WO2023054528A1 - 積層体 - Google Patents

積層体 Download PDF

Info

Publication number
WO2023054528A1
WO2023054528A1 PCT/JP2022/036296 JP2022036296W WO2023054528A1 WO 2023054528 A1 WO2023054528 A1 WO 2023054528A1 JP 2022036296 W JP2022036296 W JP 2022036296W WO 2023054528 A1 WO2023054528 A1 WO 2023054528A1
Authority
WO
WIPO (PCT)
Prior art keywords
resin layer
cured resin
layer
bis
laminate
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2022/036296
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
博貴 木下
智史 永縄
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lintec Corp
Original Assignee
Lintec Corp
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
Publication date
Application filed by Lintec Corp filed Critical Lintec Corp
Priority to JP2023551809A priority Critical patent/JPWO2023054528A1/ja
Publication of WO2023054528A1 publication Critical patent/WO2023054528A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides

Definitions

  • the present invention relates to laminates.
  • a transparent plastic film as a substrate for constituent members is being studied instead of a conventional rigid substrate such as glass.
  • plastic films are generally inferior in heat resistance to glass.
  • a transparent plastic film may be used as a substrate for forming a transparent conductive layer of the electronic device.
  • the substrate is required to have excellent optical properties at the level of an optical film, and then to have excellent heat resistance to high-temperature heat treatment related to the conductive layer and the like in the step of forming the transparent conductive layer.
  • Patent Literature 1 discloses, for example, a base layer made of a cured product of a curable resin composition as a substrate of a gas barrier laminate provided together with a transparent conductive layer or the like on the display surface side of a display device or the like.
  • the underlayer in Patent Document 1 is a curable resin composition containing a polymer component (A) such as a polyimide resin and a curable monomer (B) such as a (meth)acrylic acid derivative having a polymerizable unsaturated bond. It is a layer (cured resin layer) made of a cured product of.
  • A polymer component
  • B curable monomer
  • cured resin layer made of a cured product of.
  • an object of the present invention is to provide a laminate having a low haze value and excellent heat resistance.
  • the present inventors have made intensive studies to solve the above problems, and as a result, in a laminate containing a cured resin layer (A), a resin layer and a cured resin layer (B) in this order, the cured resin layer of the resin layer ( By providing a specific cured resin layer (B) on the side opposite to the side of A), the precipitation of the oligomer component of the resin layer is suppressed, thereby solving the above problems. completed the invention. That is, the present invention provides the following [1] to [11].
  • a laminate comprising a cured resin layer (A), a resin layer and a cured resin layer (B) in this order, wherein the cured resin layer (A) comprises a polymer component (M) containing a polyimide resin and a cured It is a layer made of a cured product of the curable resin composition 1 containing a curable monomer (P), and the curable resin layer (B) contains the polymer component (N) and/or the curable monomer (Q ), which is a layer composed of a cured product of the curable resin composition 2 containing.
  • the cured resin layer (B) further contains a filler component.
  • the resin layer is a polyester film or a polyolefin film.
  • FIG. 4 is a cross-sectional view showing another example of the laminate of the present invention.
  • the definition of being preferred can be arbitrarily selected, and it can be said that a combination of the definitions of being preferred is more preferred.
  • the description "XX to YY” means “XX or more and YY or less”.
  • the lower and upper limits described stepwise can be independently combined. For example, from the statement “preferably 10 to 90, more preferably 30 to 60", combining "preferred lower limit (10)” and “more preferred upper limit (60)” to "10 to 60” can also In this specification, for example, "(meth)acrylic acid” indicates both “acrylic acid” and “methacrylic acid”, and the same applies to other similar terms.
  • the laminate of the present invention is a laminate comprising a cured resin layer (A), a resin layer and a cured resin layer (B) in this order, wherein the cured resin layer (A) is a polymer component (M ) and a cured product of the curable resin composition 1 containing a curable monomer (P), the cured resin layer (B) is a polymer component (N) and / or a curable monomer It is characterized by being a layer made of a cured product of the curable resin composition 2 containing the body (Q).
  • the resin layer in a laminate including a cured resin layer (A), a resin layer and a cured resin layer (B) in this order, the resin layer (hereinafter sometimes referred to as "process film 1") has a cured resin layer ( A) A cured resin layer (B) made of a cured product of a curable resin composition 2 containing a polymer component (N) and/or a curable monomer (Q) on the surface opposite to the surface on the side of A) (Hereinafter, sometimes referred to as "process film 2".)
  • process film 2 By laminating, it is possible to suppress precipitation of oligomer components in the resin layer due to long-term heat treatment at high temperatures.
  • an increase in the haze value of the laminated body can be suppressed, and deterioration in defect inspection accuracy in the post-process and reduction in quality and yield due to contamination occurring in the manufacturing process can be resolved.
  • FIG. 1 is a cross-sectional view showing an example of the laminate of the present invention.
  • the laminate 1 comprises a cured resin layer (A) 2, a resin layer 3 and a cured resin layer (B) 4 in this order.
  • the cured resin layer (B) 4 as the process film 2 on the surface of the resin layer 3 as the process film 1 opposite to the surface on the cured resin layer (A) 2 side.
  • Not only precipitation of the oligomer component from the resin layer 3 into the cured resin layer (B) 4 due to the heat treatment of (1), but also precipitation of the oligomer component into the cured resin layer (A) 2 can be suppressed at the same time.
  • an increase in the haze value of the laminate 1 is suppressed, and naturally the cured resin layer (A) 2 after peeling of the process film 1 also has the same effect.
  • the haze value of the laminate is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.5% or less, and particularly preferably 1.0% or less.
  • the haze value of the laminate after heating at 150° C. for 1 hour is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.5% or less, and particularly preferably 1.0% or less. .
  • the haze value is in this range, for example, when a functional layer to be described later is formed to form a laminate, the light diffusivity of the entire laminate can be easily maintained small, and defect inspection of the cured resin layer (A) can be performed. In this case, it is possible to improve the accuracy of discovering defects such as scratches and foreign matter that are present in the cured resin layer (A).
  • the haze value was measured by the method described in Examples below.
  • the peel force between the cured resin layer (A) and the resin layer after heating at 150° C. for 1 hour is preferably 500 mN/50 mm or less, more preferably 400 mN/50 mm or less, still more preferably 300 mN/50 mm or less. , particularly preferably 250 mN/50 mm or less.
  • a release layer may be further provided between the cured resin layer (A) and the resin layer.
  • the peel force between the cured resin layer (A) and the peel layer after heating at 150° C. for 1 hour is preferably 500 mN/50 mm or less, more preferably 400 mN/50 mm or less, and still more preferably 300 mN/50 mm or less.
  • the peel force between the cured resin layer (A) and the resin layer or release layer after heating at 150° C. for 1 hour is preferably 20 mN/50 mm or more, more preferably 30 mN/50 mm or more, and still more preferably 50 mN. /50 mm or more, and particularly preferably 70 mN/50 mm or more.
  • the peel force is within this range, the process film is not peeled off during web handling, and the cured resin layer (A) can be easily removed from the resin layer as the process film 1 even before and after the heat treatment. Can be stripped.
  • the peel force was measured by the method described in the examples below.
  • the thickness of the laminate can be appropriately determined according to the intended use of the adherend, electronic device, or the like.
  • the thickness of the laminate is preferably 5 to 300 ⁇ m, more preferably 20 to 250 ⁇ m, still more preferably 50 to 200 ⁇ m, from the viewpoint of handleability.
  • FIG. 2 is a cross-sectional view showing another example of the laminate of the present invention.
  • the laminate 11 is composed of a cured resin layer (A) 2, a resin layer 3, a cured resin layer (B) 4, and a functional layer 5.
  • the functional layer 5 is laminated on the cured resin layer (A) 2, and the cured resin layer (A) 2 can be used as a layer on which the functional layer 5 is provided or as a substrate.
  • the functional layer is not particularly limited, but includes, for example, a conductive layer, an adhesive layer, an adhesive layer, an adhesive layer, a gas barrier layer, an impact absorption layer, a hard coat layer, an antireflection layer, and the like.
  • the arrangement position of the functional layer is not particularly limited.
  • materials constituting the conductive layer (electrode, transparent conductive layer, etc.) used as the functional layer include metals, alloys, metal oxides, electrically conductive compounds, mixtures thereof, and the like.
  • transparent conductive layers for example, antimony-doped tin oxide (ATO); fluorine-doped tin oxide (FTO); tin oxide, germanium-doped zinc oxide (GZO), zinc oxide, indium oxide, indium tin oxide ( ITO), semi-conductive metal oxides such as indium zinc oxide (IZO); metals such as gold, silver, chromium, nickel; mixtures of these metals and conductive metal oxides; inorganic materials such as copper iodide and copper sulfide conductive substances; organic conductive materials such as polyaniline, polythiophene, and polypyrrole; and the like.
  • Methods for forming the conductive layer include, for example, a printing method, a vapor deposition method, a sputtering method, an ion plating method, a thermal CVD method, a plasma CVD method, and the like.
  • the thickness of the conductor layer may be appropriately selected according to its use. It is usually 10 nm to 50 ⁇ m, preferably 20 nm to 20 ⁇ m.
  • the adhesive layer is a layer used, for example, when attaching the laminate to an adherend or the like.
  • the material for forming the adhesive layer is not particularly limited, and known adhesives or adhesives such as acrylic, silicone, rubber, epoxy, etc., heat sealing materials, etc. can also be used. Epoxy-based adhesive is preferable as the material constituting the .
  • the pressure-sensitive adhesive layer is a layer used, for example, when attaching the laminate to an adherend or the like.
  • adhesives used for the adhesive layer include acrylic adhesives, urethane adhesives, silicone adhesives, rubber adhesives, and the like. Among these, acrylic pressure-sensitive adhesives and urethane-based pressure-sensitive adhesives are preferred from the viewpoints of adhesive strength, transparency, and handleability.
  • a pressure-sensitive adhesive capable of forming a crosslinked structure is preferable.
  • the adhesive may be in any form such as a solvent-type adhesive, an emulsion-type adhesive, a hot-melt-type adhesive, or the like.
  • the thickness of the laminate including the functional layer is usually the sum of the thickness of the desired functional layer and the thickness of the laminate without the functional layer described above.
  • the laminate of the present invention includes a cured resin layer (A).
  • the cured resin layer (A) is a layer made of a cured product of a curable resin composition 1 containing a polymer component (M) containing a polyimide resin and a curable monomer (P).
  • the cured resin layer (A) may be a single layer or multiple layers. The method for forming the cured resin layer (A) will be described in detail in the method for manufacturing a laminate to be described later.
  • a polyimide resin is included as the polymer component (M).
  • a polyimide resin has a high glass transition temperature (Tg) and is excellent in heat resistance.
  • the polyimide resin is preferably an amorphous thermoplastic because it is possible to form a coating film by a solution casting method and it is easy to obtain a cured resin layer (A) having excellent optical isotropy.
  • polyimide resins exhibit heat resistance and are soluble in general-purpose organic solvents such as low-boiling organic solvents such as benzene and methyl ethyl ketone.
  • the amorphous thermoplastic resin means a thermoplastic resin whose melting point is not observed in differential scanning calorimetry.
  • the glass transition temperature of the polymer component (M) is preferably 250°C or higher, more preferably 290°C or higher, still more preferably 320°C or higher.
  • the polymer component (M) having a Tg of 250°C or higher it is possible to impart sufficient heat resistance to the cured resin layer (A). Heating (including solvent drying, etc.) during film coating suppresses the occurrence of deformation due to the influence of the cured resin layer (A), and as a result, the function of the functional layer of the laminate is fully realized. can be exhibited.
  • a coating film is a film obtained by coating a coating material on a base material or an object and, if necessary, performing a treatment such as drying or curing by heating.
  • the functional layer is a coating film
  • a coating material containing a component that forms the functional layer is applied on the cured resin layer (A), and dried, heated, or irradiated with an active energy ray. It is a film obtained by performing a curing treatment.
  • Tg is the maximum point of tan ⁇ (loss modulus/storage modulus) obtained by viscoelasticity measurement (measurement in tensile mode in the range of 0 to 400° C. at a frequency of 10 Hz and a heating rate of 3° C./min). means temperature.
  • the weight average molecular weight (Mw) of the polyimide resin in the polymer component (M) is preferably 100,000 or more, more preferably 100,000 or more and 280,000 or less, still more preferably 100,000 or more and 240,000 It is below.
  • the weight average molecular weight (Mw) is in this range, for example, when forming a functional layer or the like from a coating film, the cured resin layer (A) before and after heating (including solvent drying etc.) during coating of the coating film is suppressed, and as a result, the original functions of the functional layers of the laminate can be fully exhibited.
  • the molecular weight distribution (Mw/Mn) is preferably in the range of 1.0 to 5.0, more preferably 1.2 to 3.0.
  • a weight average molecular weight (Mw) and a molecular weight distribution (Mw/Mn) are polystyrene equivalent values measured by a gel permeation chromatography (GPC) method.
  • the polyimide resin is not particularly limited as long as it does not impair the effects of the present invention.
  • aromatic polyimide resin, aromatic (carboxylic acid component) - cycloaliphatic (diamine component) polyimide resin, cyclic Group (carboxylic acid component)-aromatic (diamine component) polyimide resins, cycloaliphatic polyimide resins, fluorinated aromatic polyimide resins, and the like can be used.
  • a polyimide resin having an aromatic ring structure is preferable as one aspect.
  • a polyimide resin having a fluoro group in the molecule which will be described later, is preferable.
  • a polyimide resin obtained by polymerization to polyamic acid and chemical imidization reaction using an aromatic diamine compound and a tetracarboxylic dianhydride is preferred.
  • the aromatic diamine compound is a polyimide that is soluble in a common solvent (for example, N,N-dimethylacetamide (DMAC)) and has a certain level of transparency by reacting with the tetracarboxylic dianhydride that is used together.
  • a common solvent for example, N,N-dimethylacetamide (DMAC)
  • Any aromatic diamine compound can be used as long as it provides the aromatic diamine compound.
  • aromatic diamine compounds may be used alone, or two or more aromatic diamine compounds may be used.
  • preferable aromatic diamine compounds include 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2 -bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3 ,3,3-hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4- (4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3, 3,3-hexafluoropropane,
  • tetracarboxylic dianhydride a tetracarboxylic acid that is soluble in a common solvent (eg, N,N-dimethylacetamide (DMAC)) and gives a polyimide having a predetermined transparency, like the aromatic diamine compound.
  • a common solvent eg, N,N-dimethylacetamide (DMAC)
  • Any dianhydride can be used, and specifically, 4,4′-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)diphthalic acid di anhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,4-hydroquinonedibenzoate-3,3',4,4'-tetracarboxylic acid Acid dianhydride, 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′-diphenylethertetracarboxylic dianhydride and the like are exemplified.
  • tetracarboxylic dianhydrides may be used alone, or two or more kinds of tetracarboxylic dianhydrides may be used.
  • 4,4′-(1,1,1,3,3,3-hexafluoropropane-2,2-diyl)diphthalic dianhydride and the like from the viewpoint of transparency, heat resistance and solubility in solvents preferably a tetracarboxylic dianhydride having at least one fluoro group.
  • Polymerization into polyamic acid can be carried out by reacting the above aromatic diamine compound and tetracarboxylic dianhydride while dissolving in a solvent in which the resulting polyamic acid is soluble.
  • Solvents used for polymerization to polyamic acid include solvents such as N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and dimethylsulfoxide. can be used.
  • the polymerization reaction to polyamic acid is preferably carried out while stirring in a reaction vessel equipped with a stirring device.
  • a method of dissolving a predetermined amount of an aromatic diamine compound in the above solvent, adding tetracarboxylic dianhydride while stirring to react, and obtaining polyamic acid, dissolving the tetracarboxylic dianhydride in the solvent is mentioned.
  • the temperature of the polymerization reaction to polyamic acid is not particularly limited, but it is preferably carried out at a temperature of 0 to 70°C, more preferably 10 to 60°C, and even more preferably 20 to 50°C. By performing the polymerization reaction within the above range, it is possible to obtain a high-molecular-weight polyamic acid with little coloration and excellent transparency.
  • the aromatic diamine compound and the tetracarboxylic dianhydride used for polymerization into polyamic acid are generally used in equimolar amounts. It is also possible to change the molar amount of the compound/the molar amount (molar ratio) of the aromatic diamine compound within the range of 0.95 to 1.05.
  • the molar ratio of the tetracarboxylic dianhydride and the aromatic diamine compound is preferably in the range of 1.001-1.020, more preferably 1.001-1.010.
  • the degree of polymerization of the resulting polyamic acid can be stabilized, and the unit derived from the tetracarboxylic dianhydride can be It can be placed at the end of the polymer, and as a result, it is possible to obtain a polyimide with little coloration and excellent transparency.
  • the concentration of the polyamic acid solution to be produced is preferably adjusted to an appropriate concentration (for example, about 10 to 30% by mass) so that the viscosity of the solution can be properly maintained and handling in the subsequent steps can be facilitated.
  • An imidizing agent is added to the resulting polyamic acid solution to carry out a chemical imidization reaction.
  • the imidizing agent carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, succinic anhydride, phthalic anhydride, and benzoic anhydride can be used. Preference is given to using acetic acid.
  • the equivalent of the imidizing agent to be used is at least the equivalent of the amide bond of the polyamic acid that performs the chemical imidization reaction, preferably 1.1 to 5 times the equivalent of the amide bond, and 1.5 to 4 times. is more preferable. By using the imidizing agent in a slightly excess amount with respect to the amide bond in this way, the imidization reaction can be efficiently carried out even at a relatively low temperature.
  • aliphatic, aromatic or heterocyclic tertiary amines such as pyridine, picoline, quinoline, isoquinoline, trimethylamine and triethylamine can be used as imidization accelerators.
  • imidization accelerators such as pyridine, picoline, quinoline, isoquinoline, trimethylamine and triethylamine.
  • the chemical imidization reaction temperature it is preferably carried out at 10°C or higher and lower than 50°C, more preferably at 15°C or higher and lower than 45°C.
  • a poor solvent for polyimide is added to the polyimide solution obtained by the chemical imidization reaction to precipitate polyimide to form powder, which is powderization and drying.
  • the polyimide resin it is preferable that it is compatible with low boiling point organic solvents such as benzene and methyl ethyl ketone. In particular, it is preferably soluble in methyl ethyl ketone. When it is soluble in methyl ethyl ketone, a curable resin layer (A), which will be described later, made of a cured product of the curable resin composition 1 can be easily formed by coating and drying.
  • a polyimide resin containing a fluoro group is particularly preferable from the viewpoint that it is easily dissolved in a general-purpose organic solvent having a low boiling point such as methyl ethyl ketone and that a curable resin layer is easily formed by a coating method.
  • the polyimide resin having a fluoro group is preferably an aromatic polyimide resin having a fluoro group in the molecule, and preferably has a skeleton represented by the following chemical formula in the molecule.
  • a polyimide resin having a skeleton represented by the above chemical formula has an extremely high Tg exceeding 300°C due to the high rigidity of the skeleton. Therefore, the heat resistance of the cured resin layer (A) can be greatly improved.
  • the skeleton is linear and has relatively high flexibility, which facilitates increasing the breaking elongation (A) of the cured resin layer.
  • the polyimide resin having the above skeleton can dissolve in general-purpose low-boiling organic solvents such as methyl ethyl ketone due to the presence of fluoro groups. Therefore, the cured resin layer (A) can be formed as a coating film by coating using a solution casting method, and the solvent can be easily removed by drying.
  • the polyimide resin having a skeleton represented by the above chemical formula includes 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl and 4,4′-(1,1,1,3,3,3 -Hexafluoropropane-2,2-diyl)diphthalic dianhydride can be obtained by polymerization and imidization reaction of the polyamic acid described above.
  • the polymer component (M) may further contain other components.
  • Other components include polyarylate resins.
  • a polyarylate resin is a resin composed of a polymer compound obtained by reacting an aromatic diol with an aromatic dicarboxylic acid or a chloride thereof.
  • the polyarylate resin also has a relatively high Tg, similarly to the polyimide resin, and has relatively good elongation properties.
  • the polyarylate resin is not particularly limited, and known ones can be used.
  • aromatic diols include bis(4-hydroxyphenyl)methane [bisphenol F], bis(3-methyl-4-hydroxyphenyl)methane, 1,1-bis(4′-hydroxyphenyl)ethane, 1, 1-bis(3'-methyl-4'-hydroxyphenyl)ethane, 2,2-bis(4'-hydroxyphenyl)propane [bisphenol A], 2,2-bis(3'-methyl-4'-hydroxy bis(hydroxyphenyl)alkanes such as phenyl)propane, 2,2-bis(4'-hydroxyphenyl)butane, 2,2-bis(4'-hydroxyphenyl)octane; 1,1-bis(4'- bis(hydroxyphenyl)cyclopentane, 1,1-bis(4'-hydroxyphenyl)cyclohexane [bisphenol Z], 1,1-bis(4'-hydroxyphenyl)-3,3,5-trimethylcyclohexane, etc.
  • bisphenol F bis(4-hydroxyphenyl)methan
  • phenyl)cycloalkanes bis(4-hydroxyphenyl)phenylmethane, bis(3-methyl-4-hydroxyphenyl)phenylmethane, bis(2,6-dimethyl-4-hydroxyphenyl)phenylmethane, bis(2, 3,6-trimethyl-4-hydroxyphenyl)phenylmethane, bis(3-t-butyl-4-hydroxyphenyl)phenylmethane, bis(3-phenyl-4-hydroxyphenyl)phenylmethane, bis(3-fluoro- 4-hydroxyphenyl)phenylmethane, bis(3-bromo-4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)-4-fluorophenylmethane, bis(3-fluoro-4-hydroxyphenyl)-4- Fluorophenylmethane, bis(4-hydroxyphenyl)-4-chlorophenylmethane, bis(4-hydroxyphenyl)-4
  • aromatic dicarboxylic acids or chlorides thereof include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-biphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyl ether 4,4′-dicarboxylic acid, 4,4′- diphenylsulfonedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, chlorides thereof, and the like.
  • the polyarylate-based resin to be used may be a modified polyarylate-based resin.
  • the polyarylate-based resin is preferably a resin composed of a polymer compound obtained by reacting 2,2-bis(4'-hydroxyphenyl)propane with isophthalic acid.
  • the polymer component (M) can be used singly or in combination of two or more. Also, the polymer component (M) and the polymer component (M') having a glass transition temperature of less than 250°C may be used in combination. Examples of the polymer component (M′) include polyamide resins and polyarylate resins having a Tg of less than 250° C. Polyamide resins are preferred.
  • the polyamide resin one that is soluble in an organic solvent is preferable, and a rubber-modified polyamide resin is preferable.
  • a rubber-modified polyamide resin for example, those described in JP-A-2004-035638 can be used.
  • polymer component (M) and the polymer component (M') one using a single type of polyimide resin, one using a plurality of different types of polyimide resin, and polyimide resin with polyamide resin and polyarylate resin It is preferable to add at least one of them from the viewpoint of adjusting the elongation characteristics and the viewpoint of solvent resistance.
  • the amount of the resin to be added is 100 parts by mass of the polyimide resin from the viewpoint of imparting moderate flexibility while maintaining a high Tg. , preferably 100 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, and preferably 1 part by mass or more, more preferably It is 3 parts by mass or more.
  • curable monomer (P) is a monomer having a polymerizable unsaturated bond, and is a monomer that can participate in a polymerization reaction or a polymerization reaction and a cross-linking reaction.
  • curing means a broad concept including this "polymerization reaction of monomers” or “polymerization reaction of monomers and subsequent cross-linking reaction of polymers”.
  • the molecular weight of the curable monomer (P) is generally 3,000 or less, preferably 150-2,000, more preferably 150-1,000.
  • the number of polymerizable unsaturated bonds in the curable monomer (P) is not particularly limited.
  • the curable monomer (P) is a monofunctional monomer having one polymerizable unsaturated bond, or a polyfunctional monomer such as a bifunctional to hexafunctional monomer having a plurality of good too.
  • Examples of the monofunctional monomers include monofunctional (meth)acrylic acid derivatives.
  • the monofunctional (meth)acrylic acid derivative is not particularly limited, and known compounds can be used. Examples include monofunctional (meth)acrylic acid derivatives having a nitrogen atom, monofunctional (meth)acrylic acid derivatives having an alicyclic structure, and monofunctional (meth)acrylic acid derivatives having a polyether structure. .
  • Examples of monofunctional (meth)acrylic acid derivatives having a nitrogen atom include compounds represented by the following formula.
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 2 and R 3 each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms
  • R 2 and R 3 may combine to form a ring structure
  • R 4 represents a divalent organic group.
  • the alkyl group having 1 to 6 carbon atoms represented by R 1 include a methyl group, an ethyl group, a propyl group and the like, and a methyl group is preferred.
  • Examples of organic groups having 1 to 12 carbon atoms represented by R 2 and R 3 include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group and propyl group; cycloalkyl groups having 3 to 12 carbon atoms; aromatic groups having 6 to 12 carbon atoms such as phenyl, biphenyl and naphthyl groups; These groups may have a substituent at any position. Also, R 2 and R 3 may combine to form a ring, and the ring may further have a nitrogen atom or an oxygen atom in its skeleton. Divalent organic groups represented by R 4 include groups represented by -(CH 2 ) m - and -NH-(CH 2 ) m -. Here, m is an integer of 1-10.
  • the (meth)acryloylmorpholine represented by the following formula is preferred as the monofunctional (meth)acrylic acid derivative having a nitrogen atom.
  • a curable resin layer with more excellent heat resistance can be formed.
  • Examples of monofunctional (meth)acrylic acid derivatives having an alicyclic structure include compounds represented by the following formulas.
  • R 1 has the same meaning as above, and R 5 is a group having an alicyclic structure.
  • the group having an alicyclic structure represented by R 5 includes cyclohexyl group, isobornyl group, 1-adamantyl group, 2-adamantyl group, tricyclodecanyl group and the like.
  • monofunctional (meth)acrylic acid derivatives having an alicyclic structure include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate and the like. mentioned.
  • a cured resin layer (P) having better optical properties can be formed.
  • the monofunctional (meth)acrylic acid derivative having a polyether structure includes compounds represented by the following formula.
  • R 1 has the same meaning as above, and R 6 represents an organic group having 1 to 12 carbon atoms.
  • the organic group having 1 to 12 carbon atoms represented by R 6 include alkyl groups having 1 to 12 carbon atoms such as methyl group, ethyl group and propyl group; A cycloalkyl group; an aromatic group having 6 to 12 carbon atoms such as a phenyl group, a biphenyl group and a naphthyl group; j represents an integer from 2 to 20;
  • monofunctional (meth)acrylic acid derivatives having a polyether structure include ethoxylated o-phenylphenol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, phenoxypolyethyleneglycol (meth)acrylate, and the like. .
  • a cured resin layer (A) having excellent toughness can be formed.
  • polyfunctional monomers examples include polyfunctional (meth)acrylic acid derivatives.
  • the polyfunctional (meth)acrylic acid derivative is not particularly limited, and known compounds can be used. Examples thereof include di- to hexa-functional (meth)acrylic acid derivatives.
  • Bifunctional (meth)acrylic acid derivatives include compounds represented by the following formulas.
  • R 1 has the same meaning as above, and R 7 represents a divalent organic group.
  • R 7 represents a divalent organic group. Examples of the divalent organic group represented by R 7 include groups represented by the following formulae.
  • bifunctional (meth)acrylic acid derivative represented by the above formula examples include tricyclodecanedimethanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate. , ethoxylated bisphenol A di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 9,9-bis[4-(2-acryloyloxyethoxy) phenyl]fluorene, urethane acrylate, and the like.
  • the divalent organic group represented by R7 has a tricyclodecane skeleton, propoxy
  • the divalent organic group represented by R7 has a bisphenol skeleton, 9,9-bis [4-(2-Acryloyloxyethoxy)phenyl]fluorene, etc., in which the divalent organic group represented by R 7 in the above formula preferably has a 9,9-bisphenylfluorene skeleton.
  • Urethane acrylate is preferred from the viewpoint of imparting flexibility.
  • bifunctional (meth)acrylic acid derivatives other than these include neopentyl glycol adipate di(meth)acrylate, neopentylglycol hydroxypivalate di(meth)acrylate, caprolactone-modified dicyclopentenyl di(meth)acrylate, Ethylene oxide-modified phosphoric acid di(meth)acrylate, di(acryloxyethyl)isocyanurate, allylated cyclohexyl di(meth)acrylate and the like can be mentioned.
  • Trifunctional (meth)acrylic acid derivatives include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propionic acid-modified dipentaerythritol tri(meth)acrylate, propylene oxide-modified trimethylolpropane tri(meth)acrylate. ) acrylate, tris(acryloxyethyl) isocyanurate, and the like.
  • Examples of tetrafunctional (meth)acrylic acid derivatives include pentaerythritol tetra(meth)acrylate.
  • Pentafunctional (meth)acrylic acid derivatives include propionic acid-modified dipentaerythritol penta(meth)acrylate.
  • Examples of hexafunctional (meth)acrylic acid derivatives include dipentaerythritol hexa(meth)acrylate and caprolactone-modified dipentaerythritol hexa(meth)acrylate.
  • a cyclization-polymerizable monomer may be used as the curable monomer (P).
  • a cyclization-polymerizable monomer is a monomer that has the property of being radically polymerized while being cyclized.
  • Cyclopolymerizable monomers include non-conjugated dienes, for example, ⁇ -allyloxymethyl acrylic acid-based monomers can be used, 2-allyloxymethyl acrylic acid alkyl esters having 1 to 4 carbon atoms, Cyclohexyl 2-(allyloxymethyl)acrylate is preferred, C 1-4 alkyl esters of 2-allyloxymethylacrylic acid are more preferred, and methyl 2-(allyloxymethyl)acrylate is even more preferred.
  • the curable monomer (P) can be used singly or in combination of two or more.
  • the curable monomer (P) is preferably a polyfunctional monomer because a cured resin layer (A) having excellent heat resistance and solvent resistance can be obtained.
  • the polyfunctional monomer a bifunctional (meth)acrylic acid derivative is preferable from the viewpoints that it is easily mixed with the polymer component (M) and that curing shrinkage of the polymer hardly occurs and curling of the cured product can be suppressed.
  • the curable monomer (P) contains a polyfunctional (meth)acrylate compound and a cyclopolymerizable monomer.
  • the curable monomer (P) contains a polyfunctional monomer
  • the content thereof is preferably 40% by mass or more in the total amount of the curable monomer (P), and 50 to 100% by mass. more preferred.
  • the curable resin composition 1 used in the present invention is prepared by mixing a polymer component (M), a curable monomer (P), and optionally a polymerization initiator and other components described later and dissolving them in an appropriate solvent. Or it can be prepared by dispersing.
  • the total content of the polymer component (M) and the curable monomer (P) in the curable resin composition 1 is preferably 40 with respect to the total mass of the curable resin composition 1 excluding the solvent. ⁇ 99.5% by mass, more preferably 60 to 99% by mass, still more preferably 80 to 98% by mass.
  • the content of the polymer component (M) and the curable monomer (P) in the curable resin composition 1 is the mass ratio of the polymer component (M) and the curable monomer (P), Preferably, the ratio of polymer component (M):curable monomer (P) is 20:80 to 90:10, more preferably 30:70 to 70:30.
  • the thermal shrinkage rate of the cured resin layer (A) before and after heat treatment at a high temperature is It becomes easy to fall, and breaking elongation becomes easy to be maintained.
  • the content of the polyimide resin in the polymer component (M) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total mass of the polymer component (M) excluding the solvent. , more preferably 95 to 100% by mass.
  • the polymer component (M) when using a combination of a plurality of resins having different solvent solubility, such as a combination of the polyimide resin described above and a polyamide resin or a polyarylate resin, first, the resin is added to a solvent suitable for each. After dissolving, it is preferable to add a solution in which another resin is dissolved to the low boiling point organic solvent in which the resin is dissolved.
  • the curable resin composition 1 can optionally contain a polymerization initiator.
  • Any polymerization initiator can be used without particular limitation as long as it initiates the curing reaction. Examples thereof include thermal polymerization initiators and photopolymerization initiators.
  • Thermal polymerization initiators include organic peroxides and azo compounds.
  • organic peroxides include dialkyl peroxides such as di-t-butyl peroxide, t-butylcumyl peroxide and dicumyl peroxide; diacyl peroxides such as acetyl peroxide, lauroyl peroxide and benzoyl peroxide.
  • ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide and methyl cyclohexanone peroxide
  • peroxyketals such as 1,1-bis(t-butylperoxy)cyclohexane ; t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2, Hydroperoxides such as 5-dihydroperoxide; esters; and the like.
  • Azo compounds include 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis(2-cyclopropylpropionitrile), 2,2′-azobis(2 ,4-dimethylvaleronitrile), azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo ) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and the like.
  • Photoinitiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one , 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-[4-[4-(2-hydroxy-2 -methyl-propionyl)-benzyl]phenyl]-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethyl Amino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone Alkylphenone-based photopolymerization initiators such as; -Phosphorus-based
  • 2,4,6-trimethylbenzoyl-diphenylphosphine oxide bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)- Phosphorus-based photopolymerization initiators such as phenylphosphinate and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide are preferred.
  • the curing reaction may be difficult to occur.
  • the use of the phosphorus-based photopolymerization initiator allows the curing reaction to occur using light of a wavelength that is not absorbed by the polymer component (M). can proceed efficiently.
  • a polymerization initiator can be used individually by 1 type or in combination of 2 or more types.
  • the content of the polymerization initiator is preferably 0.05 to 15% by mass, more preferably 0.05 to 10% by mass, and still more preferably 0.05 to 5% by mass with respect to the entire curable resin composition 1. .
  • the curable resin composition 1 contains a polymer component (M), a curable monomer (P), and a polymerization initiator, as well as triisopropanolamine and light such as 4,4′-diethylaminobenzophenone. It may contain a polymerization initiation aid.
  • the solvent used for preparing the curable resin composition 1 is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene and xylene; Halogenated hydrocarbon solvents such as dichloromethane, ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, monochlorobenzene; alcohol solvents such as methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether; acetone, methyl ethyl ketone, Ketone solvents such as 2-pentanone, isophorone and cyclohexanone; Ester solvents such as ethyl acetate and butyl acetate; Cellosolve solvents such as ethyl cellosolve; Ether solvents such as 1,3-dioxolane;
  • the content of the solvent in the curable resin composition 1 is not particularly limited, it is usually 0.1 to 1,000 g, preferably 1 to 100 g, per 1 g of the polymer component (M). By appropriately adjusting the amount of the solvent, the viscosity of the curable resin composition 1 can be appropriately adjusted.
  • the curable resin composition 1 may further contain known additives such as plasticizers, antioxidants, and ultraviolet absorbers within a range that does not impair the objects and effects of the present invention.
  • the cured resin layer (A) used in the present invention exhibits heat shrinkability (shrinks when heated).
  • the thermal shrinkage rate when heat-treated at 100° C. for 2 minutes is preferably 0.08% or less, more preferably 0.05% or less, and still more preferably 0.01% or less.
  • the heat shrinkage rate of the curable resin layer is in this range, the heat resistance of the curable resin layer (A) is high.
  • a manufacturing process involving heating is performed after forming the cured resin layer (A), such as forming a functional layer, heat shrinkage is suppressed, and mechanical deformation (e.g., warping, peeling, wrinkling, etc.) of the functional layer occurs.
  • thermomechanical analyzer manufactured by NETZSCH Japan, model name “TMA4000SE”
  • TMA4000SE thermomechanical analyzer
  • the rate of change in displacement in the longitudinal direction (a value expressed as a percentage of the amount of displacement with respect to the chuck-to-chuck distance of 20 mm) was defined as the rate of thermal change.
  • the obtained value takes a negative value, it means that the cured resin layer (A) has shrunk (heat shrinkage), and when it takes a positive value, it means that the cured resin layer (A) has stretched. .
  • the breaking elongation of the cured resin layer (A) is preferably 2.5% or more, more preferably 3.0% or more, and still more preferably 3.5% or more.
  • the breaking elongation of the cured resin layer (A) is in this range, for example, if it is 2.5% or more, it becomes easy to adjust the breaking elongation of the laminate including the functional layer to about 2% or more, resulting in In general, it becomes easier to obtain a laminate having excellent flexibility.
  • the measurement of elongation at break can be evaluated, for example, by the following method.
  • a cured resin layer (A) having a thickness of 5 ⁇ m was cut into a test piece of 15 mm ⁇ 150 mm, and the elongation at break was measured according to JIS K7127:1999. Specifically, the test piece was subjected to a tensile test at a speed of 200 mm/min after setting the distance between chucks to 100 mm using a tensile tester (manufactured by Shimadzu Corporation, Autograph). %) was measured. When the test piece did not have a yield point, the tensile breaking strain was taken as the breaking elongation.
  • the in-plane retardation of the curable resin layer (A) is preferably 2.0 nm or less, more preferably 1.5 nm or less, still more preferably 1.0 nm or less, even more preferably 0.5 nm or less, and particularly preferably is 0.3 nm or less.
  • the in-plane retardation was calculated by the following formula (1).
  • Re( ⁇ ) (nx ⁇ ny) ⁇ d (1)
  • Re ( ⁇ ) is the in-plane retardation of the cured resin layer measured with light of wavelength ⁇ nm at 23° C.
  • Re (450) is measured with light of wavelength 450 nm at 23° C. This is the in-plane retardation of the cured resin layer.
  • nx is the refractive index in the direction in which the in-plane refractive index is maximized (that is, the slow axis direction), and “ny” is the direction perpendicular to the slow axis in the plane (that is, the fast axis direction), and d is the thickness (nm) of the cured resin layer.
  • the retardation in the thickness direction is usually ⁇ 500 nm or less, preferably ⁇ 450 nm or less.
  • the value (birefringence) obtained by dividing the in-plane retardation by the thickness of the cured resin layer is usually 100 ⁇ 10 ⁇ 5 or less, preferably 20 ⁇ 10 ⁇ 5 or less.
  • the cured resin layer (A) is excellent in optical isotropy and can be preferably used as a member for optical applications.
  • the in-plane retardation was measured by the method described in Examples described later.
  • the thickness of the cured resin layer (A) is not particularly limited, and may be appropriately adjusted according to the purpose of the laminate having the functional layer, for example.
  • the thickness of the cured resin layer (A) is usually 50 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 0.1 to 20 ⁇ m, even more preferably 0.1 to 15 ⁇ m, particularly preferably 0.2 to 10 ⁇ m.
  • the thickness of the cured resin layer (A) is within this range, even when a laminate including a functional layer is formed, the thickness of the laminate can be prevented from increasing, and a thin laminate can be obtained. can be done.
  • a thin laminate is preferable because the laminate does not cause an increase in the thickness of the entire applicable device in applications such as devices that require thinner devices.
  • the amount of stretching strain of the outermost layer can be reduced when the laminate is bent, and the flexibility of the laminate can be improved.
  • flexibility after mounting of the laminate can be secured.
  • the cured resin layer (A) used in the present invention has excellent solvent resistance. Because of its excellent solvent resistance, the surface of the cured resin layer (A) hardly dissolves even when an organic solvent is used to form another layer on the surface of the cured resin layer (A). Therefore, for example, even when a functional layer is formed on the surface of the cured resin layer (A) using a resin solution containing an organic solvent, the components of the cured resin layer (A) do not easily penetrate into the functional layer. The original functions of the functional layer are less likely to deteriorate. From the above viewpoint, the gel fraction of the cured resin layer (A) is preferably 80% or higher, more preferably 85% or higher, still more preferably 87% or higher, and particularly preferably 90% or higher.
  • the cured resin layer (A) having a gel fraction of 80% or more is excellent in solvent resistance.
  • the surface of the cured resin layer (A) is hardly dissolved, and a laminate having excellent solvent resistance can be easily obtained.
  • the gel fraction is obtained by performing the following operations (a), (b), and (c), and comparing the weight of the measured structure after drying to the structure before immersion in MEK (methyl ethyl ketone) solvent Calculated by dividing by body weight.
  • the cured resin layer (A) was wrapped with a mesh ( ⁇ _UX SCREEN 150-035/380TW manufactured by NBC Meshtec Co., Ltd.) and stapled to form a structure, and the weight of the structure was measured.
  • the laminate of the present invention includes a resin layer.
  • the resin layer is used as the process film 1 for forming the cured resin layer (A).
  • the process film 1 is preferably sheet-like or film-like.
  • sheet-like or film-like includes not only a long one but also a short flat plate-like one.
  • the process film 1 is not particularly limited, but polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, and plastic films such as polyolefin films such as polyethylene and polypropylene are preferable. Further, the process film 1 may have a release layer provided on the plastic film from the viewpoint of ease of handling.
  • the release layer can be formed by a known method using a conventionally known release agent such as a silicone-based release agent, a fluorine-based release agent, an alkyd-based release agent, an olefin-based release agent, and the like.
  • the thickness of the release layer is not particularly limited, but is usually 0.02 to 2.00 ⁇ m, more preferably 0.05 to 1.50 ⁇ m.
  • the thickness of the process film 1 is preferably 1 to 500 ⁇ m, more preferably 5 to 300 ⁇ m, from the viewpoint of ease of handling.
  • the average surface roughness (arithmetic mean roughness Ra) of the surface of the process film 1 facing the cured resin layer (A) is preferably 0.5 nm to 10.0 nm, more preferably 0.8 nm to 5.0 nm.
  • the maximum surface roughness (maximum cross-sectional height Rt) is preferably 10 nm to 800 nm, more preferably 20 nm to 500 nm.
  • Arithmetic mean roughness Ra and maximum cross-sectional height Rt were determined by the methods described in the examples below.
  • the process film 1 is usually peeled off in a predetermined process depending on the use of the laminate.
  • the laminate of the present invention includes a cured resin layer (B).
  • the cured resin layer (B) is a layer made of a cured product of the curable resin composition 2 containing the polymer component (N) and/or the curable monomer (Q).
  • the curable resin layer (B) may be a single layer or multiple layers.
  • the cured resin layer (B) layer has a function of suppressing precipitation of the oligomer component of the resin layer, and is used as the process film 2 .
  • the method for forming the cured resin layer (B) will be described in detail in the method for manufacturing a laminate to be described later.
  • the cured resin layer (B) may contain a polymer component (N).
  • the polymer component (N) include thermoplastic resins.
  • the thermoplastic resin is preferably a thermoplastic resin having a ring structure such as an aromatic ring structure or an alicyclic structure, and more preferably a thermoplastic resin having an aromatic ring structure.
  • thermoplastic resins include polyimide-based resins, polysulfone-based resins, polyarylate-based resins, polycarbonate-based resins, and alicyclic hydrocarbon-based resins.
  • polyimide resin the same resin as used for the polymer component (M) can be used.
  • polyarylate-based resin the same one used as the polymer component (M) described above can be used.
  • the polysulfone-based resin is a polymer having a sulfone group ( --SO.sub.2-- ) in its main chain, and is not particularly limited, and known resins can be used.
  • polysulfone-based resins examples include polyethersulfone resins, polysulfone resins, polyphenylsulfone resins, and the like.
  • the polysulfone-based resin used in the present invention may be a modified polysulfone-based resin.
  • Specific examples of polysulfone-based resins include resins made of polymer compounds having repeating units represented by the following (a) to (h).
  • polysulfone-based resin polyethersulfone resin or polysulfone resin is preferable.
  • the polycarbonate-based resin is not particularly limited, and known ones can be used.
  • Examples of polycarbonate-based resins include aromatic polycarbonate resins and aliphatic polycarbonate resins. Among them, aromatic polycarbonate resins are preferable because they are excellent in heat resistance, mechanical strength, transparency, and the like.
  • aromatic polycarbonate resin a method of reacting an aromatic diol and a carbonate precursor by an interfacial polycondensation method or a melt transesterification method, a method of polymerizing a carbonate prepolymer by a solid phase transesterification method, or a method of polymerizing a cyclic carbonate compound. It can be obtained by a method of polymerizing by a ring-opening polymerization method.
  • aromatic diol include those exemplified for the polyarylate resin in the polymer component (M).
  • Carbonate precursors include, for example, carbonyl halides, carbonate esters, haloformates, and the like, and specific examples include phosgene, diphenyl carbonate, dihaloformates of dihydric phenols, and the like.
  • An alicyclic hydrocarbon resin is a polymer having a cyclic hydrocarbon group in its main chain.
  • the alicyclic hydrocarbon resin is not particularly limited, and known resins can be used.
  • Examples of alicyclic hydrocarbon resins include monocyclic cyclic olefin polymers, norbornene polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrides thereof. .
  • Specific examples thereof include APEL (ethylene-cycloolefin copolymer manufactured by Mitsui Chemicals, Inc.), ARTON (norbornene-based polymer manufactured by JSR), Zeonor (norbornene-based polymer manufactured by Nippon Zeon Co., Ltd.), and the like.
  • Thermoplastic resins can be used singly or in combination of two or more.
  • the resins as the polymer component (N) described above it has a high Tg and excellent heat resistance.
  • a polyimide resin is particularly preferred.
  • the curable monomer (Q) is a monomer having a polymerizable unsaturated bond and capable of participating in a polymerization reaction or a polymerization reaction and a cross-linking reaction.
  • the same curable monomer (P) as described above can be used, and the number of polymerizable unsaturated bonds in the curable monomer (Q) is not particularly limited.
  • the curable monomer (Q) is a monofunctional monomer having one polymerizable unsaturated bond, or a multifunctional monomer such as a bifunctional to hexafunctional monomer having a plurality of There may be.
  • the curable monomer (Q) can be used singly or in combination of two or more.
  • the cured resin layer (B) preferably further contains a filler component.
  • a filler component By including a filler component, the heat resistance is improved and the deposition of the oligomer component from the adjacent resin layer is easily suppressed.
  • filler components include, but are not limited to, silicon oxides, titanium oxides, alumina (Al 2 O 3 ), zirconia (ZrO 2 ), and the like.
  • the silicon oxide is preferably particulate silicon oxide. Examples include particles of silicon dioxide (silica).
  • the average particle size of the silicon oxide used in the present invention is not particularly limited, but is usually 0.10 to 3 ⁇ m.
  • the silicon oxide may be obtained by any manufacturing method, and the surface thereof may be treated with a surface treatment agent such as a silane coupling agent, and the surface treatment may be an acryloyl group. It may be a silane coupling agent having
  • the average particle diameter of the filler component can be obtained by, for example, measuring the particle size distribution using a laser diffraction particle size analyzer (Malvern Co., Mastersizer 3000).
  • the curable resin composition 2 used in the present invention includes the above-described polymer component (N) and / or curable monomer (Q), and preferably a filler component, and optionally the above-described curable monomer ( It can be prepared by mixing the polymerization initiator and other components used in P) and dissolving or dispersing them in an appropriate solvent.
  • the total content of the polymer component (N) and the curable monomer (Q) in the curable resin composition 2 is , preferably 40 to 99.5% by mass, more preferably 60 to 99% by mass, and still more preferably 80 to 98% by mass, based on the total mass of the curable resin composition 2 excluding the solvent.
  • the content of the polymer component (N) and the curable monomer (Q) in the curable resin composition 2 is the mass ratio of the polymer component (N) and the curable monomer (Q)
  • the ratio of polymer component (N):curable monomer (Q) is 20:80 to 90:10, more preferably 30:70 to 70:30.
  • the content of the thermoplastic resin in the polymer component (N) is preferably 70 to 100% by mass, more preferably 80 to 100% by mass, based on the total mass of the polymer component (N) excluding the solvent. %, more preferably 95 to 100 mass %.
  • the content of the filler component is preferably 30-70% by mass, more preferably 45-65% by mass, relative to the total mass excluding the solvent. When the content of the filler component is within this range, the heat resistance of the cured resin layer (B) is further improved, and precipitation of the oligomer component from the resin layer is more easily suppressed.
  • the solvent and solvent content used for preparing the curable resin composition 2 are the same as the solvent and solvent content used for preparing the curable resin composition 1 described above.
  • the curable resin composition 2 may further contain known additives such as plasticizers, antioxidants, and ultraviolet absorbers within a range that does not impair the objects and effects of the present invention.
  • curable resin composition 2 Commercially available products of the curable resin composition 2 include, for example, the product name “Opstar Z7530” manufactured by Arakawa Chemical Industries, Ltd., the product names “Opstar Z7524”, “Opstar Z7537” and “Opstar TU4086” manufactured by Arakawa Chemical Industries, etc.
  • the thickness of the cured resin layer (B) may be adjusted as appropriate, for example, in consideration of adhesion with the resin layer, mechanical strength, and the like.
  • the thickness of the cured resin layer (B) is usually 50 ⁇ m or less, preferably 20 ⁇ m or less, more preferably 0.1 to 20 ⁇ m, even more preferably 0.3 to 10 ⁇ m, particularly preferably 0.5 to 5 ⁇ m.
  • the method for producing a laminate of the present invention includes the following (Step 1) to (Step 5).
  • the method of applying the curable resin composition 1 onto the process film 1 is not particularly limited, and includes a spin coating method, a spray coating method, a bar coating method, a knife coating method, a roll coating method, a blade
  • a spin coating method such as a coating method, a die coating method, or a gravure coating method can be used.
  • the method for drying the obtained coating film is not particularly limited, and conventionally known drying methods such as hot air drying, hot roll drying, and infrared irradiation can be used.
  • the drying temperature of the coating film is usually 30 to 150°C, preferably 50 to 130°C.
  • the method for curing the cured resin layer (A) (coating film) is not particularly limited, and known methods can be employed.
  • the cured resin layer (A) (coating film) is formed using the curable resin composition 1 containing a thermal polymerization initiator, the cured resin layer (A) (coating film) is heated. By doing so, the cured resin layer (A) (coating film) can be cured.
  • the heating temperature is usually 30 to 150°C, preferably 50 to 130°C.
  • the cured resin layer (A) (coating film) when the cured resin layer (A) (coating film) is formed using the curable resin composition 1 containing a photopolymerization initiator, the cured resin layer (A) (coating film) can be cured by irradiation with energy rays. Active energy rays can be applied using a high-pressure mercury lamp, an electrodeless lamp, a xenon lamp, or the like.
  • the wavelength of the active energy ray is preferably 200-400 nm, more preferably 350-400 nm.
  • the illuminance of the active energy rays is usually in the range of 50-1,000 mW/cm 2 , preferably 70-300 mW/cm 2 .
  • the amount of active energy rays is in the range of 50 to 5,000 mJ/cm 2 , preferably 300 to 4,000 mJ/cm 2 .
  • the irradiation time is usually 0.1 to 1,000 seconds, preferably 1 to 500 seconds, more preferably 10 to 100 seconds. In consideration of the heat load of the light irradiation process, the irradiation may be performed multiple times in order to satisfy the aforementioned light amount.
  • a filter that absorbs light of a wavelength unnecessary for the curing reaction is interposed to activate the active energy ray.
  • the curable resin composition 1 may be irradiated with energy rays.
  • the filter absorbs light of a wavelength that is unnecessary for the curing reaction and degrades the polymer component (M). It becomes easy to obtain a resin layer (A).
  • a resin film such as a polyethylene terephthalate film can be used as the filter.
  • a resin film When a resin film is used, it is preferable to provide a step of laminating a resin film such as a polyethylene terephthalate film on the cured resin layer (A) (coating film) between steps 1 and 2.
  • the resin film is usually peeled off after step 2.
  • the cured resin layer (A) (coating film) can also be cured by irradiating the cured resin layer (A) (coating film) with an electron beam.
  • the curable resin layer (A) (coating film) can be cured usually without using a photopolymerization initiator.
  • an electron beam accelerator or the like can be used.
  • the irradiation dose is usually in the range of 10 to 1,000 krad.
  • the irradiation time is usually 0.1 to 1,000 seconds, preferably 1 to 500 seconds, more preferably 10 to 100 seconds.
  • Curing of the cured resin layer (coating film) (A) may be performed under an inert gas atmosphere such as nitrogen gas, if necessary. Curing in an inert gas atmosphere makes it easier to prevent oxygen, moisture, and the like from interfering with curing.
  • Step 3 the method of applying the curable resin composition 2 onto the process film 2 and the method of drying the resulting cured resin layer (B) (coating film) are the same as those in (Step 1) described above. It can be done in a similar way.
  • the cured resin layer (B) (coating film) can be cured by the same method as in (Step 2) described above.
  • this step becomes unnecessary.
  • Step 5 as a method for forming a desired functional layer on the cured resin layer (A) obtained in (Step 2), the method described above is appropriately adopted depending on the functional layer to be used. be able to.
  • the manufacturing method including the above (step 1) to (step 5) uses the process film 1 and the process film 2 to form the cured resin layer (A), or the cured resin layer (A) and the functional layer. Form.
  • the laminate according to one aspect of the present invention can be efficiently, continuously, and easily produced.
  • Haze value The laminates prepared in Examples and Comparative Examples are cut into 50 mm x 50 mm test pieces, and the test pieces are measured according to JIS K7136: 2000 with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product Haze value (%) was measured using the name "SH-7000"). Furthermore, the test piece was heat-treated (150° C., 1 hour) using an oven (manufactured by Espec Co., Ltd., model name “SPHH202”), and then the haze value (%) was measured in the same manner.
  • the surface roughness of the surface of the process film 1 (resin layer) on which the cured resin layer (A) is formed that is, the average surface roughness (arithmetic mean roughness Ra) and the maximum surface roughness ( Maximum cross-sectional height Rt) is measured in a measurement area of 100 ⁇ m ⁇ 100 ⁇ m, using an optical interference surface profile measuring device (manufactured by Veeco Metrology Group, product name “WYKO WT1100”), PSI mode (Phase Shift Interferometry) interferometry) at a magnification of 50 times.
  • an optical interference surface profile measuring device manufactured by Veeco Metrology Group, product name “WYKO WT1100”
  • PSI mode Phase Shift Interferometry
  • Example 1 Preparation of laminate Curable resin compositions 1 and 2 were prepared as follows.
  • M polymer component
  • MEK methyl ethyl ketone
  • curable monomer (P) 122 parts by mass of tricyclodecanedimethanol diacrylate (A-DCP, molecular weight 304.4, manufactured by Shin-Nakamura Chemical Co., Ltd.) as a curable monomer (P), and a polymerization initiator, (2,4,6-Trimethylbenzoyl)-phenylphosphine oxide (manufactured by BASF, Irgacure TPO) of 5 parts by mass was added and mixed to prepare a curable resin composition 1.
  • the curable monomer (A) and the polymerization initiator do not contain a solvent and are all raw materials having a solid content of 100%.
  • a curable resin composition 2 containing a curable monomer (Q) and silica particles [manufactured by Arakawa Chemical Industries, Ltd., product name “OPSTAR Z7530”, silica particles with acryloyl groups A mixture of a substance to be bound, a polyfunctional acrylate monomer and oligomer, a photopolymerization initiator, a solvent, and other additives: Energy ray curing containing 43% by weight of silica fine particles and 28% by weight of a polyfunctional acrylate monomer and oligomer type compound, 2% by mass of photopolymerization initiator, 23% by mass of methyl ethyl ketone, and 4% by mass of other additives] were prepared.
  • a polyethylene terephthalate (PET) film manufactured by Toyobo Co., Ltd., product name “Cosmoshine A4100”, thickness 50 ⁇ m
  • the curable resin composition 1 was applied to the surface opposite to the adhesive layer surface, and the obtained coating film was dried by heating at 100° C. for 2 minutes.
  • the illuminance at a light wavelength of 365 nm is 130 mW/cm 2 and the light amount is 700 mJ/cm 2 (manufactured by Heraus, ultraviolet light meter, UV Under the conditions of Power Puck (registered trademark) II), a curing reaction was performed by irradiating ultraviolet rays in a nitrogen atmosphere to form a cured resin layer (A) having a thickness of 5 ⁇ m. Furthermore, the curable resin composition 2 was applied to the easy-adhesion layer surface of the PET film, and the obtained coating film was dried by heating at 100° C. for 2 minutes.
  • the haze value of the obtained laminate, the peeling force between the cured resin layer (A) and the resin layer, and the surface roughness [average surface roughness ( Arithmetic mean roughness Ra) and maximum surface roughness (maximum cross-sectional height Rt)] were evaluated. Table 1 shows the results.
  • Example 2 A laminate was produced in the same manner as in Example 1, except that another polyethylene terephthalate (PET) film (manufactured by Toray Industries, Inc., product name “Lumirror T60”, thickness 50 ⁇ m) was used as the process film 1 .
  • PET polyethylene terephthalate
  • the haze value of the obtained laminate, the peeling force between the cured resin layer (A) and the resin layer, and the surface roughness [average surface roughness ( Arithmetic mean roughness Ra) and maximum surface roughness (maximum cross-sectional height Rt)] were evaluated. Table 1 shows the results.
  • Example 1 A laminate (two-layer configuration of a cured resin layer (A) and a resin layer) was produced in the same manner as in Example 1 except that the curable resin composition 2 was used and the curable resin layer (B) was not formed.
  • the haze value of the obtained laminate, the peeling force between the cured resin layer (A) and the resin layer, and the surface roughness [average surface roughness ( Arithmetic mean roughness Ra) and maximum surface roughness (maximum cross-sectional height Rt)] were evaluated. Table 1 shows the results.
  • the laminates of Examples 1 and 2 which have the cured resin layer (B) on the surface opposite to the cured resin layer (A) side of the resin layer, have the cured resin layer (B) on the opposite surface. Compared to the laminate of Comparative Example 1, which does not have It can be seen that the force is maintained within the peelable range of peeling force regardless of the surface roughness of the resin layer used.
  • the laminate of the present invention precipitation of the oligomer component derived from the resin layer is suppressed at high temperatures, and the haze value is maintained.
  • Substrates such as members, or members and substrates such as optical films, for example, flexible organic EL displays, liquid crystal displays, members constituting transparent conductive layers such as ITO used for touch panels, and their substrates, antireflection It is expected to be applied to hard coat films, polarizing plate protective films for polarizing plates, and the like.
  • Laminate 2 Cured resin layer (A) 3: resin layer 4: cured resin layer (B) 5: Functional layer

Landscapes

  • Laminated Bodies (AREA)
PCT/JP2022/036296 2021-09-30 2022-09-28 積層体 Ceased WO2023054528A1 (ja)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023551809A JPWO2023054528A1 (https=) 2021-09-30 2022-09-28

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021161623 2021-09-30
JP2021-161623 2021-09-30

Publications (1)

Publication Number Publication Date
WO2023054528A1 true WO2023054528A1 (ja) 2023-04-06

Family

ID=85780731

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/036296 Ceased WO2023054528A1 (ja) 2021-09-30 2022-09-28 積層体

Country Status (3)

Country Link
JP (1) JPWO2023054528A1 (https=)
TW (1) TW202330251A (https=)
WO (1) WO2023054528A1 (https=)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003005365A (ja) * 2001-06-25 2003-01-08 Goo Chemical Co Ltd 紫外線硬化性樹脂組成物及びドライフィルム
JP2010162733A (ja) * 2009-01-14 2010-07-29 Asahi Kasei E-Materials Corp 硬化性樹脂組成物、印刷原版及び印刷版
JP2014024894A (ja) * 2012-07-24 2014-02-06 Mitsubishi Gas Chemical Co Inc ポリイミド樹脂、ポリイミド樹脂硬化物およびポリイミドフィルム
JP2016017089A (ja) * 2014-07-04 2016-02-01 三井化学株式会社 硬化性樹脂組成物、添加剤用組成物およびその用途
JP2016078399A (ja) * 2014-10-21 2016-05-16 大日本印刷株式会社 透明導電性積層体、及び該透明導電性積層体を用いたタッチパネル

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003005365A (ja) * 2001-06-25 2003-01-08 Goo Chemical Co Ltd 紫外線硬化性樹脂組成物及びドライフィルム
JP2010162733A (ja) * 2009-01-14 2010-07-29 Asahi Kasei E-Materials Corp 硬化性樹脂組成物、印刷原版及び印刷版
JP2014024894A (ja) * 2012-07-24 2014-02-06 Mitsubishi Gas Chemical Co Inc ポリイミド樹脂、ポリイミド樹脂硬化物およびポリイミドフィルム
JP2016017089A (ja) * 2014-07-04 2016-02-01 三井化学株式会社 硬化性樹脂組成物、添加剤用組成物およびその用途
JP2016078399A (ja) * 2014-10-21 2016-05-16 大日本印刷株式会社 透明導電性積層体、及び該透明導電性積層体を用いたタッチパネル

Also Published As

Publication number Publication date
TW202330251A (zh) 2023-08-01
JPWO2023054528A1 (https=) 2023-04-06

Similar Documents

Publication Publication Date Title
JP7724215B2 (ja) 光学用フィルム、光学用フィルムの製造方法、透明導電フィルム、及び、ガスバリアフィルム
JP7401463B2 (ja) ガスバリア性積層体
JP6082354B2 (ja) 硬化性樹脂組成物、硬化性樹脂成形体、硬化樹脂成形体およびそれらの製造方法、並びに積層体
JP6214399B2 (ja) 硬化性樹脂組成物、硬化性樹脂成形体、硬化樹脂成形体及びそれらの製造方法、並びに積層体
JP7603659B2 (ja) 透明導電フィルム用積層体、透明導電フィルム、及び、透明導電フィルムの製造方法
JP7398394B2 (ja) ガスバリア性積層体
KR20230164674A (ko) 적층체
WO2023054528A1 (ja) 積層体
JP7828814B2 (ja) 積層体、透明導電フィルム、及び、透明導電フィルムの製造方法
KR102962160B1 (ko) 투명 도전 필름용 적층체, 투명 도전 필름, 및, 투명 도전 필름의 제조 방법
WO2022203067A1 (ja) 硬化性樹脂組成物及びそれを用いた硬化樹脂層
WO2022203071A1 (ja) 硬化性樹脂組成物及びそれを用いた硬化樹脂層
JP7821614B2 (ja) 構成体
JP2023086574A (ja) 硬化樹脂層
JP2023114821A (ja) 光学フィルム

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22876394

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023551809

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 22876394

Country of ref document: EP

Kind code of ref document: A1