material, or a powder or an aqueous solution of Compound A and Compound B to a wet fiber material is preferred.
  • the compound A and the compound B may be added simultaneously, or may be added separately.
  • the form of the fiber raw material is preferably cotton or thin sheet, but is not particularly limited.
  • Compound A used in this embodiment is at least one selected from a compound having a phosphate group and a salt thereof.
  • the compound having a phosphate group include, but are not limited to, phosphoric acid, lithium salt of phosphoric acid, sodium salt of phosphoric acid, potassium salt of phosphoric acid, ammonium salt of phosphoric acid, and the like.
  • the lithium salt of phosphoric acid include lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate.
  • Examples of the sodium salt of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, and sodium polyphosphate.
  • Examples of the potassium salt of phosphoric acid include potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate.
  • Examples of the ammonium salt of phosphoric acid include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate.
  • phosphoric acid and phosphoric acid are introduced efficiently from the viewpoint that the introduction efficiency of phosphate groups is high, the fibrillation efficiency is easily improved in the fibrillation process described later, the cost is low, and the industrial application is easy.
  • Sodium salt, potassium salt of phosphoric acid, and ammonium salt of phosphoric acid are preferable.
  • Sodium dihydrogen phosphate or disodium hydrogen phosphate is more preferable.
  • the compound A is preferably used as an aqueous solution because the uniformity of the reaction is increased and the efficiency of introducing a phosphate group is increased.
  • the pH of the aqueous solution of Compound A is not particularly limited, but is preferably 7 or less because the efficiency of introduction of phosphate groups is increased, and more preferably pH 3 or more and pH 7 or less from the viewpoint of suppressing the hydrolysis of pulp fibers.
  • the pH of the aqueous solution of Compound A may be adjusted by, for example, using a phosphoric acid group-containing compound that exhibits acidity and an alkalinity, and changing the amount ratio thereof. You may adjust pH of the aqueous solution of the compound A by adding an inorganic alkali or an organic alkali to the thing which shows acidity among the compounds which have a phosphoric acid group.
  • the amount of compound A added to the fiber raw material is not particularly limited, but when the amount of compound A added is converted to phosphorus atomic weight, the amount of phosphorus atom added to the fiber raw material (absolute dry mass) is 0.5 mass% to 100 mass%. Or less, more preferably 1% by mass or more and 50% by mass or less, and most preferably 2% by mass or more and 30% by mass or less. If the amount of phosphorus atoms added to the fiber raw material is within the above range, the yield of fine fibrous cellulose can be further improved. When the addition amount of phosphorus atoms with respect to the fiber raw material exceeds 100% by mass, the effect of improving the yield reaches a peak and the cost of the compound A to be used increases. On the other hand, a yield can be raised by making the addition amount of the phosphorus atom with respect to a fiber raw material more than the said lower limit.
  • Examples of the compound B used in this embodiment include urea, thiourea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea, 1-ethylurea and the like. Further, dimethylurea, diethylurea, tetramethylurea, benzoleinurea, hydantoin, or the like may be used.
  • Compound B is preferably used as an aqueous solution like Compound A. Moreover, since the uniformity of reaction increases, it is preferable to use the aqueous solution in which both compound A and compound B are dissolved.
  • the amount of compound B added to the fiber raw material is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 100% by mass or more, and 150% by mass or more. It is particularly preferred that The amount of compound B added to the fiber raw material (absolute dry mass) is preferably 500% by mass or less, more preferably 400% by mass or less, further preferably 350% by mass or less, and 300% by mass. % Or less is particularly preferable.
  • amides or amines may be included in the reaction system.
  • amides include formamide, dimethylformamide, acetamide, dimethylacetamide and the like.
  • amines include methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine, and the like. Among these, triethylamine is known to work as a good reaction catalyst.
  • the heat treatment temperature it is preferable to select a temperature at which a phosphate group can be efficiently introduced while suppressing thermal decomposition and hydrolysis reaction of the fiber. Specifically, it is preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower, and further preferably 130 ° C. or higher and 200 ° C. or lower. In addition, 150 degreeC or more and 200 degrees C or less may be sufficient as heat processing temperature. Moreover, you may use a vacuum dryer, an infrared heating apparatus, and a microwave heating apparatus for a heating.
  • the concentration of the compound A in the fiber raw material may be uneven, and the introduction of phosphate groups on the fiber surface may not proceed uniformly.
  • a very thin sheet-like fiber material is used, or the fiber material and Compound A are kneaded or stirred with a kneader or the like and dried by heating or reduced pressure. The method should be taken.
  • the heating device used for the heat treatment is preferably a device that can always discharge the moisture retained by the slurry and the moisture generated by the addition reaction of the fibers such as phosphate groups to the hydroxyl group of the fiber, such as a blower oven. Etc. are preferred. If water in the system is always discharged, the hydrolysis reaction of the phosphate ester bond, which is the reverse reaction of the esterification, can be suppressed, and the acid hydrolysis of the sugar chain in the fiber can also be suppressed. A fine fiber having a high axial ratio can be obtained.
  • the heat treatment time is also affected by the heating temperature, but it is preferably 1 second or more and 300 minutes or less, preferably 1 second or more and 1000 seconds or less after moisture is substantially removed from the fiber raw material slurry. Preferably, it is 10 seconds or more and 800 seconds or less.
  • the amount of phosphate groups introduced can be within a preferred range by setting the heating temperature and the heating time to appropriate ranges.
  • the amount of phosphate group introduced is preferably 0.1 mmol / g or more, more preferably 0.14 mmol / g or more, and 0.2 mmol / g or more per 1 g (mass) of fine fibrous cellulose. More preferably, it is more preferably 0.3 mmol / g or more, still more preferably 0.4 mmol / g or more, particularly preferably 0.5 mmol / g or more, and 0.6 mmol / g. Most preferably, it is g or more.
  • the amount of phosphate groups introduced is preferably 3.5 mmol / g or less, more preferably 3.0 mmol / g or less, and 2.5 mmol / g per 1 g (mass) of fine fibrous cellulose. Or less, more preferably 2.0 mmol / g or less, and particularly preferably 1.8 mmol / g or less.
  • the amount of phosphate group introduced into the fiber material can be measured by a conductivity titration method. Specifically, by performing the defibration process step, after treating the resulting fine fibrous cellulose-containing slurry with an ion exchange resin, by determining the change in electrical conductivity while adding an aqueous sodium hydroxide solution, The amount introduced can be measured.
  • first region the electrical conductivity rapidly decreases
  • second region the conductivity starts to increase slightly
  • third region the conductivity increment increases
  • the boundary point between the second region and the third region is defined as a point at which the amount of change in conductivity twice, that is, the increase (inclination) in conductivity is maximized. That is, three areas appear.
  • the amount of alkali required in the first region is equal to the amount of strongly acidic groups in the slurry used for titration
  • the amount of alkali required in the second region is the amount of weakly acidic groups in the slurry used for titration. Will be equal.
  • the amount of alkali required in the second region is reduced compared to the amount of alkali required in the first region.
  • the amount of strongly acidic groups coincides with the amount of phosphorus atoms regardless of the presence or absence of condensation, so that the amount of phosphate groups introduced (or the amount of phosphate groups) or the amount of substituent introduced (or the amount of substituents) is simply When said, it represents the amount of strongly acidic group. That is, the alkali amount (mmol) required in the first region of the curve shown in FIG. 8 is divided by the solid content (g) in the titration target slurry to obtain the substituent introduction amount (mmol / g).
  • the phosphate group introduction step may be performed at least once, but may be repeated a plurality of times. In this case, more phosphoric acid groups are introduced, which is preferable.
  • the fine fibrous cellulose has a carboxyl group, for example, a compound having a carboxylic acid-derived group, a derivative thereof, or an acid anhydride or a derivative thereof, such as the TEMPO oxidation treatment described above.
  • a carboxyl group can be introduce
  • the compound having a carboxyl group is not particularly limited, and examples thereof include dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid and itaconic acid, and tricarboxylic acid compounds such as citric acid and aconitic acid. .
  • the acid anhydride of the compound having a carboxyl group is not particularly limited, but examples thereof include acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride. It is done.
  • the derivative of the compound having a carboxyl group is not particularly limited, and examples thereof include an acid anhydride imidized compound having a carboxyl group and an acid anhydride derivative of a compound having a carboxyl group. Although it does not specifically limit as an acid anhydride imidation thing of a compound which has a carboxyl group, Imidation thing of dicarboxylic acid compounds, such as maleimide, succinic acid imide, and phthalic acid imide, is mentioned.
  • the acid anhydride derivative of the compound having a carboxyl group is not particularly limited.
  • at least some of the hydrogen atoms of the acid anhydride of the compound having a carboxyl group such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride, etc. are substituted (for example, alkyl group, phenyl group, etc. ) Are substituted.
  • the amount of carboxyl groups introduced is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and 0.3 mmol / g or more per 1 g (mass) of fine fibrous cellulose. Is more preferably 0.5 mmol / g or more.
  • the amount of carboxyl group introduced is preferably 3.5 mmol / g or less, more preferably 3.0 mmol / g or less, further preferably 2.5 mmol / g or less, and 2.0 mmol / g. It is particularly preferred that it is g or less.
  • a cationic substituent may be introduced into the fine fibrous cellulose as an ionic substituent.
  • a cationic substituent can be introduced into the fiber raw material by adding a cationizing agent and an alkali compound to the fiber raw material and causing the fiber raw material to react.
  • the cationizing agent one having a quaternary ammonium group and a group that reacts with a hydroxyl group of cellulose can be used.
  • the group that reacts with the hydroxyl group of cellulose include an epoxy group, a functional group having a halohydrin structure, a vinyl group, and a halogen group.
  • the cationizing agent include glycidyltrialkylammonium halides such as glycidyltrimethylammonium chloride and 3-chloro-2-hydroxypropyltrimethylammonium chloride or halohydrin type compounds thereof.
  • the alkali compound contributes to the promotion of the cationization reaction.
  • Alkali compounds include alkali metal hydroxides or alkaline earth metal hydroxides, alkali metal carbonates or alkaline earth metal carbonates, alkali metal phosphates or alkaline earth metal phosphates, etc.
  • Organic alkali compounds such as ammonia, aliphatic amines, aromatic amines, aliphatic ammoniums, aromatic ammoniums, heterocyclic compounds and their hydroxides, carbonates, phosphates, etc. It may be.
  • the introduction amount of the cationic substituent can be measured using, for example, elemental analysis.
  • alkali treatment When manufacturing a fine fibrous cellulose, you may perform an alkali treatment between a substituent introduction
  • the alkali compound contained in the alkali solution is not particularly limited, but may be an inorganic alkali compound or an organic alkali compound.
  • the solvent in the alkaline solution may be either water or an organic solvent.
  • the solvent is preferably a polar solvent (polar organic solvent such as water or alcohol), and more preferably an aqueous solvent containing at least water.
  • a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is particularly preferred because of its high versatility.
  • the temperature of the alkali solution in an alkali treatment process is not specifically limited, 5 to 80 degreeC is preferable and 10 to 60 degreeC is more preferable.
  • the immersion time in the alkaline solution in the alkali treatment step is not particularly limited, but is preferably 5 minutes or longer and 30 minutes or shorter, and more preferably 10 minutes or longer and 20 minutes or shorter.
  • the usage-amount of the alkaline solution in an alkali treatment is not specifically limited, It is preferable that it is 100 mass% or more and 100,000 mass% or less with respect to the absolute dry mass of a phosphate group introduction
  • the phosphate group-introduced fiber may be washed with water or an organic solvent before the alkali treatment step.
  • the alkali treatment in order to improve the handleability, it is preferable to wash the alkali-treated phosphate group-introduced fiber with water or an organic solvent before the defibrating treatment step.
  • the substituent-introduced fiber is defibrated in the defibrating process.
  • the fiber is usually defibrated using a defibrating apparatus to obtain a fine fibrous cellulose-containing slurry, but the processing apparatus and the processing method are not particularly limited.
  • a defibrating apparatus a high-speed defibrator, a grinder (stone mill type pulverizer), a high-pressure homogenizer, an ultra-high pressure homogenizer, a high-pressure collision type pulverizer, a ball mill, a bead mill, or the like can be used.
  • a device for wet grinding such as a disk type refiner, a conical refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, or a beater should be used. You can also.
  • the defibrating apparatus is not limited to the above.
  • Preferable defibrating treatment methods include a high-speed defibrator, a high-pressure homogenizer, and an ultra-high pressure homogenizer that are less affected by the grinding media and less concerned about contamination.
  • a polar organic solvent in addition to water, a polar organic solvent can be used.
  • polar organic solvents include alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc), and the like, but are not particularly limited.
  • alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butyl alcohol.
  • ketones include acetone and methyl ethyl ketone (MEK).
  • ethers include diethyl ether and tetrahydrofuran (THF).
  • THF tetrahydrofuran
  • the dispersion medium may be one type or two or more types. Further, the dispersion medium may contain a solid content other than the fiber raw material, such as urea having hydrogen bonding property.
  • the fibrillation treatment may be performed after the fine fibrous cellulose is concentrated and dried.
  • the concentration and drying methods are not particularly limited, and examples thereof include a method of adding a concentrating agent to a slurry containing fine fibrous cellulose, a generally used dehydrator, a press, and a method using a dryer.
  • a well-known method for example, the method described in WO2014 / 024876, WO2012 / 107642, and WO2013 / 121086 can be used.
  • the concentrated fine fibrous cellulose may be formed into a sheet. The sheet can be pulverized to perform a defibrating process.
  • the equipment used for pulverization of fine fibrous cellulose includes high-speed fibrillators, grinders (stone mill type pulverizers), high-pressure homogenizers, ultra-high pressure homogenizers, high-pressure collision type pulverizers, ball mills, bead mills, disk type refiners, and conicals.
  • An apparatus for wet pulverization such as a refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, a beater, and the like can be used, but is not particularly limited.
  • the fine fibrous cellulose-containing product having a phosphoric acid group obtained by the above-described method is a fine fibrous cellulose-containing slurry, which may be diluted with water so as to have a desired concentration.
  • the fine fibrous cellulose-containing slurry is formed into a sheet by a method described later to form a fiber layer.
  • the adhesive layer is a layer that joins the fiber layer and the resin layer. Since the laminated body of this invention is equipped with the adhesive bond layer which joins a fiber layer and a resin layer, mechanical strength, such as a bending elastic modulus and a linear expansion coefficient, is excellent rather than the laminated body which does not have an adhesive bond layer.
  • Dry coating amount of one layer of adhesive layer 0.5 g / m 2 or more preferably, 1.0 g / m 2 or more preferably, 1.5 g / m 2 or more is more preferable.
  • dry coating amount is, for example, it is possible to a 100 g / m 2 or less, preferably 5.0 g / m 2 or less, 4.0 g / m 2, more preferably below 3.0 g / m 2 or less is more preferable.
  • the dry coating amount of one layer of the adhesive layer is not less than the above lower limit value, sufficient adhesion between the fiber layer and the resin layer is obtained, and the mechanical strength is further improved. Further, when the dry coating amount of one layer of the adhesive layer is not more than the above upper limit value, the total light transmittance can be increased and haze can be suppressed low.
  • the thickness of one layer of the adhesive layer is, for example, preferably 0.1 ⁇ m or more, more preferably 0.5 ⁇ m or more, further preferably 1 ⁇ m or more, and particularly preferably 2 ⁇ m or more. preferable. Further, the thickness of one layer of the adhesive layer is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, further preferably 30 ⁇ m or less, further preferably 20 ⁇ m or less, and further preferably 10 ⁇ m or less. It is particularly preferable that the thickness is 7 ⁇ m or less. When the thickness of one layer of the adhesive layer is equal to or more than the lower limit value, sufficient adhesion between the fiber layer and the resin layer is obtained, and the mechanical strength is further improved.
  • the total thickness of the adhesive layers is within the above range.
  • the thickness of the adhesive layer constituting the laminated body is a value measured by cutting a cross section of the laminated body with an ultramicrotome UC-7 (manufactured by JEOL) and observing the cross section with an electron microscope. .
  • the adhesive layer is composed mainly of (meth) acrylate polymer, ⁇ -olefin copolymer, ethylene-vinyl acetate copolymer, polyvinyl alcohol, polyurethane, styrene-butadiene copolymer, polyvinyl chloride, epoxy. It is preferable to include one or more adhesives selected from resins, melamine resins, silicone resins, casein, natural rubber, and starch.
  • “as a main component” means 50% by mass or more based on the total mass (100% by mass) of the adhesive layer.
  • an embodiment including a (meth) acrylic acid ester polymer which is excellent in the balance between improvement in adhesion and mechanical strength and improvement in transparency, is also given as a preferred example.
  • a complex of a compound having a silica particle and / or a silanol group and a (meth) acrylic acid ester polymer is also a preferable embodiment from the viewpoint of improving adhesion.
  • the (meth) acrylic acid ester polymer is a polymer obtained by graft polymerization of a synthetic resin other than (meth) acrylic resin such as epoxy resin and urethane resin, and (meth) acrylic acid ester and other monomers. And a copolymer obtained by copolymerization.
  • the molar fraction of monomers other than (meth) acrylic acid ester in the copolymer is 50 mol% or less. Further, in the (meth) acrylic acid ester polymer (100% by mass), the content of the synthetic resin other than the graft-polymerized (meth) acrylic resin is 50% by mass or less.
  • a covalent bond is formed between the hydroxyl group of the fiber layer and / or the functional group introduced into the cellulose fiber and the main component of the adhesive layer from the viewpoint of increasing the adhesion to the fiber layer. More preferably, the compound is included.
  • the type of the compound that forms a covalent bond is preferably at least one of compounds including a silanol group, an isocyanate group, a carbodiimide group, an epoxy group, and an oxazoline group.
  • a compound containing a silanol group or an isocyanate group which is excellent in reactivity with the hydroxyl group of the fiber layer and / or the functional group introduced into the cellulose fiber, is more preferable.
  • the main component of the adhesive layer is more preferably a compound that induces a physical interaction with the resin layer from the viewpoint of increasing the adhesion with the resin layer. That is, the closer the solubility parameter (SP value) of the main component of the adhesive layer and the resin layer is, the better.
  • SP value solubility parameter
  • the difference in SP value between the main component of the adhesive layer and the resin layer is preferably 10 or less, more preferably 5 or less, and even more preferably 1 or less.
  • the main component of the adhesive layer and the synthetic resin constituting the resin layer are preferably different from each other.
  • the adhesive layer includes a functional group (A) that forms a covalent bond with a (meth) acryloyl group, and further includes a functional group (B) and a functional group (B) that form a covalent bond with a hydroxyl group. It may contain at least one selected from hydrolyzable groups. That is, the adhesive layer may include a functional group (A) and a group derived from the functional group (B) or the functional group (B). In this invention, the interlayer adhesiveness in a laminated body can be improved by making an adhesive bond layer contain such multiple types of functional group.
  • the adhesive layer preferably includes the compound a having the functional group (A) and the compound b having the functional group (B), but the functional group (A) and the functional group (B) are at least one by one.
  • the compound may be contained in the molecule.
  • the compound a which has a functional group (A) is a polymer (resin) which has a functional group (A), and both a functional group (A) and a functional group (B) are contained in one molecule.
  • such a compound is also preferably a polymer (resin).
  • the functional group (A) that forms a covalent bond with the (meth) acryloyl group includes a (meth) acryloyl group (H 2 C ⁇ CR 1 —C ( ⁇ O) —) and H 2 C ⁇ CR 2 —CH ( It is preferably at least one selected from the group represented by —OH) —.
  • “(meth) acryloyl group” means an acryloyl group or a methacryloyl group.
  • R 1 and R 2 are a hydrogen atom or a methyl group.
  • the polymer (resin) having the functional group (A) is at least one selected from a (meth) acryloyl group and a group represented by H 2 C ⁇ CR 2 —CH (—OH) —.
  • Acrylic resin having at least one selected from a (meth) acryloyl group and a group represented by H 2 C ⁇ CR 2 —CH (—OH) — is preferred. It is more preferable that the acrylic resin has both a (meth) acryloyl group and a group represented by H 2 C ⁇ CR 2 —CH (—OH) — graft-polymerized.
  • the functional group (B) that forms a covalent bond with the hydroxyl group is preferably at least one selected from an isocyanate group, a carbodiimide group, an epoxy group, an alkoxysilyl group, a silanol group, and an oxazoline group, and is an isocyanate group Is more preferable.
  • the hydrolyzable group of the functional group (B) is a group obtained by hydrolyzing the functional group described above, and is a group derived from the functional group (B).
  • the compound b having a functional group (B) is preferably an isocyanate compound.
  • the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
  • the isocyanate compound includes polyisocyanates such as biuret type, nurate type, and adduct type, and such polyisocyanate can also be used. Of these, nurate type polyisocyanate is preferable from the viewpoint of suppressing coloring due to heating and deterioration over time.
  • the compound b detected in the adhesive layer may be a hydrolyzed group obtained by hydrolyzing at least one isocyanate group of the isocyanate compound.
  • the functional group (A) is a group that forms a covalent bond with the acryloyl group of the acrylic monomer polymer contained in the resin layer.
  • the functional group (B) is a group that forms a covalent bond with the hydroxyl group of the fine fibrous cellulose contained in the fiber layer.
  • the functional group (B) is a group covalently bonded to a hydroxyl group contained in the compound having the functional group (A).
  • the functional group (B) is a group covalently bonded to a hydroxyl group in the following structure contained in the adhesive layer, but the group to which the functional group (B) is covalently bonded is not limited thereto.
  • R 2 represents a hydrogen atom or a methyl group.
  • a compound a having at least one functional group (A) and a hydroxyl group and a compound b having two or more functional groups (B) in one molecule are contained in the adhesive composition forming the adhesive layer.
  • the hydroxyl group of compound a first forms a covalent bond with the first functional group (B) of compound b
  • the functional group (A) of compound a has a polymer of acrylic monomers contained in the resin layer.
  • the 2nd functional group (B) of the compound b forms a covalent bond with the hydroxyl group which the fine fibrous cellulose contained in a fiber layer has.
  • the fine fibrous cellulose contained in the fiber layer and the polymer of the acrylic monomer contained in the resin layer are linked by a crosslinked structure in which the functional groups of the compound a and the compound b are covalently bonded. That is, the component contained in the adhesive layer forms a covalent bond with any of the component contained in the fiber layer and the component contained in the resin layer. Since the adhesive layer includes a series of cross-linked structures as described above, it is considered that the adhesion between the layers in the laminate is improved.
  • the adhesive layer is preferably a coated adhesive layer formed by coating, and the composition (coating liquid) for forming the adhesive layer contains a compound a having at least one functional group (A) and one hydroxyl group. And the compound b having two or more functional groups (B) in one molecule is preferably included. More preferably, the compound a has a (meth) acryloyl group and at least one group represented by H 2 C ⁇ CR 2 —CH (—OH) —.
  • the functional group (A) contained in the compound a contains two or more groups represented by H 2 C ⁇ CR 2 —CH (—OH) —
  • the first H 2 C ⁇ CR 2 The group represented by —CH (—OH) — is counted as the functional group (A)
  • the second group represented by H 2 C ⁇ CR 2 —CH (—OH) — represents the number of hydroxyl groups.
  • Is counted as In forming the adhesive layer it includes a step of curing after applying such a composition, and in this curing step, each functional group forms a covalent bond. In the adhesive layer after curing, the remaining functional groups (A) and functional groups (B) that have not been subjected to covalent bonding will be detected.
  • the hydrolyzable group of the functional group (B) is detected from the adhesive layer instead of the functional group (B). May be. Further, a structure in which each functional group is covalently bonded may be detected to confirm that each functional group is included.
  • a functional group (B) is a group which forms a covalent bond with the hydroxyl group which the fine fibrous cellulose contained in a fiber layer has, even if it forms a covalent bond with the other substituent which a fine fibrous cellulose has. Good.
  • a covalent bond may be formed with the phosphate group —O ⁇ Na + which is an ionic substituent of the fine fibrous cellulose.
  • Examples of the functional group (A), the functional group (B), and the hydrolyzable group detection device for the functional group (B) include a nuclear magnetic resonance analyzer, an infrared spectrometer, an X-ray photoelectron analyzer, and a Raman spectrometer. Etc.
  • the cross-section of the adhesive layer may be analyzed and laminated by physical polishing. The polished surface may be analyzed after the body is polished and the adhesive layer is exposed.
  • the adhesive layer preferably contains a resin, and more preferably contains a polymer (resin) having a functional group (A). That is, the adhesive layer is preferably a layer obtained by polymerizing and curing a curable composition containing a curable monomer component constituting such a resin by a known curing method. Examples of the curing method include thermal curing and radiation curing, and thermal curing is preferable. Examples of radiation include infrared rays, visible rays, ultraviolet rays, electron beams, and the like, but light that is an electromagnetic wave having a wavelength of 1 nm to 1000 nm is preferable. More preferred is an electromagnetic wave having a wavelength of 200 nm to 450 nm, and still more preferred is an ultraviolet ray having a wavelength of 300 nm to 400 nm.
  • the curable composition forming the adhesive layer contains a polymerization initiator. For this reason, since at least one part of a polymerization initiator will remain also in an adhesive bond layer, it is preferable that an adhesive bond layer contains a polymerization initiator. When the curable composition contains a polymerization initiator, the hardness of the adhesive layer can be adjusted.
  • thermo polymerization initiator that generates radicals and acids by heating to the curable composition. It is also preferable to add a photopolymerization initiator that generates radicals and acids by radiation such as ultraviolet rays to the curable composition.
  • thermal polymerization initiator examples include hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxycarbonate, peroxyketal, and ketone peroxide. Specifically, benzoyl peroxide, diisopropyl peroxycarbonate, t-butyl peroxy (2-ethylhexanoate) dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl hydro Peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, or the like can be used. These polymerization initiators may be used alone or in combination of two or more. When thermal polymerization is initiated during light irradiation, it becomes difficult to control the polymerization. Therefore, the thermal polymerization initiator preferably has a 1 minute half-life temperature of 120 ° C. or higher and 300 ° C. or lower.
  • the addition amount of the thermal polymerization initiator is preferably 0.1% by mass or more and 2% by mass or less, and more preferably 0.3% by mass or more and 1% by mass or less with respect to the total mass of the curable monomer component. preferable.
  • photopolymerization initiator examples include a photo radical generator or a photo cationic polymerization initiator.
  • a photoinitiator may be used independently or may use 2 or more types together.
  • Examples of the photo radical generator include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyl diphenylphosphine oxide, or 2,4,6-trimethylbenzoyl diphenyl. Hosifin oxide and the like. Among these, benzophenone or 2,4,6-trimethylbenzoyldiphenylphosphine oxide is preferable.
  • a photocationic polymerization initiator is a compound that initiates cationic polymerization upon irradiation with radiation such as ultraviolet rays or electron beams, such as aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, and the like. Can be mentioned.
  • Aromatic sulfonium salts include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenylsulfonio).
  • Phenyl] sulfide bishexafluoroborate bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoro, diphenyl-4- (phenylthio) Phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (phenylthio) phenylsulfur Nium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis
  • Aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecyl) Phenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexaflu
  • aromatic diazonium salt examples include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, and the like.
  • Aromatic ammonium salts include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2- Cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2- Examples thereof include cyanopyridinium tetrafluoroborate and 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate.
  • (2,4-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron salt includes (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron.
  • UVI6990 UVI6979 manufactured by Union Carbide
  • SP-150 SP-170
  • SP-172 manufactured by ADEKA
  • Irgacure 261 manufactured by Ciba Geigy
  • Irgacure 250 Rhodia SILPI PI2074, JMF-2456 manufactured by Rhodia
  • Sun Aid SI-60L SI-80L
  • SI-100L SI-110L
  • SI-180L SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.
  • a curing agent for curing the cationic polymerizable monomer may be added.
  • the curing agent include amine compounds, compounds such as polyaminoamide compounds synthesized from amine compounds, tertiary amine compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenol compounds, thermal latent cationic polymerization catalysts. Or dicyanamide and derivatives thereof.
  • a photosensitizer can be added.
  • Specific examples include pyrene, perylene, acridine orange, thioxanthone, 2-chlorothioxanthone, and benzoflavin.
  • the addition amount of the photopolymerization initiator is preferably 0.001% by mass to 5% by mass and more preferably 0.01% by mass to 2% by mass with respect to the total mass of the curable monomer component. Preferably, it is 0.05 mass% or more and 0.1 mass% or less.
  • the adhesive layer may include a urethane (meth) acrylate resin.
  • the urethane (meth) acrylate resin is a (meth) acrylate resin having a urethane bond.
  • the urethane (meth) acrylate resin contains a urethane unit and an acrylic unit.
  • the urethane unit is a unit represented by the following structural formula.
  • R 1 is a linking group containing two or more isocyanate structures or a structure derived from an isocyanate structure
  • R 2 is a linking group containing two or more hydroxyl groups or a group derived from a hydroxyl group. It is.
  • the acrylic unit is a unit represented by the following structural formula.
  • R 1 represents a hydrogen atom or a methyl group.
  • P / Q is 0.1 or more and 0.9 or less. It is preferable. P / Q is more preferably 0.8 or less, and further preferably 0.7 or less.
  • the resin layer has a first layer and a second layer, and the first layer contains an alkyl (meth) acrylate resin
  • P / Q is preferably 0.6 or less. More preferably, it is 5 or less.
  • the content (% by mass) of the urethane unit can be measured by analysis using a nuclear magnetic resonance apparatus, an infrared spectroscopic analyzer, or a trace nitrogen analyzer.
  • the acrylic unit content (% by mass) can be measured by a nuclear magnetic resonance apparatus or an infrared spectroscopic analyzer.
  • the glass transition temperature of the urethane (meth) acrylate resin contained in the adhesive layer is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and further preferably 70 ° C. or higher. Moreover, it is preferable that the glass transition temperature of urethane (meth) acrylate resin is 200 degrees C or less.
  • the resin layer is a layer mainly composed of a resin such as a natural resin or a synthetic resin.
  • a main component refers to the component contained 50 mass% or more with respect to the total mass of a resin layer.
  • the content of the resin is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass with respect to the total mass of the resin layer. The above is particularly preferable.
  • content of resin can also be 100 mass%, and may be 95 mass% or less.
  • Examples of natural resins include rosin resins such as rosin, rosin ester, and hydrogenated rosin ester.
  • the synthetic resin is preferably at least one selected from, for example, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyethylene resin, polypropylene resin, polyimide resin, polystyrene resin, and acrylic resin.
  • the synthetic resin is preferably at least one selected from polycarbonate resin and acrylic resin, and more preferably polycarbonate resin.
  • the acrylic resin is preferably at least one selected from polyacrylonitrile and poly (meth) acrylate.
  • polycarbonate constituting the resin layer examples include aromatic polycarbonate resins and aliphatic polycarbonate resins. These specific polycarbonate resins are known and include, for example, the polycarbonate resins described in JP 2010-023275 A.
  • the resin layer may contain an optional component other than the synthetic resin.
  • an optional component other than the synthetic resin.
  • areas such as a filler, a pigment, dye, and an ultraviolet absorber, is mentioned, for example.
  • the thickness of one layer of the resin layer is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, further preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, and 20 ⁇ m or more. Is more preferably 50 ⁇ m or more, even more preferably 100 ⁇ m or more, and most preferably 200 ⁇ m or more. Further, the thickness of one layer of the resin layer may be 500 ⁇ m or more, or 1000 ⁇ m or more. Note that the upper limit of the thickness of the resin layer is not particularly limited, and is appropriately set depending on the application. For example, the thickness may be about 10 mm to 50 mm.
  • the thickness of one layer of the resin layer is preferably 15 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less. Depending on the application, 500 ⁇ m or less may be preferable.
  • the thickness of the resin layer is equal to or greater than the lower limit, the mechanical strength of the laminate is sufficiently stabilized.
  • the laminated body contains multiple resin layers, it is preferable that the total thickness of the resin layers is within the above range.
  • the thickness of the resin layer constituting the laminate is measured by cutting a cross section of the laminate with an ultramicrotome UC-7 (manufactured by JEOL) and observing the cross section with an electron microscope, a magnifying glass, or visually. Value.
  • the resin layer may include a polymer of an acrylic monomer.
  • the resin layer is preferably a coating resin layer formed by coating, and the coating liquid (resin composition) for forming the resin layer preferably contains an acrylic monomer.
  • the resin layer is preferably a coated resin layer formed by coating, and is preferably a layer obtained by polymerizing and curing a resin composition containing an acrylic monomer by a known curing method.
  • the curing method include heat curing and radiation curing, and radiation curing is preferable.
  • a polymerization initiator is contained in the resin composition forming the resin layer.
  • the resin layer preferably contains a polymerization initiator.
  • a polymerization initiator added to a resin composition the thermal polymerization initiator and photoinitiator which were mentioned above can be illustrated.
  • the coating liquid (resin composition) for forming the resin layer may contain an acrylic monomer or a prepolymer of the acrylic monomer.
  • a prepolymer may be comprised from 1 type of acrylic monomers mentioned later, and may be comprised combining 2 or more types.
  • the prepolymer may be a copolymer obtained by copolymerizing an acrylic monomer described later with a urethane structure or an epoxy structure.
  • acrylic monomers examples include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and neopentyl.
  • the acrylic monomer is preferably at least one selected from pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and 1,10-decanediol diacrylate.
  • An acrylic monomer may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the acrylic monomer it is also preferable to use a monofunctional alkyl (meth) acrylate in combination with the polyfunctional acrylic monomer described above.
  • the monofunctional alkyl (meth) acrylate include pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, N-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, lauryl (meth) acrylate, (meth ) Stearyl acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexy
  • the resin layer may have a single layer structure or a multilayer structure.
  • the resin layer includes a first layer disposed on the adhesive layer side, and a first layer disposed on the one surface side of the first layer and on the opposite side of the adhesive layer. It is preferable to have two layers. In the second aspect, it is also preferable to use a resin layer having such a multilayer structure.
  • FIG. 9 is a cross-sectional view illustrating the configuration of the laminate 10 when the fiber layer 3 includes the first layer 11 and the second layer 12. As shown in FIG. 9, the first layer 11 is laminated so as to be in contact with the adhesive layer 2 and constitutes the laminate 10.
  • the first layer preferably contains an acrylic resin.
  • the second layer preferably contains at least one selected from polycarbonate resin and acrylic resin, and more preferably contains polycarbonate resin.
  • the first layer preferably contains an acrylic resin.
  • the acrylic resin is, for example, a polymer of an acrylic monomer having at least one selected from alkyl groups, hydroxyl groups, epoxy groups, alkoxy groups, ethylene oxide groups, amino groups, amide groups, carboxyl groups, urethane groups, and phenyl groups.
  • the acrylic resin is more preferably a polymer of an acrylic monomer having at least one selected from an alkyl group and an epoxy group. That is, the first layer preferably includes at least one selected from alkyl (meth) acrylate resins and epoxy (meth) acrylate resins.
  • alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, butyl (meth) acrylate, and hexyl (meth).
  • the alkyl (meth) acrylate is preferably methyl (meth) acrylate or ethyl (meth) acrylate, and more preferably methyl (meth) acrylate.
  • the epoxy (meth) acrylate examples include glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate.
  • the epoxy (meth) acrylate is a polymer obtained by graft polymerization of components other than epoxy (meth) acrylate, such as urethane (meth) acrylate, and epoxy (meth) acrylate and other monomers are copolymerized.
  • the content of components other than the epoxy (meth) acrylate in the copolymer is preferably 50% by mass or less.
  • the second layer preferably contains a polycarbonate resin, and the preferred polycarbonate resin is as described above.
  • the resin layer has the first layer and the second layer
  • such a layer structure may be formed by applying the other layer to any one layer, or the first layer and the second layer may be formed.
  • the layer structure may be formed by co-extruding the constituent resin.
  • the resin layer is preferably formed by coextrusion.
  • the resin layer can be formed by co-extrusion of an alkyl (meth) acrylate resin and a polycarbonate resin. That is, the resin layer may be a coextruded film.
  • a resin composition containing a monomer or a polymer component constituting the first layer is applied on at least one surface of the second layer.
  • a layer may be formed.
  • a bar coater, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater, or the like is used as a coating machine that coats the monomer constituting the first layer or a resin composition containing a polymer component.
  • a bar coater, a die coater, a curtain coater, and a spray coater are preferable because the thickness can be made more uniform. It is preferable to provide a curing step after coating.
  • a hardening process a heating process, a light irradiation process, etc. can be mentioned, for example.
  • the surface of the resin layer on the fiber layer side may be subjected to surface treatment. Further, one surface of the second layer, that is, the surface on the first layer side may be subjected to surface treatment.
  • the surface treatment method include corona treatment, plasma discharge treatment, UV irradiation treatment, electron beam irradiation treatment, and flame treatment.
  • the surface treatment is preferably at least one selected from corona treatment and plasma discharge treatment.
  • the plasma discharge treatment is preferably a vacuum plasma discharge treatment.
  • the surface on the fiber layer side of the resin layer may form a fine uneven structure.
  • one surface of the second layer that is, the surface on the first layer side may be subjected to surface treatment.
  • the surface has a fine concavo-convex structure
  • the adhesion between the fiber layer and the resin layer or the adhesion between the first layer and the second layer can be more effectively enhanced.
  • the fiber layer side surface of the resin layer has a fine concavo-convex structure, such a structure is formed by processing steps such as blast processing, emboss processing, etching processing, corona processing, plasma discharge processing, etc. Is preferred.
  • the fine concavo-convex structure refers to a structure in which the number of concave portions present on a single straight line having a length of 1 mm drawn at an arbitrary location is 10 or more.
  • the fiber layer is peeled off from the resin layer, and then the fiber layer side surface of the resin layer is contacted with a stylus type surface roughness meter ( Measurements can be made by scanning with the Kosaka Laboratory, Surfcoder series).
  • the number of uneven portions can be measured from an observation image of a scanning probe microscope (manufactured by Hitachi High-Tech Science Co., Ltd., AFM5000II and AFM5100N).
  • the laminate of the present invention may further have an inorganic film (hereinafter also referred to as an inorganic layer).
  • the inorganic layer may be laminated on the fiber layer side or may be laminated on the resin layer side.
  • an inorganic layer may be laminated
  • the material constituting the inorganic layer is not particularly limited, but for example, aluminum, silicon, magnesium, zinc, tin, nickel, titanium; these oxides, carbides, nitrides, oxycarbides, oxynitrides, or oxycarbonitrides Or a mixture thereof. From the viewpoint that high moisture resistance can be stably maintained, silicon oxide, silicon nitride, silicon oxide carbide, silicon oxynitride, silicon oxycarbonitride, aluminum oxide, aluminum nitride, aluminum oxide carbide, aluminum oxynitride, or these Mixtures are preferred.
  • the method for forming the inorganic layer is not particularly limited.
  • a method for forming a thin film is roughly classified into a chemical vapor deposition method (chemical vapor deposition, CVD) and a physical film deposition method (physical vapor deposition, PVD), and either method may be adopted.
  • CVD method include plasma CVD using plasma, and catalytic chemical vapor deposition (Cat-CVD) in which a material gas is contact pyrolyzed using a heating catalyst.
  • Cat-CVD catalytic chemical vapor deposition
  • PVD method include vacuum deposition, ion plating, and sputtering.
  • an atomic layer deposition method (Atomic Layer Deposition, ALD) can also be employed.
  • the ALD method is a method of forming a thin film in units of atomic layers by alternately supplying source gases of respective elements constituting a film to be formed to a surface on which a layer is formed.
  • the film forming speed is slow, there is an advantage that it is possible to form a thin film with few defects because it can cleanly cover even a complicated surface more than the plasma CVD method.
  • the ALD method has an advantage that the film thickness can be controlled on the nano order and it is relatively easy to cover a wide surface.
  • the ALD method can be expected to improve the reaction rate, lower the temperature, and reduce the unreacted gas by using plasma.
  • the thickness of the inorganic layer is not particularly limited, for example, when it is intended to exhibit moisture proof performance, it is preferably 5 nm or more, more preferably 10 nm or more, and further preferably 20 nm or more. From the viewpoint of transparency and flexibility, the thickness of the inorganic layer is preferably 1000 nm or less, more preferably 800 nm or less, and even more preferably 600 nm or less.
  • the laminated body of this invention can be manufactured by joining a fiber layer and a resin layer with an adhesive agent.
  • a known method is applied as a method of applying the adhesive to the laminated surface of the fiber layer or the resin layer.
  • a laminated material in which the fiber layer and the adhesive layer are laminated is obtained by applying an adhesive to at least one surface that becomes the laminated surface of the fiber layer using a coater or the like, and drying.
  • the method of manufacturing a laminated body is mentioned by joining a resin layer to the adhesive bond layer of the said laminated material.
  • the dry application quantity of the adhesive bond layer mentioned above can be adjusted by adjusting the quantity which apply
  • a method for bonding the resin layer to the adhesive layer of the laminated material a method of placing a resin sheet material constituting the resin layer on the adhesive layer of the laminated material and performing hot pressing can be given. Also, a laminated material is placed in an injection mold, and the adhesive layer is exposed on the injection space side (center side inside the mold), and the resin is heated and melted in the mold. And a resin layer made of the injected resin is bonded to the adhesive layer of the laminated material. From the viewpoint of improving the adhesion between the fiber layer and the resin layer, it is preferable to produce a laminate by an injection molding method.
  • the laminated material 6 by which an adhesive bond layer is formed on both surfaces of a fiber layer is produced by apply
  • a resin sheet 7 to be installed in an injection mold together with the laminated material 6 is prepared.
  • the resin sheet 7 becomes the resin layer 1 by being thermocompression bonded to the laminated material 6 by the injection pressure of the injected resin in the mold.
  • the resin sheet 7 and the laminated material 6 are sequentially placed at two locations on the inner wall surface of the flat plate mold 5 for injection molding, and fixed with the heat-resistant tape 4.
  • the flat metal mold 5 is assembled by arranging the inner wall surface of the flat metal mold 5 on which the resin sheet 7 and the laminated material 6 are placed so as to correspond to the positions of the upper surface and the lower surface of the formed laminated body 10D. Then, the resin 10 heated and melted from the injection port 5a is injected at an appropriate pressure, and molded at an appropriate temperature, an appropriate mold clamping force, and an appropriate holding time, whereby a laminate 10D is obtained. If necessary, both end portions including the heat-resistant tape 4 can be cut to obtain a finished laminate 10D.
  • the pressure for injecting the resin is, for example, preferably 10 MPa to 500 MPa, more preferably 50 MPa to 400 MPa, and further preferably 100 MPa to 300 MPa.
  • the resin melting temperature at the time of molding is, for example, preferably 100 to 400 ° C., more preferably 150 to 400 ° C., and further preferably 200 to 400 ° C.
  • the mold clamping force at the time of molding is preferably, for example, 200 kN to 100,000 kN, more preferably 500 kN to 50,000 kN, and even more preferably 1000 kN to 10,000 kN.
  • the holding time at the time of molding is, for example, preferably from 0.1 to 600 seconds, more preferably from 1 to 300 seconds, and further preferably from 10 to 60 seconds.
  • the mold temperature at the time of molding is preferably 100 to 400 ° C., more preferably 100 to 300 ° C., and still more preferably 150 to 250 ° C.
  • a cellulose containing a finely divided cellulose fiber is treated by wet grinding or dry grinding using a known grinding machine or paper-making beating machine. Fiber is obtained. Moreover, the refined
  • the fiber layer for example, a fiber slurry in which cellulose fibers are dispersed in a dispersion medium is prepared, and the fiber layer (fiber sheet) is formed by papermaking or coating (coating) and drying. Is mentioned.
  • ⁇ Coating process> In the coating process, a fine fibrous cellulose-containing slurry is applied onto a substrate, and the fine fibrous cellulose-containing sheet formed by drying this is peeled from the substrate to obtain a sheet (fiber layer). It is a process. By using a coating apparatus and a long base material, sheets can be continuously produced. Although the density
  • the quality of the base material used in the coating process is not particularly limited, but the one with higher wettability to the fine fibrous cellulose-containing slurry may be able to suppress the sheet shrinkage during drying, but is formed after drying. It is preferable to select a sheet that can be easily peeled off.
  • a resin plate or a metal plate is preferable, but is not particularly limited.
  • resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc., and those whose surfaces are oxidized, stainless steel A plate, a brass plate or the like can be used.
  • the frame may be fixed and used.
  • the quality of the damming frame is not particularly limited, but it is preferable to select one that can easily peel off the edge of the sheet attached after drying. Among them, a molded resin plate or metal plate is preferable, but is not particularly limited.
  • resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc., and those whose surfaces are oxidized, stainless steel
  • resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc., and those whose surfaces are oxidized, stainless steel
  • a molded plate, brass plate, or the like can be used.
  • a coating machine for coating the fine fibrous cellulose-containing slurry for example, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater or the like can be used.
  • a die coater, a curtain coater, and a spray coater are preferable because the thickness can be made more uniform.
  • the coating temperature is not particularly limited, but is preferably 20 ° C or higher and 45 ° C or lower, more preferably 25 ° C or higher and 40 ° C or lower, and further preferably 27 ° C or higher and 35 ° C or lower. If the coating temperature is equal to or higher than the above lower limit value, the fine fibrous cellulose-containing slurry can be easily applied. If the coating temperature is equal to or lower than the upper limit value, volatilization of the dispersion medium during the coating can be suppressed.
  • the coating step it is preferable to apply the slurry so that the finished basis weight of the sheet is 10 g / m 2 or more and 100 g / m 2 or less, preferably 20 g / m 2 or more and 50 g / m 2 or less.
  • the basis weight is within the above range, a fiber layer having excellent strength can be obtained.
  • the step of obtaining a fiber layer containing fine fibrous cellulose preferably includes a step of drying the fine fibrous cellulose-containing slurry coated on the substrate.
  • a drying method Either a non-contact drying method or the method of drying while restraining a sheet
  • the non-contact drying method is not particularly limited, but a method of drying by heating with hot air, infrared rays, far infrared rays or near infrared rays (heating drying method) or a method of drying in vacuum (vacuum drying method) is applied. Can do. Although the heat drying method and the vacuum drying method may be combined, the heat drying method is usually applied. Although drying by infrared rays, far infrared rays, or near infrared rays can be performed using an infrared device, a far infrared device, or a near infrared device, it is not particularly limited.
  • the heating temperature in the heat drying method is not particularly limited, but is preferably 20 ° C. or higher and 120 ° C.
  • the heating temperature is not less than the above lower limit value, the dispersion medium can be volatilized quickly, and if it is not more than the above upper limit value, it is possible to suppress the cost required for heating and to prevent the fine fibrous cellulose from being discolored by heat. .
  • the obtained fine fibrous cellulose-containing sheet is peeled off from the base material, but when the base material is a sheet, the fine fibrous cellulose-containing sheet and the base material are wound while being laminated to form a fine fibrous form.
  • the fine fibrous cellulose-containing sheet may be peeled from the process substrate immediately before use of the cellulose-containing sheet.
  • the oxygen-containing organic compound when adding an arbitrary component to a fiber layer, it is preferable that the oxygen-containing organic compound contains in the fine fibrous cellulose dispersion liquid.
  • the content of the oxygen-containing organic compound is preferably 1 part by mass or more and 40 parts by mass or less, and preferably 10 parts by mass or more and 30 parts by mass with respect to 100 parts by mass of the fine fibrous cellulose contained in the fine fibrous cellulose dispersion. It is more preferable that the amount is 15 parts by mass or more and 25 parts by mass or less.
  • the step of obtaining a fiber layer containing fine fibrous cellulose may include a step of papermaking the fine fibrous cellulose-containing slurry.
  • Examples of the paper machine in the paper making process include a continuous paper machine such as a long-mesh type, a circular net type, and an inclined type, and a multi-layered paper machine combining these.
  • known paper making such as hand making may be performed.
  • the fine fibrous cellulose-containing slurry is filtered and dehydrated on a wire to obtain a wet paper sheet, and then the sheet is obtained by pressing and drying.
  • the solid content concentration of the slurry is not particularly limited, but is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more.
  • the solid content concentration of the slurry is preferably 10% by mass or less, and more preferably 5% by mass or less.
  • the slurry may contain known papermaking chemicals such as a sizing agent and a paper strength enhancer, if necessary.
  • the filter cloth at the time of filtration is not particularly limited, but it is important that the fine fibrous cellulose does not pass through and the filtration rate is not too slow.
  • seat, fabric, and porous film which consist of organic polymers are preferable.
  • the organic polymer is not particularly limited, but non-cellulosic organic polymers such as polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and the like are preferable.
  • Specific examples include a porous film of polytetrafluoroethylene having a pore size of 0.1 ⁇ m to 20 ⁇ m, for example, 1 ⁇ m, polyethylene terephthalate or polyethylene woven fabric having a pore size of 0.1 ⁇ m to 20 ⁇ m, for example, 1 ⁇ m, but is not particularly limited.
  • This manufacturing apparatus discharges a slurry containing fine fibrous cellulose onto the upper surface of an endless belt, squeezes a dispersion medium from the discharged slurry, generates a web, and dries the web to dry the fiber sheet. And a drying section to produce.
  • An endless belt is disposed from the squeezing section to the drying section, and the web generated in the squeezing section is conveyed to the drying section while being placed on the endless belt.
  • the dehydration method normally used by manufacture of paper is mentioned, After dehydrating with a long net, a circular net, a slanted wire, etc., it dehydrates with a roll press. Is preferred.
  • the drying method is not particularly limited, and examples thereof include methods used in paper production. For example, methods such as a cylinder dryer, a Yankee dryer, hot air drying, a near infrared heater, and an infrared heater are preferable.
  • Examples of the method for drying the slurry to form the fiber sheet include heat drying, air drying, and vacuum drying. You may pressurize in parallel with drying.
  • the heating temperature is preferably about 50 ° C to 250 ° C. Within the above temperature range, drying can be completed in a short time, and discoloration and coloring can be suppressed.
  • the pressure is preferably 0.01 MPa to 5 MPa. When the pressure is within the above range, generation of cracks and wrinkles can be suppressed, and the density of the fiber layer can be increased.
  • the finished basis weight of the sheet 1 g / m 2 or more 200 g / cm 2 are preferred, more preferably 10 g / m 2 or more 100g / cm 2, 25g / m 2 or more 75 g / cm 2 is more preferred.
  • the basic weight of the fiber sheet is a value measured by the method described in JIS P 8124: 2011.
  • the optional component in the fiber slurry it is preferable to uniformly mix the optional component in the fiber slurry to form a fiber layer in which the optional component is dispersed.
  • drying is gentle in the process of forming the fiber layer by drying the fiber slurry formed by papermaking or coating the fiber slurry. It is possible to suppress the occurrence of cracks and wrinkles in the fiber layer. As a result, a high-density and transparent film-like fiber layer can be formed.
  • the fiber layer may be impregnated with an optional component.
  • the optional component is a hydrophilic polymer
  • the hydrophilic polymer can be uniformly contained in the fiber layer with higher efficiency than the subsequent impregnation of the hydrophilic polymer into the fiber layer.
  • the optional component added to the fiber layer increases, the content of cellulose fibers relative to the total mass of the fiber layer is relatively lowered. Therefore, the content of the cellulose fiber in the fiber layer can be adjusted to the preferred range described above by appropriately adjusting the addition amount of the optional component.
  • Density of the fiber sheet used in the production of the laminate is preferably not more than 1.0 g / cm 3 or more 1.7g / cm 3, 1.2g / cm 3 or more 1.65 g / cm 3 and more preferably less, 1. More preferably, it is 4 g / cm 3 or more and 1.6 g / cm 3 or less.
  • the density of the fiber sheet is a value calculated from the basis weight and thickness of the fiber sheet in accordance with JIS standard P8118: 2014.
  • the density of a fiber sheet is a density containing arbitrary components other than a cellulose fiber.
  • a step of obtaining a fiber layer containing fine fibrous cellulose having a fiber width of 1000 nm or less, and a (meth) acryloyl group and a covalent bond are formed on at least one surface of the fiber layer Applying a composition containing a functional group (A) and a functional group (B) that forms a covalent bond with a hydroxyl group to form an adhesive layer; and applying a resin composition containing an acrylic monomer; Forming the step.
  • the step of obtaining the fiber layer in the first aspect is the same as the step described above.
  • a functional group (A) that forms a covalent bond with the (meth) acryloyl group and a functional group (B) that forms a covalent bond with the hydroxyl group are included on at least one surface of the fiber layer. Apply the composition.
  • the functional group (A) and the functional group (B) it is preferable to select each of the functional groups described above.
  • the functional group (A) is preferably at least one selected from a (meth) acryloyl group and a group represented by H 2 C ⁇ CR 2 —CH (—OH) —.
  • B) is preferably at least one selected from an isocyanate group, a carbodiimide group, an epoxy group, an alkoxysilyl group, a silanol group, and an oxazoline group.
  • the composition containing the functional group (A) and the functional group (B) includes a compound a having at least one functional group (A) and a hydroxyl group, and a compound b having at least two functional groups (B). However, it may contain a compound having at least one functional group (A) and one functional group (B) in one molecule.
  • the compound a having at least one functional group (A) and one hydroxyl group is preferably a polymer (resin) having a functional group (A).
  • the polymer (resin) having a functional group (A) is an acrylic having at least one selected from a (meth) acryloyl group and a group represented by H 2 C ⁇ CR 2 —CH (—OH) —. It is preferably a resin, and particularly preferably an acrylic resin in which at least one selected from a (meth) acryloyl group and a group represented by H 2 C ⁇ CR 2 —CH (—OH) — is graft-polymerized preferable.
  • the compound b having at least two functional groups (B) is preferably an isocyanate compound.
  • the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.
  • the isocyanate compound includes polyisocyanates such as biuret type, nurate type, and adduct type, and such polyisocyanate can also be used. Of these, nurate type polyisocyanate is preferable from the viewpoint of suppressing coloring due to heating and deterioration over time.
  • the compound a preferably has at least one functional group (A) and one hydroxyl group, and the hydroxyl group of the compound a first forms a covalent bond with the first functional group (B) of the compound b.
  • a functional group (A) forms a covalent bond with the acryloyl group which the polymer of the acrylic monomer contained in a resin layer has.
  • the 2nd functional group (B) of the compound b forms a covalent bond with the hydroxyl group which the fine fibrous cellulose contained in a fiber layer has.
  • the fine fibrous cellulose contained in the fiber layer and the polymer of the acrylic monomer contained in the resin layer are linked by a crosslinked structure in which the functional groups of the compound a and the compound b are covalently bonded.
  • the functional group (B) may be contained in an amount of 0.5 mol or more and 5.0 mol or less with respect to 1 mol of the functional group (A). Preferably, 0.5 mol or more and 3.0 mol or less are contained.
  • the composition containing the functional group (A) and the functional group (B) further contains a polymerization initiator.
  • a polymerization initiator the polymerization initiator mentioned above can be illustrated.
  • a photoinitiator is contained in the composition containing a functional group (A) and a functional group (B).
  • the composition containing the functional group (A) and the functional group (B) may further contain a solvent.
  • the solvent include esters such as ethyl acetate, butyl acetate, and propyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl, dibutyl ketone, and cyclohexanone, aromatic solvents such as toluene, xylene, and hexane, and organic solvents such as hydrocarbons.
  • esters such as ethyl acetate, butyl acetate, and propyl acetate
  • ketones such as methyl ethyl ketone, methyl isobutyl, dibutyl ketone, and cyclohexanone
  • aromatic solvents such as toluene, xylene, and hexane
  • organic solvents such as hydrocarbons.
  • the step of forming the adhesive layer includes a functional group (A) that forms a covalent bond with a (meth) acryloyl group and a functional group (B) that forms a covalent bond with a hydroxyl group on at least one surface of the fiber layer.
  • Apply the composition As a coating machine that can be used in the coating process, for example, a bar coater, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater, or the like can be used.
  • a polymerization step more preferably a thermal polymerization step.
  • the thermal polymerization step for example, it is preferable to heat at 70 to 200 ° C. for 0.1 to 10 hours.
  • a method of drying by heating with hot air, infrared rays, far infrared rays or near infrared rays (heating drying method) or a method of drying in vacuum (vacuum drying method) can be applied.
  • a photopolymerization step may be employed, and the thermal polymerization step and the photopolymerization step may be performed simultaneously.
  • photopolymerization step the 450nm UV light below or 300 nm, it is preferable to irradiate with 10 mJ / cm 2 or more 8000 mJ / cm 2 or less.
  • a resin composition containing at least one selected from an acrylic monomer and a prepolymer of the acrylic monomer is applied.
  • an acrylic monomer contained in a resin composition the acrylic monomer mentioned above can be illustrated.
  • the acrylic monomer is preferably at least one selected from pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, and 1,10-decanediol diacrylate.
  • the acrylic monomer mentioned above and the copolymer by which the urethane structure and the epoxy structure were copolymerized can be illustrated.
  • the resin composition preferably contains a solvent.
  • the solvent include esters such as ethyl acetate, butyl acetate, and propyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl, dibutyl ketone, and cyclohexanone, aromatic solvents such as toluene, xylene, and hexane, and organic solvents such as hydrocarbons.
  • esters such as ethyl acetate, butyl acetate, and propyl acetate
  • ketones such as methyl ethyl ketone, methyl isobutyl, dibutyl ketone, and cyclohexanone
  • aromatic solvents such as toluene, xylene, and hexane
  • organic solvents such as hydrocarbons.
  • the resin composition further contains a polymerization initiator.
  • a polymerization initiator the polymerization initiator mentioned above can be illustrated.
  • a photoinitiator is contained in a resin composition.
  • the resin composition is applied on the surface of the adhesive layer formed on at least one surface of the fiber layer.
  • a coating machine that can be used in the coating process, for example, a bar coater, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater, or the like can be used.
  • heating step for example, a method of heating and drying with hot air, infrared rays, far infrared rays or near infrared rays (heating drying method), a method of drying in a vacuum (vacuum drying method) can be employed.
  • the resin composition After volatilizing the solvent, it is preferable to provide a step of curing the resin composition.
  • the amount of radiation to be irradiated is arbitrary as long as the photopolymerization initiator is in a range that generates radicals.
  • the lamp used for radiation irradiation include a metal halide lamp, a high pressure mercury lamp, an ultraviolet LED lamp, and an electrodeless mercury lamp.
  • photopolymerization and thermal polymerization may be performed simultaneously.
  • the resin composition is heated and cured in the range of 70 ° C. or higher and 200 ° C. or lower simultaneously with irradiation.
  • a step of obtaining a fiber layer containing fibrous cellulose having a fiber width of 1000 nm or less, and a resin composition containing urethane (meth) acrylate on at least one surface of the fiber layer The step of coating and forming an adhesive layer and the step of laminating a resin layer on one surface of the adhesive layer on the side opposite to the fiber layer may be included.
  • the step of obtaining the fiber layer in the second aspect is the same as the step described above.
  • a resin composition containing urethane (meth) acrylate is applied onto at least one surface of the fiber layer.
  • the resin composition preferably contains at least urethane (meth) acrylate, and further contains a crosslinking agent such as an isocyanate compound.
  • the resin composition may contain a polymerization initiator.
  • the resin composition may contain an arbitrary dilution solvent in order to adjust the coatability.
  • a coating machine for coating a resin composition containing urethane (meth) acrylate for example, a bar coater, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater or the like can be used. It is preferable to provide a step of curing the resin after coating. In the curing step, heating is preferably performed so that the temperature is 20 ° C. or higher and 150 ° C. or lower. The heating time is preferably from 0.1 hour to 10 hours.
  • the resin layer is laminated on one surface of the adhesive layer and on the surface opposite to the fiber layer. That is, in the step of laminating the resin layer, the fiber layer and the resin layer are bonded via the adhesive layer.
  • the fiber layer and the resin layer are laminated via the adhesive layer, and then sandwiched between the fiber layer side and the resin layer side with a plate-like object such as a metal plate and pressed.
  • the press pressure is preferably 0.1 MPa or more, more preferably 0.5 MPa or more, further preferably 1 MPa or more, and may be 3 MPa or more. Further, the press pressure is preferably 20 MPa or less, and more preferably 10 MPa or less.
  • the heating temperature is preferably 20 ° C. or higher and 250 ° C. or lower.
  • the pressing time is preferably 10 seconds or more and 10 minutes or less.
  • the manufacturing process of the laminated body of the present invention includes a first layer and a second surface disposed on one side of the first layer and on the side opposite to the adhesive layer before the step of laminating the resin layers. It is preferable to further include a step of forming a resin layer having a layer.
  • the resin layer may be formed by coating the other layer on one of the first layer and the second layer, and the resin constituting the first layer and the second layer is coextruded. May be formed.
  • the step of forming the resin layer preferably includes a step of applying an epoxy (meth) acrylate-containing composition on the second layer.
  • the second layer preferably includes at least one selected from a polycarbonate resin and an acrylic resin, and more preferably includes a polycarbonate resin. That is, the first layer of the resin layer includes an epoxy (meth) acrylate resin, the second layer includes a polycarbonate resin, and the resin layer is coated with an epoxy (meth) acrylate-containing composition on the second layer. It is preferable that it is formed. It is preferable that an epoxy (meth) acrylate containing composition contains an epoxy (meth) acrylate at least.
  • an epoxy (meth) acrylate containing composition performs the polymerization reaction of the acrylic unit of epoxy (meth) acrylate, and the polymerization reaction based on an epoxy group, it may contain a polymerization initiator. Furthermore, the epoxy (meth) acrylate-containing composition may contain an arbitrary dilution solvent in order to adjust the coating property.
  • the step of forming the resin layer is preferably a step of forming the first layer and the second layer by coextrusion.
  • the second layer preferably includes at least one selected from a polycarbonate resin and an acrylic resin, and more preferably includes a polycarbonate resin. That is, the first layer of the resin layer includes an alkyl (meth) acrylate resin, the second layer includes a polycarbonate resin, and the resin layer is formed by coextrusion of the first layer and the second layer. Is preferred.
  • a resin layer can be formed by coextrusion of an alkyl (meth) acrylate resin and a polycarbonate resin.
  • the step of forming the resin layer at least one surface of the resin layer may be subjected to surface treatment, or at least one surface of the second layer in the resin layer may be subjected to surface treatment.
  • the surface treatment for example, corona treatment, plasma discharge treatment, UV irradiation treatment, electron beam irradiation treatment, flame treatment or the like can be performed.
  • the step of forming the resin layer may include a step of forming a fine concavo-convex structure, and may include a step of forming a fine concavo-convex structure on at least one surface of the second layer in the resin layer. Examples of the process for forming the fine concavo-convex structure include a blasting process, an embossing process, an etching process, a corona process, and a plasma discharge process.
  • a laminate sheet having a fiber layer and an adhesive layer is placed in an injection mold so that the adhesive layer is exposed, and the laminate is placed in the mold.
  • a method of injecting and joining a resin that has been heated and melted is also included.
  • a preferred embodiment of the laminate of the present invention is a laminate that is transparent and has high mechanical strength and low haze. From the viewpoint of utilizing excellent optical characteristics, it is suitable for applications of light-transmitting substrates such as display elements, illumination elements, various display devices, and various solar cells. More specifically, the laminate can be used as a flexible display, a touch panel, a liquid crystal display, a plasma display, an organic EL display, a field emission display, a rear projection television display, or the like, or an LED element. Moreover, a laminated body can also be used as substrates for solar cells such as silicon-based solar cells and dye-sensitized solar cells. For use as a substrate, a barrier film, ITO, TFT or the like may be laminated.
  • the laminate of the present invention includes automobiles, railway vehicles, airplanes, houses, office buildings, factories and other window materials, glazing, interior materials, skins, bumper and other automobiles, railway vehicles, aircraft materials, and PC housings. It can also be used as a structural material for home appliance parts, packaging materials, building materials, civil engineering materials, marine products, and other industrial materials.
  • window material you may laminate
  • the laminate of the present invention is provided with an adhesive layer between the resin layer and the fiber layer. Therefore, sufficient adhesion between the resin layer and the fiber layer can be obtained without using a fiber layer having a void such as a nonwoven fabric.
  • a fiber layer having no voids or few voids has a high density and a large reinforcing effect on the laminate.
  • a high density is also advantageous in terms of transparency.
  • the resin layer can be strongly bonded to the adhesive layer provided on the surface of the fiber layer by injection molding the resin forming the resin layer. it can.
  • Example A1> (Preparation of fine fibrous cellulose suspension A) 265 g of sodium dihydrogen phosphate dihydrate and 197 g of disodium hydrogen phosphate were dissolved in 538 g of water to obtain an aqueous solution of a phosphoric acid compound (hereinafter referred to as “phosphorylation reagent”).
  • phosphorylation reagent a phosphoric acid compound
  • Softwood bleached kraft pulp (manufactured by Oji Holdings Co., Ltd., moisture 50 mass%, Canadian standard freeness (CSF) 700 ml measured according to JIS P8121) is diluted with ion-exchanged water so that the water content is 80 mass%.
  • a pulp suspension was obtained.
  • 210 g of the phosphorylating reagent was added to 500 g of this pulp suspension, and the mixture was dried with a blast dryer (Yamato Scientific Co., Ltd., DKM400) at 105 ° C. while occasionally kneading until the mass became constant.
  • heat treatment was performed for 1 hour while occasionally kneading with a blow dryer at 150 ° C. to introduce phosphate groups into the cellulose.
  • the amount of phosphate groups introduced at this time was 0.98 mmol / g.
  • Ion exchange water was added to the pulp obtained after washing and dewatering to make a 1.0 mass% pulp suspension.
  • This pulp suspension was passed through a homogenizing chamber 5 times with a high-pressure homogenizer (“Panda Plus 2000” manufactured by NiroSoavi) at an operating pressure of 1200 bar to obtain a fine fibrous cellulose suspension.
  • the treatment chamber was passed 5 times with a wet atomization apparatus ("Ultimizer” manufactured by Sugino Machine Co., Ltd.) at a pressure of 245 MPa to obtain a fine fibrous cellulose suspension A.
  • the average fiber width of the fine fibrous cellulose constituting the suspension A was 5 nm.
  • Laminate C is applied so that the adhesive layer of laminate C (size: 150 mm x 150 mm) faces the injection space side of the mold on the inner wall surface of the lower mold of the flat mold for injection molding (size: 150 mm x 150 mm).
  • a flat mold for injection molding formed by combining the lower mold with the laminated material C fixed and the upper mold is set in an injection molding tester (NEX140, manufactured by Nissei Plastic Industry Co., Ltd.) and heated to 300 ° C.
  • Molten polycarbonate resin (Panlite L-1250Y, manufactured by Teijin Ltd.) was injected at a pressure of 200 MPa and molded at a mold temperature of 200 ° C., a clamping force of 1300 kN, and a holding time of 30 seconds to obtain a laminate of Example A1. It was. The total thickness of the obtained laminate was 1500 ⁇ m, and the laminated structure was laminated in the order of polycarbonate layer (thickness 1465 ⁇ m) / adhesive layer (thickness about 2 ⁇ m) / fiber sheet B (thickness 33 ⁇ m). (See FIG. 2).
  • Example A2> (Production of laminate) Two laminated materials C were placed on the inner wall surface of the lower mold, and fixed with heat-resistant tape. In addition, two laminated materials C were placed on the inner wall surface of the upper mold and fixed with heat-resistant tape. Under the present circumstances, it arrange
  • the laminated structure is as follows: fiber sheet B (thickness 33 ⁇ m) / adhesive layer (thickness about 2 ⁇ m) / fiber sheet B (thickness 33 ⁇ m) / adhesive layer (thickness 2 ⁇ m) / polycarbonate layer (thickness 1360 ⁇ m) / The adhesive layer (thickness: about 2 ⁇ m) / fiber sheet B (thickness: 33 ⁇ m) / adhesive layer (thickness: about 2 ⁇ m) / fiber sheet B (thickness: 33 ⁇ m) was laminated in this order (see FIG. 3). ).
  • Example A4> (Production of laminate) Laminated polycarbonate resin sheet (Teijin, Panlite PC-1151, thickness 1.0 mm, size: 150 mm ⁇ 150 mm) on the inner wall of the lower mold for injection molding flat plate mold (size: 150 mm ⁇ 150 mm) Material D (size: 150 mm ⁇ 150 mm) was placed in order and fixed with heat-resistant tape.
  • a flat mold for injection molding which is a combination of a lower mold in which a polycarbonate resin sheet and a laminate D are fixed, and an upper mold is set in an injection molding tester (NEX140, manufactured by Nissei Plastic Industry Co., Ltd.), at 300 ° C.
  • a polycarbonate resin (Panlite L-1250Y, manufactured by Teijin Limited) heated and melted at a pressure of 200 MPa was molded at a mold temperature of 200 ° C., a clamping force of 1300 kN, and a holding time of 30 seconds. A laminate was obtained.
  • die was thermocompression-bonded with respect to the laminated material D with the heat and pressure of the polycarbonate inject
  • the total thickness of the obtained laminate was 2000 ⁇ m, and the laminated structure was polycarbonate layer (thickness 963 ⁇ m) / adhesive layer (thickness 2 ⁇ m) / fiber sheet B (thickness 33 ⁇ m) / adhesive layer ( The thickness was 2 ⁇ m) / polycarbonate layer (thickness 1000 ⁇ m) in this order (see FIG. 1).
  • Example A5> Polyethylene oxide (manufactured by Wako Pure Chemical Industries, Ltd .: molecular weight 1,000,000), which is a hydrophilic polymer, as an oxygen-containing organic compound is added to the fine fibrous cellulose suspension A to 20 parts by mass with respect to 100 parts by mass of the fine fibrous cellulose.
  • the concentration was adjusted so that the solid content concentration of the fine fibrous cellulose was 0.5% by mass.
  • the suspension is weighed so that the sheet basis weight is 300 g / m 2 , developed (cast) on a commercially available acrylic plate, and dried in an oven at 50 ° C. to obtain a fiber sheet E (fiber layer). It was.
  • a laminated material F was obtained in the same manner as the laminated material C except that the fiber sheet B of the laminated material C was changed to the fiber sheet E.
  • One laminated material F was placed on the inner wall surface of the lower mold and fixed with heat-resistant tape. Further, one laminated material F was placed on the inner wall surface of the upper mold and fixed with heat-resistant tape. Under the present circumstances, it arrange
  • a laminate of Example A5 in which a total of two laminates F were laminated was obtained. The total thickness of the obtained laminate was 1760 ⁇ m.
  • the laminated structure is as follows: fiber sheet B (thickness: 198 ⁇ m) / adhesive layer (thickness: about 2 ⁇ m) / polycarbonate layer (thickness: 1360 ⁇ m) / adhesive layer (thickness: about 2 ⁇ m) / fiber sheet B (thickness: 198 ⁇ m) (See FIG. 5).
  • Example A6> (Production of laminated material H) On one sheet of polycarbonate film (Lumirror S10 manufactured by Toray Industries Inc.), one sheet of laminated material D is laminated, and further, the polycarbonate film and the laminated material D are alternately laminated, for a total of six polycarbonate films, A laminated material H in which a total of 6 laminated materials D were alternately laminated was obtained. (Production of laminate) One laminated material H was placed on the inner wall surface of the lower mold and fixed with heat-resistant tape. Further, one laminated material H was placed on the inner wall surface of the upper mold and fixed with heat-resistant tape.
  • the laminated structure is polycarbonate layer (thickness 50 ⁇ m) / adhesive layer (thickness about 2 ⁇ m) / fiber sheet B (thickness 33 ⁇ m) / adhesive layer (thickness about 2 ⁇ m) / polycarbonate layer (thickness 50 ⁇ m) / Adhesive layer (thickness: about 2 ⁇ m) / fiber sheet B (thickness: 33 ⁇ m) / adhesive layer (thickness: about 2 ⁇ m) / polycarbonate layer (thickness: 50 ⁇ m) / adhesive layer (thickness: about 2 ⁇ m) / fiber sheet B (Thickness 33 ⁇ m) / adhesive layer (thickness about 2 ⁇ m) / polycarbonate layer (thickness 50 ⁇ m) / adhesive layer (thickness about 2 ⁇ m) / fiber sheet B (thickness 33 ⁇ m) / adhesive layer (thickness about 2 ⁇ m) / polycarbonate layer (thickness 50 ⁇ m)
  • Example A7> Polyethylene oxide (manufactured by Wako Pure Chemical Industries, Ltd .: molecular weight 1,000,000), which is a hydrophilic polymer, as an oxygen-containing organic compound is added to the fine fibrous cellulose suspension A to 20 parts by mass with respect to 100 parts by mass of the fine fibrous cellulose. was added as follows. The concentration was adjusted so that the solid content concentration of the fine fibrous cellulose was 0.5% by mass. The suspension is weighed so that the sheet basis weight is 660 g / m 2 , developed (cast) on a commercially available acrylic plate, and dried in an oven at 50 ° C. to obtain a fiber sheet I (fiber layer). It was.
  • a molten polycarbonate resin (Panlite L-1250Y, manufactured by Teijin Limited) was injected at a pressure of 200 MPa and molded at a mold temperature of 200 ° C., a clamping force of 1300 kN, and a holding time of 30 seconds to obtain an intermediate laminate. Subsequently, a polycarbonate layer was laminated by injection molding similar to the above on the other adhesive layer of the laminated material K constituting the intermediate laminated body to obtain a laminated body of Example A7.
  • the total thickness of the obtained laminate L is 1760 ⁇ m, and the laminated structure is polycarbonate layer (thickness 680 ⁇ m) / adhesive layer (thickness about 2 ⁇ m) / fiber sheet I (thickness 396 ⁇ m) / adhesive
  • the layer was laminated in the order of layer (thickness: about 2 ⁇ m) / polycarbonate layer (thickness: 680 ⁇ m) (see FIG. 7).
  • ⁇ Comparative Example A2> (Production of laminate) Except having changed the laminated material C into the fiber sheet B, it carried out similarly to Example A1, and obtained the laminated body of comparative example A2.
  • the total thickness of the obtained laminate was 1500 ⁇ m, and the laminated structure was a two-layer structure in which a polycarbonate layer (thickness 1467 ⁇ m) / fiber sheet B (thickness 33 ⁇ m) were laminated in this order.
  • ⁇ Comparative Example A3> (Preparation of cellulose suspension K) Ion-exchanged water was added to softwood bleached kraft pulp (manufactured by Oji Holdings Co., Ltd., moisture 50 mass%, Canadian standard freeness (CSF) 700 ml measured according to JIS P8121), and 1.0 mass% Made into a pulp suspension. This pulp suspension was treated with a laboratory refiner (manufactured by Aikawa Tekko Co., Ltd.) at 10,000 rpm for 5 hours to obtain a cellulose suspension K. The average fiber width of this cellulose was 3 ⁇ m.
  • the suspension K was weighed so that the sheet basis weight was 50 g / m 2 , developed on a commercially available acrylic plate, and dried in an oven at 50 ° C. to obtain a fiber sheet. Furthermore, on one surface of the fiber sheet, 100 parts by weight of urethane acrylic resin (manufactured by Taisei Fine Chemical Co., Ltd., Acryt 8UA-347A) and 9.7 parts by weight of an isocyanurate compound (manufactured by Asahi Kasei Chemicals Co., Ltd., TPA-100) Were coated with a bar coater and dried to obtain a fiber sheet L provided with an adhesive layer on the fiber sheet. The dry coating amount of this adhesive layer was 1.5 g / m 2 .
  • the average fiber width of the cellulose fibers constituting the fiber layer of the laminate is obtained by cutting out the cross section of the laminate with an ultramicrotome UC-7 (manufactured by JEOL) and observing the fiber layer with an electron microscope image It is the value measured by.
  • “width” means the distance from one end to the other end of the cellulose fiber, which is the shorter one.
  • Thickness measurement method The thickness of one layer of the fiber layer constituting the laminate was measured by observing the cross section of the laminate with an ultramicrotome UC-7 (manufactured by JEOL) and observing the cross section with an electron microscope image. Value.
  • the basis weight of one layer of the fiber layer constituting the laminate is determined by cutting only the fiber layer of the laminate with an ultramicrotome UC-7 (manufactured by JEOL), in accordance with JIS standard P8124: 2011, Calculated. Based on JIS standard P8118: 2014, the density of one layer of the fiber layer which comprises a laminated body was computed from the basic weight computed here and the thickness measured by the said method.
  • the total light transmittance of one layer of the fiber layer constituting the laminate is cut by ultramicrotome UC-7 (manufactured by JEOL) so that only the fiber layer of the laminate remains, and JIS The measurement was performed using a haze meter (“HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with the standard K7361: 1997.
  • HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd.
  • ⁇ Measurement method of haze The haze of one layer of the fiber layer constituting the laminate is cut by ultramicrotome UC-7 (manufactured by JEOL) so that only the fiber layer of the laminate remains, and conforms to JIS standard K7136: 2000 The measurement was performed using a haze meter (“HM-150” manufactured by Murakami Color Research Laboratory Co., Ltd.).
  • ⁇ Adhesion> The obtained laminate was cut to obtain five samples each having a width of 10 mm and a length of 50 mm from each laminate.
  • an Olfa cutter knife was inserted into the adhesive layer between the fiber layer and the resin layer, and the degree of peeling between the fiber layer and the resin layer was determined according to the following criteria. It was evaluated with.
  • Double-circle The fiber layer and the resin layer were not able to be peeled off at all for all the five samples.
  • ⁇ Four of the five samples did not peel at all, and only one of them peeled about 1 mm. This level of delamination is not a problem in practice.
  • X In all the five samples, the fiber layer and the resin layer were completely separated.
  • Total light transmittance> The total light transmittance of the obtained laminate was measured using a haze meter ("HM-150" manufactured by Murakami Color Research Laboratory Co., Ltd.) in accordance with JIS standard K7361: 1997.
  • HM-150 manufactured by Murakami Color Research Laboratory Co., Ltd.
  • JIS standard K7136 2000.
  • the linear expansion coefficient of the obtained laminate was measured in a temperature range of 100 to 150 ° C. using a thermal analyzer (TMA7100 manufactured by Hitachi, Ltd.) in accordance with JIS standard K7197: 2012.
  • Example A1 provided with a fiber layer, an adhesive layer, and a resin layer is excellent in adhesion, and can achieve both high transparency and a low linear expansion coefficient.
  • Example A2 in which a plurality of fiber layers are laminated, a high elastic modulus and a low linear expansion coefficient are obtained while maintaining adhesion and transparency.
  • Example A3 stronger adhesiveness is obtained by using an adhesive in which silica is combined with acrylic resin.
  • Example A4 the resin was provided on both sides of the fiber layer with the adhesive layer interposed therebetween, so that the adhesiveness was good, the coefficient of linear expansion was low, and a thicker laminate was obtained.
  • Comparative Example A1 having only the resin layer had a very high linear expansion coefficient, although the transparency was high.
  • Comparative Example A2 without an adhesive layer the adhesion between the fiber layer and the resin layer was insufficient, and the linear expansion coefficient was higher than that of the Examples.
  • Comparative Example A3 using a cellulose suspension K having a fiber width of 1000 nm or more had low transparency and a significantly high linear expansion coefficient.
  • the ratio (presence ratio) of the thickness of the fiber layer in the surface vicinity of each laminated body is seen, the higher elasticity rate and the lower linear expansion coefficient are obtained, so that the ratio is high in an Example.
  • the amount of phosphate group introduced was measured by diluting cellulose with ion-exchanged water so that the content was 0.2% by mass, and then treating with ion-exchange resin and titrating with alkali.
  • ion-exchange resin 1/10 by volume of a strongly acidic ion exchange resin (manufactured by Organo Corporation, Amberjet 1024: conditioned) is added to the 0.2 mass% cellulose-containing slurry, followed by shaking treatment for 1 hour. went. Thereafter, the mixture was poured onto a mesh having an opening of 90 ⁇ m to separate the resin and the slurry.
  • a metal frame for damming (a metal frame having an inner dimension of 180 mm ⁇ 180 mm) was disposed on the acrylic plate so as to have a predetermined basis weight.
  • a fine fibrous cellulose-containing sheet (fiber layer) was obtained.
  • the thickness of the fine fibrous cellulose-containing sheet measured with a stylus thickness meter (Milltron 1202D, manufactured by Marl) is 29.8 ⁇ m, and the density calculated by dividing the basis weight by the thickness is 1.51 g / cm 3. Met.
  • [Lamination of adhesive layer] 100 parts by mass of an acrylic resin grafted with an acryloyl group (manufactured by Taisei Fine Chemical Co., Ltd., Acryt 8KX-012C), 38 parts by mass of a polyisocyanate compound (manufactured by Asahi Kasei Chemicals Co., Ltd., TPA-100), a radical polymerization initiator (manufactured by BASF, Irgacure 184) 2 parts by mass were mixed to obtain an adhesive composition. Next, the adhesive composition was applied to one surface of the fine fibrous cellulose-containing sheet with a bar coater, and then heated and cured at 100 ° C. for 1 hour to laminate an adhesive layer.
  • a polyisocyanate compound manufactured by Asahi Kasei Chemicals Co., Ltd., TPA-100
  • a radical polymerization initiator manufactured by BASF, Irgacure 184
  • the adhesive layer was laminated
  • the thickness of the adhesive layer was 5 ⁇ m on one side.
  • UV conveyor device (Eye Graphics Co., Ltd., ECS-4011GX) was irradiated with ultraviolet rays at 500 mJ / cm 2 was used to cure the resin composition to form a resin layer. Further, a resin layer was formed on the other surface of the adhesive layer laminated sheet (A) by the same procedure. The thickness of the resin layer was 10 ⁇ m on one side. By the above procedure, a laminate in which resin layers were laminated on both surfaces of the adhesive layer laminated sheet (A) was obtained.
  • Example B2> [Lamination of resin layer] 100 parts by mass of an acrylic resin (made by Arakawa Chemical Industry Co., Ltd., Beam Set 710) containing pentaerythritol tetraacrylate as a main component, 100 parts by mass of methyl ethyl ketone, and 5 parts by mass of a radical polymerization initiator (manufactured by BASF, Irgacure 184) A resin composition was obtained. Next, the resin composition was applied to one surface of the adhesive layer laminated sheet (A) obtained in Example B1 with a bar coater, and then heated at 100 ° C. for 5 minutes to volatilize methyl ethyl ketone.
  • an acrylic resin made by Arakawa Chemical Industry Co., Ltd., Beam Set 710
  • pentaerythritol tetraacrylate 100 parts by mass of methyl ethyl ketone
  • a radical polymerization initiator manufactured by BASF, Irgacure 184
  • UV conveyor device (Eye Graphics Co., Ltd., ECS-4011GX) was irradiated with ultraviolet rays at 500 mJ / cm 2 was used to cure the resin composition to form a resin layer. Further, a resin layer was formed on the other surface of the adhesive layer laminated sheet (A) by the same procedure. The thickness of the resin layer was 10 ⁇ m on one side. By the above procedure, a laminate in which resin layers were laminated on both surfaces of the adhesive layer laminated sheet (A) was obtained.
  • Example B3> [Lamination of resin layer] 100 parts by mass of an acrylic resin (made by Arakawa Chemical Industry Co., Ltd., Beam Set 710) having 100% of dipentaerythritol hexaacrylate as a main component, 100 parts by mass of methyl ethyl ketone, and 5 parts by mass of a radical polymerization initiator (manufactured by BASF, Irgacure 184) are mixed. Thus, a resin composition was obtained. Next, the resin composition was applied to one surface of the adhesive layer laminated sheet (A) obtained in Example B1 with a bar coater, and then heated at 100 ° C. for 5 minutes to volatilize methyl ethyl ketone.
  • UV conveyor device (Eye Graphics Co., Ltd., ECS-4011GX) was irradiated with ultraviolet rays at 500 mJ / cm 2 was used to cure the resin composition to form a resin layer. Further, a resin layer was formed on the other surface of the adhesive layer laminated sheet (A) by the same procedure. The thickness of the resin layer was 10 ⁇ m on one side. By the above procedure, a laminate in which resin layers were laminated on both surfaces of the adhesive layer laminated sheet (A) was obtained.
  • Example B4 [Creation of glass cell for resin layer molding]
  • Two adhesive layer laminated sheets (A) obtained in Example B1 were cut into dimensions of 120 mm in length and 55 mm in width. Next, a gap of 95 mm in length, 40 mm in width, and 2 mm in thickness is provided in the center of silicon rubber having a length of 125 mm, a width of 60 mm, and a thickness of 2 mm.
  • the adhesive layer laminated sheet (A) was inserted along the inner periphery of the silicon rubber.
  • FIG. 10 is a diagram of the resin layer molding glass cell 200 produced as described above, as viewed from above, and is a schematic diagram of the resin layer molding glass cell with the upper glass plate removed. As shown in FIG. 10, in the resin layer-forming glass cell 200, an adhesive layer laminated sheet (A) 130, silicon rubber 120, and a glass plate 110 are disposed around the inner space.
  • silicon rubber is inserted and sealed in the opening, and the resin composition is cured by irradiating UV rays of 300 mJ / cm 2 20 times using a UV conveyor device (ECS-4011GX, manufactured by Eye Graphics Co., Ltd.). I let you. Thereafter, the glass plate and the silicon rubber were removed, and a laminate in which fine fibrous cellulose-containing sheets (fiber layers) were laminated on both surfaces of a 1920 ⁇ m thick resin layer via an adhesive layer was obtained.
  • a UV conveyor device ECS-4011GX, manufactured by Eye Graphics Co., Ltd.
  • Example B1 ⁇ Comparative Example B1>
  • the adhesive layer was not laminated.
  • Other procedures were the same as in Example B1, and a laminate was obtained.
  • Example B2 ⁇ Comparative Example B2>
  • the adhesive layer was not laminated.
  • Other procedures were the same as in Example B2, and a laminate was obtained.
  • Example B3 ⁇ Comparative Example B3>
  • the adhesive layer was not laminated.
  • Other procedures were the same as in Example B3 to obtain a laminate.
  • Example B5> [Lamination of adhesive layer]
  • a polyester resin UV coat anchor agent (Arakawa Chemical Industry Co., Ltd., Aracoat AP2510) 76 parts by mass, a curing agent (Arakawa Chemical Industry Co., Ltd., Alacoat CL2502) 10 parts by mass and methyl ethyl ketone 14 parts by mass were mixed to prepare an adhesive composition. Obtained.
  • the adhesive composition was applied to one surface of the fine fibrous cellulose-containing sheet (fiber layer) obtained in Example B1, using a bar coater, and then cured by heating at 100 ° C. for 3 minutes to bond.
  • the agent layer was laminated.
  • the adhesive layer was laminated
  • Example B6> A resin layer was laminated on the adhesive layer laminated sheet (B) obtained in Example B5 by the same procedure as in Example B2, to obtain a laminate.
  • Example B7 A resin layer was laminated on the adhesive layer laminated sheet (B) obtained in Example B5 in the same procedure as in Example B3 to obtain a laminate.
  • a silsesquioxane resin Arakawa Chemical Industries, Composeran SQ107
  • HBSQ202 a curing agent
  • UV conveyor device (Eye Graphics Co., Ltd., ECS-4011GX) by irradiating ultraviolet rays of 300 mJ / cm 2 was used to laminate the adhesive layer by curing the adhesive composition. Furthermore, the adhesive layer was laminated
  • an adhesive layer laminated sheet (C) in which an adhesive layer was laminated on both surfaces of the fine fibrous cellulose-containing sheet was obtained.
  • Example B9 A resin layer was laminated on the adhesive layer laminated sheet (B) obtained in Example B8 in the same procedure as in Example B2 to obtain a laminate.
  • Example B10> A resin layer was laminated on the adhesive layer laminated sheet (B) obtained in Example B8 in the same procedure as in Example B3 to obtain a laminate.
  • Total light transmittance Based on JIS K 7361, the total light transmittance was measured using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-150).
  • the laminate was placed in a constant temperature and humidity chamber (KCL-2000, manufactured by Tokyo Science Instruments Co., Ltd.) at a temperature of 85 ° C. and a relative humidity of 85%, and allowed to stand for 240 hours. Thereafter, the laminate was placed in an environment having a temperature of 23 ° C. and a relative humidity of 50% for 1 hour. After that, in accordance with JIS K 5400, 100 pieces of 1 mm 2 crosscuts were put on the surface of the laminated body on the fiber layer side, cellophane tape (manufactured by Nichiban Co., Ltd.) was applied thereon, and a load of 1.5 kg / cm 2 After pressing, it was peeled away in the 90 ° direction. The adhesiveness between the resin layer and the fiber layer (fine fibrous cellulose-containing sheet) was evaluated based on the number of cells separated.
  • KCL-2000 constant temperature and humidity chamber
  • Examples B5 to B7 using a polyester resin as the adhesive layer and Examples B8 to 10 using a silsesquioxane resin the initial adhesion was relatively good, but the adhesion after the acceleration test was As a result, there is a concern about practical problems in applications where use is expected under severe conditions.
  • Comparative Example B1 had better adhesion than Examples B6 and B7, when compared with the same resin layer, the initial adhesion was better when the adhesive layer was present.
  • an inorganic film laminate can be produced by the following procedure.
  • An aluminum oxide film is formed on the stacked body using an atomic layer deposition apparatus (PUNSON, SUNALE R-100B).
  • TMA trimethylaluminum
  • H 2 O the oxidation of TMA.
  • the chamber temperature is set to 150 ° C.
  • the TMA pulse time is 0.1 seconds
  • the purge time is 4 seconds
  • the H 2 O pulse time is 0.1 seconds
  • the purge time is 4 seconds.
  • Example B6 (Production Example 2 of Inorganic Film Laminate)> Using the laminate obtained in Examples B1 to B4, an inorganic film laminate can be produced by the following procedure. A silicon oxynitride film is formed on the stacked body using a plasma CVD apparatus (ICP-CVD roll-to-roll apparatus manufactured by Cellvac). The laminate is bonded to the upper surface of the carrier film (PET film) with a double-sided tape and placed in a vacuum chamber. The temperature in the vacuum chamber is set to 50 ° C., and the inflow gas is silane, ammonia, oxygen, and nitrogen.
  • a plasma CVD apparatus ICP-CVD roll-to-roll apparatus manufactured by Cellvac
  • a plasma discharge is generated and film formation is performed for 45 minutes to obtain an inorganic film laminate in which a silicon oxynitride film having a thickness of 500 nm is laminated on one side of the laminate. Furthermore, an inorganic film laminated body in which a silicon oxynitride film having a thickness of 500 nm is laminated on both surfaces of the laminated body can also be obtained by performing film formation on the opposite surface in the same procedure.
  • the obtained chemical solution-impregnated pulp was dried and heat-treated for 200 seconds with a hot air dryer at 165 ° C. to introduce phosphate groups into cellulose in the pulp.
  • the amount of phosphate groups introduced at this time was 0.98 mmol / g.
  • the amount of phosphate group introduced was measured by diluting cellulose with ion-exchanged water so that the content was 0.2% by mass, and then treating with ion-exchange resin and titrating with alkali.
  • ion-exchange resin 1/10 by volume of a strongly acidic ion exchange resin (manufactured by Organo Corporation, Amberjet 1024: conditioned) is added to the 0.2 mass% cellulose-containing slurry, followed by shaking treatment for 1 hour. went. Thereafter, the mixture was poured onto a mesh having an opening of 90 ⁇ m to separate the resin and the slurry.
  • a metal frame for damming (a metal frame having an inner dimension of 180 mm ⁇ 180 mm) was disposed on the acrylic plate so as to have a predetermined basis weight.
  • [Lamination of adhesive layer] 100 parts by mass of urethane acrylate having a urethane / acrylic ratio of 2/8 (manufactured by Taisei Fine Chemical Co., Ltd., Acryt 8UA-347A) and 9.7 parts by mass of isocyanurate compound (manufactured by Asahi Kasei Chemicals Co., Ltd., Duranate TPA-100) are mixed. Resin composition A was obtained. Next, on one surface of the fiber layer, the resin composition A was applied with a bar coater and dried with a constant temperature dryer at 100 ° C. for 1 hour. By the above procedure, a laminated sheet A in which an adhesive layer was laminated on one surface of the fiber layer was obtained.
  • the resin composition B was cured by irradiating with UV light of 500 mJ / cm 2 using a UV conveyor device (ECS-4011GX, manufactured by Eye Graphics Co., Ltd.).
  • a resin layer having an epoxy urethane acrylate resin layer was formed on the polycarbonate film.
  • Example C2 when the laminated sheet A and the resin layer were laminated, the press pressure was changed from 1 MPa to 5 MPa. Other procedures were the same as in Example C1, and a laminate in which the fiber layer was laminated with the resin layer via the adhesive layer was obtained.
  • Example C3 When laminating the adhesive layer of Example C1, instead of urethane acrylate having a urethane / acryl ratio of 2/8, urethane acrylate having a urethane / acryl ratio of 4/6 (manufactured by Taisei Fine Chemical Co., Ltd., ACRYT 8UA-540) )It was used. Other procedures were the same as in Example C1, and a laminate in which the fiber layer was laminated with the resin layer via the adhesive layer was obtained.
  • Example C4 In Example C3, when the laminated sheet A and the resin layer were laminated, the press pressure was changed from 1 MPa to 5 MPa. Other procedures were the same as in Example C1, and a laminate in which the fiber layer was laminated with the resin layer via the adhesive layer was obtained.
  • Example C5 In Example C2, instead of a resin layer having an epoxy urethane acrylate resin layer on a polycarbonate film, a coextruded film (Iupilon MR-DF02U: thickness 300 ⁇ m) formed by coextruding a polycarbonate resin and an acrylic resin is used. did. When the laminated sheet A and the resin layer were laminated, the coextruded film was laminated so that the acrylic resin side surface of the coextruded film was in contact with the adhesive layer side surface of the laminated sheet A. Other procedures were the same as in Example C2, and a laminate in which the fiber layer was laminated with the resin layer via the adhesive layer was obtained.
  • a coextruded film Iupilon MR-DF02U: thickness 300 ⁇ m
  • Example C1 ⁇ Comparative Example C1>
  • the adhesive layer was not laminated. Further, the resin composition B was not applied in the formation of the resin layer. Other procedures were the same as in Example C1, and a laminate in which the fiber layer was laminated with the resin layer without an adhesive layer was obtained.
  • Example C6 ⁇ Reference Example C6>
  • the resin composition A was composed of 100 parts by mass of an acrylic resin in which an acryloyl group was graft-polymerized (Acryt 8KX-012C, manufactured by Taisei Fine Chemical Co., Ltd.) and an isocyanate compound (Asahi Kasei Chemicals).
  • BASF Irgacure 184
  • the thickness of the laminated body was measured with a stylus type thickness meter (manufactured by Marl, Millitron 1202D).
  • the thickness of the laminated sheet A Prior to laminating the laminated sheet A and the resin layer, the thickness of the laminated sheet A is measured with a stylus thickness meter (Milltron 1202D, manufactured by Marl), and the thickness of the fiber layer is subtracted from the thickness of the laminated sheet A. Then, the thickness of the adhesive layer in the laminate was calculated.
  • a stylus thickness meter manufactured by Marl
  • Total light transmittance of laminate Based on JIS K 7361, the total light transmittance of the laminate was evaluated using a haze meter (manufactured by Murakami Color Research Laboratory Co., Ltd., HM-150).
  • Example C7 (Production Example 1 of multilayer laminate)> The multilayer laminated body by which the resin layer was laminated
  • Two laminates obtained in any of Examples C1 to C5 are prepared, and water is applied to each fiber layer with a bar coater.
  • the fiber layer surfaces of the two laminates are bonded together, and a rubber roller is pressed from the resin layer side of one laminate and pressed.
  • the laminated body bonded together is dried at 100 ° C. for 1 hour with a constant temperature dryer, whereby a multilayer laminated body in which the resin layers are laminated on both surfaces of the fiber layer is obtained.
  • Example C8 (Production Example 2 of Multilayer Laminate)> Two laminates obtained in any of Examples C1 to C5 are prepared, and a UV curable acrylic adhesive (Z-587, manufactured by Aika Kogyo Co., Ltd.) is applied to each fiber layer with a bar coater. . Next, the fiber layer surfaces of the two laminates are bonded together, and a rubber roller is pressed from the resin layer side of one laminate and pressed. Further, UV light of 500 mJ / cm 2 was irradiated three times from the resin layer side of the laminated body using a UV conveyor device (ECS-4011GX, manufactured by Eye Graphics Co., Ltd.) to give a UV curable acrylic adhesive. By curing, a multilayer laminate in which resin layers are laminated on both sides of the fiber layer is obtained.
  • a UV curable acrylic adhesive Z-587, manufactured by Aika Kogyo Co., Ltd.
  • Example C9 (Production Example 3 of Multilayer Laminate)> Using the laminate obtained in any of Examples C1 to C5, a multilayer laminate in which resin layers are laminated on both sides by the following procedure is obtained. First, 100 parts by mass of an acrylic resin grafted with an acryloyl group (manufactured by Taisei Fine Chemical Co., Ltd., Acryt 8KX-012C) and 38 parts by mass of a polyisocyanate compound (manufactured by Asahi Kasei Chemicals Co., Ltd., TPA-100) are mixed to obtain a resin composition. obtain. Next, the resin composition is applied to the cellulose fiber-containing layer of the laminate with a bar coater. Furthermore, the multilayer laminated body by which the resin layer was laminated
  • an acrylic resin grafted with an acryloyl group manufactured by Taisei Fine Chemical Co., Ltd.,
  • Example C10 (Production Example 1 of inorganic film laminate)> With respect to the laminate obtained in any of Examples C1 to 5 or the multilayer laminate obtained in any of Examples C6 to 8, using an atomic layer deposition apparatus (“SUNALE R-100B” manufactured by Picosun), An aluminum oxide film is formed.
  • As an aluminum raw material trimethylaluminum (TMA) and H 2 O are used for the oxidation of TMA.
  • the chamber temperature is set to 150 ° C.
  • the TMA pulse time is 0.1 seconds
  • the purge time is 4 seconds
  • the H 2 O pulse time is 0.1 seconds
  • the purge time is 4 seconds.
  • Example C11 Plasma CVD apparatus ("ICP-CVD roll-to-roll apparatus” manufactured by Celbach) for the laminate obtained in any of Examples C1 to 5 or the multilayer laminate obtained in any of Examples C6 to 8 )
  • a laminate or a multilayer laminate is bonded to the upper surface of a carrier film (PET film) with a double-sided tape and placed in a vacuum chamber.
  • the temperature in the vacuum chamber is set to 50 ° C.
  • the inflow gas is silane, ammonia, oxygen, and nitrogen.
  • a plasma discharge is generated and film formation is performed for 45 minutes to obtain a laminate or an inorganic film laminate in which a silicon oxynitride film having a thickness of 500 nm is laminated on one surface of a multilayer laminate. Furthermore, by forming a film on the opposite surface in the same procedure, it is also possible to obtain a laminated body or an inorganic film laminated body in which a silicon oxynitride film having a film thickness of 500 nm is laminated on both surfaces of the multilayer laminated body. .

Landscapes

  • Laminated Bodies (AREA)

Abstract

La présente invention concerne l'obtention d'un corps stratifié offrant d'excellentes propriétés d'adhérence intercouche. À cet effet, l'invention propose un corps stratifié qui comprend une couche de fibres formée à partir de fibres de cellulose ayant des largeurs de fibre inférieures ou égales à 1000 nm, une couche de résine, et une couche adhésive disposée entre la couche de fibres et la couche de résine.
PCT/JP2016/077088 2015-09-18 2016-09-14 Corps stratifié WO2017047632A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US15/760,898 US11065850B2 (en) 2015-09-18 2016-09-14 Laminate
EP16846503.7A EP3351374B1 (fr) 2015-09-18 2016-09-14 Stratifié
KR1020187010239A KR102196197B1 (ko) 2015-09-18 2016-09-14 적층체
CN201680054470.3A CN108136714B (zh) 2015-09-18 2016-09-14 积层体

Applications Claiming Priority (8)

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JP2015-185305 2015-09-18
JP2015185305 2015-09-18
JP2015223845A JP6641912B2 (ja) 2015-11-16 2015-11-16 積層体及び積層体の製造方法
JP2015-223845 2015-11-16
JP2016008854A JP6620567B2 (ja) 2016-01-20 2016-01-20 積層体及び積層体の製造方法
JP2016-008854 2016-01-20
JP2016-038360 2016-02-29
JP2016038360A JP6701807B2 (ja) 2015-09-18 2016-02-29 積層体

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CN109795176A (zh) * 2017-11-16 2019-05-24 上纬企业股份有限公司 积层体及成形体
WO2020230513A1 (fr) * 2019-05-10 2020-11-19 王子ホールディングス株式会社 Substrat de formation de motif
WO2021079850A1 (fr) * 2019-10-21 2021-04-29 王子ホールディングス株式会社 Feuille stratifiée et stratifié
JP2021066171A (ja) * 2019-10-21 2021-04-30 王子ホールディングス株式会社 積層シート及び積層体
WO2021131380A1 (fr) * 2019-12-24 2021-07-01 王子ホールディングス株式会社 Feuille et procédé de production d'une feuille
WO2022145389A1 (fr) * 2020-12-28 2022-07-07 王子ホールディングス株式会社 Stratifié et procédé de fabrication de stratifié

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JP2014065837A (ja) * 2012-09-26 2014-04-17 Toppan Printing Co Ltd ガスバリア層形成用塗工液の製造方法、ガスバリア性積層体及び包装材料
JP2015146244A (ja) * 2014-02-03 2015-08-13 凸版印刷株式会社 透明導電性フィルムおよびこの製造方法
JP2015146243A (ja) * 2014-02-03 2015-08-13 凸版印刷株式会社 透明導電性フィルムおよびこの製造方法

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JP2014065837A (ja) * 2012-09-26 2014-04-17 Toppan Printing Co Ltd ガスバリア層形成用塗工液の製造方法、ガスバリア性積層体及び包装材料
JP2015146244A (ja) * 2014-02-03 2015-08-13 凸版印刷株式会社 透明導電性フィルムおよびこの製造方法
JP2015146243A (ja) * 2014-02-03 2015-08-13 凸版印刷株式会社 透明導電性フィルムおよびこの製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109795176A (zh) * 2017-11-16 2019-05-24 上纬企业股份有限公司 积层体及成形体
WO2020230513A1 (fr) * 2019-05-10 2020-11-19 王子ホールディングス株式会社 Substrat de formation de motif
JP2020185680A (ja) * 2019-05-10 2020-11-19 王子ホールディングス株式会社 パターン形成用基材
WO2021079850A1 (fr) * 2019-10-21 2021-04-29 王子ホールディングス株式会社 Feuille stratifiée et stratifié
JP2021066171A (ja) * 2019-10-21 2021-04-30 王子ホールディングス株式会社 積層シート及び積層体
WO2021131380A1 (fr) * 2019-12-24 2021-07-01 王子ホールディングス株式会社 Feuille et procédé de production d'une feuille
WO2022145389A1 (fr) * 2020-12-28 2022-07-07 王子ホールディングス株式会社 Stratifié et procédé de fabrication de stratifié

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