WO2022203071A1

WO2022203071A1 - Curable resin composition and cured resin layer using same

Info

Publication number: WO2022203071A1
Application number: PCT/JP2022/014634
Authority: WO
Inventors: 奈菜菊田; 博貴木下
Original assignee: リンテック株式会社
Priority date: 2021-03-26
Filing date: 2022-03-25
Publication date: 2022-09-29
Also published as: JPWO2022203071A1; TW202248226A

Abstract

Provided is a curable resin composition that exhibits a small percentage reduction in the storage modulus, a small coefficient of linear expansion, and an excellent heat resistance. Also provided is a cured resin layer that is a cured product from the curable resin composition. The curable resin composition comprises a polymer component (A) and a curable monomer (B) that has three or more curable functional groups. The cured resin layer comprises a cured product from this curable resin composition.

Description

Curable resin composition and cured resin layer using the same

The present invention relates to a curable resin composition and a cured resin layer using the same.

In recent years, various electronic devices, including display devices such as liquid crystal displays and organic electroluminescence (EL) displays, thermoelectric conversion elements, etc., have been configured to achieve thinness, weight reduction, flexibility, etc. As a member for supporting, it is being studied to use a thin transparent plastic film instead of a conventional rigid substrate such as glass or ceramics.
However, plastic films are generally inferior to glass in heat resistance. For example, when a transparent plastic film is used as a support substrate for the electronic device or the like, it often undergoes a heat history at high temperatures during the manufacturing process. At that time, mechanical damage or the like is received, which acts on the elements inside the electronic device, and causes problems such as the occurrence of a short circuit, which degrades the device performance and shortens the life of the device.
For example, Patent Literature 1 relating to a gas barrier laminate used for display devices and the like describes a cured product of a curable resin composition containing a polymer component (A) and a curable monomer (B) as a plastic film. An underlayer is disclosed which consists of:

WO2020/138206

However, as the underlayer of Patent Document 1, although the one using a curable monomer (B) having two curable functional groups is specifically studied, storage related to heat history at high temperature A decrease in elastic modulus, coefficient of linear expansion, and the like have not been sufficiently studied.

In view of the above, the present invention provides a curable resin composition having a small decrease in storage modulus, a small coefficient of linear expansion, and excellent heat resistance, and a cured resin layer that is a cured product of the curable resin composition. The challenge is to

The present inventors have made intensive studies to solve the above problems, and as a result, the cured resin layer is formed of a curable monomer (B The present inventors have found that the above problems can be solved by forming a layer made of a cured product of a curable resin composition containing ), and completed the present invention.
That is, the present invention provides the following [1] to [10].
[1] A curable resin composition containing a polymer component (A) and a curable monomer (B) having three or more curable functional groups.
[2] The curable resin composition according to [1] above, wherein the polymer component (A) has a glass transition temperature of 250°C or higher.
[3] The curable resin composition according to [1] or [2] above, wherein the polymer component (A) has a weight average molecular weight of 100,000 or more.
[4] The curable resin composition according to any one of [1] to [3] above, wherein the polymer component (A) is a polyimide resin.
[5] The cured resin according to any one of [1] to [4] above, wherein the cured resin layer comprises a cured product of the curable resin composition and has a thickness of 20 μm or less. layer.
[6] Reduction rate R of the storage elastic modulus (E' ₁₅₀ ) at 150° C. to the storage elastic modulus (E' ₃₀ ) at 30° C. of the cured resin layer (<(E' ₃₀ -E' ₁₅₀ )/E' ₃₀ >×100) is 45% or less, the cured resin layer according to the above [5].
[7] The cured resin layer according to [5] or [6] above, wherein the cured resin layer has a linear expansion coefficient of 95 ppm/K or less at 30°C to 150°C.
[8] The cured resin layer according to any one of [5] to [7] above, wherein the cured resin layer has a total light transmittance of 85% or more.
[9] The cured resin layer according to any one of [5] to [7] above, wherein the cured resin layer has a haze value of 1.0% or less.
[10] The cured resin layer according to any one of [5] to [9] above, comprising a functional layer on the cured resin layer.

According to the present invention, there is provided a curable resin composition having a small decrease rate of storage elastic modulus, a small linear expansion coefficient and excellent heat resistance, and a curable resin layer which is a cured product of the curable resin composition. can be done.

It is a sectional view showing an example of a cured resin layer of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram which shows an example of the laminated body using the cured resin layer of this invention.

In the present specification, 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.
In this specification, the description "XX to YY" means "XX or more and YY or less".
In this specification, for preferred numerical ranges (for example, ranges of content etc.), 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.

[Curable resin composition]
The curable resin composition of the present invention is characterized by containing a polymer component (A) and a curable monomer (B) having three or more curable functional groups.

<Polymer component (A)>
The curable resin composition of the present invention contains a polymer component (A).

As the polymer component (A), a thermoplastic resin is preferable, and an amorphous thermoplastic resin is more preferable. By using an amorphous thermoplastic resin, it becomes easier to obtain a cured resin layer having excellent transparency, which will be described later. In addition, since amorphous thermoplastic resins are generally easily dissolved in organic solvents, it is possible to efficiently form a cured resin layer composed of a cured product of a curable resin composition using a solution casting method, as described later. can.
Here, 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 (A) is preferably 250°C or higher, more preferably 290°C or higher, still more preferably 320°C or higher. By using the polymer component (A) having a Tg of 250° C. or higher, a cured resin layer having sufficiently excellent heat resistance can be obtained. If the Tg of the polymer component (A) is less than 250° C., the cured resin layer cannot be imparted with sufficient heat resistance, and for example, the functional layer contained in the later-described laminate is formed from the coating film. In such a case, the cured resin layer may be affected by heating during application of the coating film, causing deformation, etc. As a result, the functional layer of the laminate cannot fully exhibit its original function. There is fear.
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. When the functional layer is a coating film, the coating material containing the component forming the functional layer described later is applied on the cured resin layer, and cured by either or both of drying, heating, irradiation of active energy rays, etc. It is a film obtained by processing.
Here, Tg is the maximum point of tan δ (loss modulus/storage modulus) obtained by viscoelasticity measurement (measurement in tensile mode in the range of 0 to 250° C. at a frequency of 11 Hz and a heating rate of 3° C./min). means temperature.

The polymer component (A) is particularly preferably soluble in low-boiling general-purpose organic solvents such as benzene and methyl ethyl ketone (MEK). If it is soluble in a general-purpose organic solvent, it becomes easy to form a curable resin layer by coating.

A particularly preferable polymer component (A) is an amorphous thermoplastic resin having a Tg of 250°C or higher, which is soluble in low-boiling general-purpose organic solvents such as benzene and methyl ethyl ketone.

From the viewpoint of heat resistance, the polymer component (A) is preferably a thermoplastic resin having a ring structure such as an aromatic ring structure or an alicyclic structure, more preferably a thermoplastic resin having an aromatic ring structure.

Specific examples of the polymer component (A) include polyimide resins and polyarylate resins having a Tg of 250°C or higher. These resins generally have a high Tg and excellent heat resistance, and since they are amorphous thermoplastic resins, they can be formed into a coating film by a solution casting method. Among these, polyimide resins are preferred because they have a high Tg and excellent heat resistance, and are easy to obtain those that are soluble in general-purpose organic solvents while exhibiting good heat resistance.

The polyimide resin is not particularly limited as long as it does not impair the effects of the present invention. For example, 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 a fluoro group in the molecule is particularly preferred.
Specifically, 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. Any aromatic diamine compound can be used as long as it provides the aromatic diamine compound. Specifically, m-phenylenediamine, p-phenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,4' -diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, 3 , 3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 2,2-bis(3-aminophenyl)propane, 2 -(3-aminophenyl)-2-(4-aminophenyl)propane, 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, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4 -bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 3,3'-bis(4-aminophenoxy)biphenyl, 3,4'-bis(3-aminophenoxy) Biphenyl, bis[4-(4-aminophenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfide, bis[4-(3-aminophenoxy)phenyl]sulfide, bis[3-(4 -aminophenoxy)phenyl]sulfide, bis[3-(3-aminophenoxy)phenyl]sulfide, bis[3-(4-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenyl)]sulfone, bis [3-(3-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenyl)]sulfone, bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-amino phenoxy)phenyl] ether, bis[3-(3-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]methane, bis[4-(4-aminophenoxy)phenyl L]methane, bis[3-(3-aminophenoxy)phenyl]methane, bis[3-(4-aminophenoxy)phenyl]methane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]propane, 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-hexafluoro Propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[3-(4-aminophenoxy)phenyl ]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis[4-(4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 1, 3-bis[4-(4-amino-6-fluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4 ,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl and the like. .

These aromatic diamine compounds may be used alone, or two or more aromatic diamine compounds may be used. From the viewpoint of transparency and heat resistance, 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, 2,2-bis[3-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 1,3-bis[4-( 4-amino-6-trifluoromethylphenoxy)-α,α-dimethylbenzyl]benzene, 3,3′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis(trifluoro Examples include aromatic diamine compounds having a fluoro group such as methyl)-4,4'-diaminobiphenyl, and at least one of the aromatic diamine compounds used is preferably an aromatic diamine compound having a fluoro group, particularly 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl is preferred. By using an aromatic diamine compound having a fluoro group, it becomes easy to obtain transparency, heat resistance, and solubility in a solvent.

As the 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. 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. These 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. For example, 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. A method of obtaining polyamic acid by adding an aromatic diamine compound while stirring and reacting, a method of obtaining polyamic acid by alternately adding an aromatic diamine compound and a tetracarboxylic dianhydride and reacting them, etc. are 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.

In addition, 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 1.001-1.02, more preferably 1.001-1.01. By making the tetracarboxylic dianhydride slightly excessive relative to the aromatic diamine compound in this way, 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. As 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.

For the chemical imidization reaction, aliphatic, aromatic or heterocyclic tertiary amines such as pyridine, picoline, quinoline, isoquinoline, trimethylamine and triethylamine can be used as imidization accelerators. By using such amines, the imidization reaction can be efficiently carried out at a low temperature, and as a result, it becomes possible to suppress coloring during the imidization reaction, making it easier to obtain a more transparent polyimide.

Although there are no particular restrictions on 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. By performing the chemical imidization reaction at a temperature of 10° C. or more and less than 50° C., coloration during the imidization reaction can be suppressed, and a polyimide having excellent transparency can be obtained.

After that, if necessary, 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 is preferably soluble in low-boiling 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, it is possible to easily form a curable resin layer, which will be described later, comprising a cured product of the curable resin composition 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 can be greatly improved. In addition, the skeleton is linear and has relatively high flexibility, which facilitates increasing the breaking elongation of the cured resin layer. Furthermore, 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 coating can be performed using a solution casting method to form a curable resin layer as a coating film, 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.

A polyarylate resin is a resin made of a polymer compound obtained by reacting an aromatic diol with an aromatic dicarboxylic acid or its chloride. Polyarylate resins also have relatively high Tg and relatively good elongation properties. The polyarylate resin is not particularly limited, and known ones can be used.

Examples of 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. 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-bromophenylmethane, bis(3,5-dimethyl-4-hydroxyphenyl)-4-fluorophenylmethane , 1,1-bis(4′-hydroxyphenyl)-1-phenylethane [bisphenol P], 1,1-bis(3′-methyl-4′-hydroxyphenyl)-1-phenylethane, 1,1- Bis(3′-t-butyl-4′-hydroxyphenyl)-1-phenylethane, 1,1-bis(3′-phenyl-4′-hydroxyphenyl)-1-phenylethane, 1,1-bis( 4′-hydroxyphenyl)-1-(4′-nitrophenyl)ethane, 1,1-bis(3′ -bromo-4′-hydroxyphenyl)-1-phenylethane, 1,1-bis(4′-hydroxyphenyl)-1-phenylpropane, bis(4-hydroxyphenyl)diphenylmethane, bis(4-hydroxyphenyl)di bis(hydroxyphenyl)phenylalkanes such as benzylmethane; bis(hydroxyphenyl)ethers such as bis(4-hydroxyphenyl)ether and bis(3-methyl-4-hydroxyphenyl)ether; bis(4-hydroxyphenyl) ) ketones, bis (hydroxyphenyl) ketones such as bis (3-methyl-4-hydroxyphenyl) ketone; bis (4-hydroxyphenyl) sulfide, bis (3-methyl-4-hydroxyphenyl) sulfide and other bis ( hydroxyphenyl) sulfides; bis(4-hydroxyphenyl) sulfoxide, bis(3-methyl-4-hydroxyphenyl) sulfoxide and other bis(hydroxyphenyl) sulfoxides; bis(4-hydroxyphenyl) sulfone [bisphenol S], Bis(hydroxyphenyl)sulfones such as bis(3-methyl-4-hydroxyphenyl)sulfone; 9,9-bis(4′-hydroxyphenyl)fluorene, 9,9-bis(3′-methyl-4′- bis(hydroxyphenyl)fluorenes such as hydroxyphenyl)fluorene;

Examples of 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. Further, the polyarylate-based resin to be used may be a modified polyarylate-based resin. Among these, 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 weight average molecular weight (Mw) of the polymer component (A) is preferably 100,000 or more, more preferably 100,000 to 3,000,000, still more preferably 100,000 to 2,000,000, and particularly preferably is in the range of 100,000 to 500,000. Also, the molecular weight distribution (Mw/Mn) is preferably in the range of 1.0 to 5.0, more preferably 2.0 to 4.5. 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. By setting Mw to 100,000 or more, it becomes easy to increase the breaking elongation of the cured resin layer.

The polymer component (A) can be used singly or in combination of two or more. Also, the polymer component (A) and the polymer component (A') having a glass transition temperature of less than 250°C may be used in combination. Examples of the polymer component (A′) include polyamide resins and polyarylate resins having a Tg of less than 250° C. Polyamide resins are preferred.

As the polyamide resin, one that is soluble in an organic solvent is preferable, and a rubber-modified polyamide resin is preferable. As the rubber-modified polyamide resin, for example, those described in JP-A-2004-035638 can be used.

As the polymer component (A) and the polymer component (A'), 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.

When adding a polyamide resin or a polyarylate resin having a Tg of less than 250 ° C. to the polyimide resin, 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, 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 (B)>
The curable resin composition of the present invention contains a curable monomer (B) having 3 or more curable functional groups.

The curable monomer (B) is a monomer having a curable functional group (polymerizable unsaturated bond), and is a monomer that can participate in a polymerization reaction or a polymerization reaction and a cross-linking reaction. In this specification, the term "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 (B) is generally 3,000 or less, preferably 100-2,000, more preferably 100-1,500.
The number of curable functional groups (polymerizable unsaturated bonds) in the curable monomer (B) is 3 or more. When the number of curable functional groups in the curable monomer (B) is less than 3, the storage elastic modulus, linear expansion coefficient, etc. of the cured resin layer described later, which is the curable resin composition and its cured product, The heat resistance related to may decrease. The number of curable functional groups in the curable monomer (B) is preferably 3 to 10, more preferably 4 to 8, still more preferably 4 to 6, particularly preferably 4. . When the number of curable functional groups in the curable monomer (B) is within this range, when used in combination with the polymer component (A), the rate of decrease in storage elastic modulus is small even at high temperatures, and linear A curable resin composition having a small coefficient of expansion and excellent heat resistance and a cured resin layer as a cured product thereof can be obtained.

Examples of the polyfunctional monomers 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 tri- to hexa-functional (meth)acrylic acid derivatives.

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, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. mentioned.

Pentafunctional (meth)acrylic acid derivatives include propionic acid-modified dipentaerythritol penta(meth)acrylate.

Hexafunctional (meth)acrylic acid derivatives include dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

A cyclization-polymerizable monomer may be used as the curable monomer (B). 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, α-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.
In addition, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2 '-[oxybis(methylene)]bis-2-propenoate, di(i-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-butyl)-2,2'- [oxybis(methylene)]bis-2-propenoate, di(n-hexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl-2,2'-[oxybis(methylene)]bis Cyclopolymerizable monomers such as -2-propenoate can also be used.

The curable monomer (B) can be used singly or in combination of two or more.
The content of the curable monomer (B) having three or more curable functional groups is preferably 40% by mass or more, more preferably 50 to 100% by mass, based on the total amount of the curable monomer (B). , more preferably 80 to 100% by mass, particularly preferably 90 to 100% by mass.

The curable resin composition of the present invention comprises a polymer component (A), a curable monomer (B) having three or more curable functional groups, and optionally a polymerization initiator and other components described later. It can be prepared by mixing and dissolving or dispersing in a suitable solvent.

The total content of the polymer component (A) and the curable monomer (B) having three or more curable functional groups in the curable resin composition is the total content of the curable resin composition excluding the solvent. It is preferably 40 to 99.5% by mass, more preferably 60 to 99% by mass, still more preferably 80 to 98% by mass, based on the mass.

The content of the polymer component (A) and the curable monomer (B) having three or more curable functional groups in the curable resin composition is the polymer component (A) and three or more cured The mass ratio with the curable monomer (B) having a functional group is preferably polymer component (A): curable monomer (B) having 3 or more curable functional groups = 20: 80-90:10, more preferably 30:70-80:20.
In the curable resin composition, when the mass ratio of the polymer component (A):the curable monomer (B) having 3 or more curable functional groups is within this range, the resulting cured resin layer is cured at high temperatures. The decrease rate of the storage elastic modulus is suppressed, the heat resistance related to the coefficient of linear expansion is more likely to be improved, and the solvent resistance of the cured resin layer is more likely to be maintained.

As the polymer component (A), when using a combination of a plurality of resins with 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 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.
Examples of 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 photoinitiators such as phenylphosphinate and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide; bis(η ⁵ -2,4-cyclopentadien-1-yl) )-Bis[2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl]titanium titanocene-based photopolymerization initiator; 1,2-octanedione-1-[4-(phenylthio)- 2-(O-benzoyloxime)], ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) and other oxime esters Photopolymerization initiator; benzophenone, p-chlorobenzophenone, benzoylbenzoic acid, o-methylbenzoylbenzoate, 4-methylbenzophenone, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl-diphenyl benzophenones such as sulfide, 3,3′-dimethyl-4-methoxybenzophenone, 2,4,6-trimethylbenzophenone, 4-(13-acryloyl-1,4,7,10,13-pentoxatridecyl)-benzophenone Photopolymerization initiator; thioxanthone, 2-chlorothioxanthone, 3-methylthioxanthone, 2,4-dimethylthioxanthone thioxanthone-based photopolymerization initiators such as tilthioxanthone, 2,4-diisopropylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, and 4-isopropylthioxanthone; is mentioned.

Among the above photoinitiators, 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.
When the polymer component (A) is a thermoplastic resin having an aromatic ring, the polymer component (A) absorbs ultraviolet rays, and as a result, the curing reaction may be difficult to occur. However, by using the above phosphorus-based photopolymerization initiator, it is possible to efficiently proceed the curing reaction using light of a wavelength that is not absorbed by the polymer component (A).
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, relative to the entire curable resin composition.

In addition to the polymer component (A), a curable monomer (B) having three or more curable functional groups, and a polymerization initiator, the curable resin composition includes triisopropanolamine and 4 , 4'-diethylaminobenzophenone or the like may be contained.

The solvent used for preparing the curable resin composition 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; and dichloromethane. , ethylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, monochlorobenzene and other halogenated hydrocarbon solvents; methanol, ethanol, propanol, butanol, propylene glycol monomethyl ether and other alcohol solvents; acetone, methyl ethyl ketone, 2 - ketone solvents such as 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 is not particularly limited, but is usually 0.1 to 1,000 g, preferably 1 to 50 g, per 1 g of polymer component (A). By appropriately adjusting the amount of the solvent, the viscosity of the curable resin composition can be appropriately adjusted.

In addition, the curable resin composition 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.

<Cured resin layer>
The cured resin layer consists of a cured product of a curable resin composition containing a polymer component (A) and a curable monomer (B) having three or more curable functional groups.
FIG. 1 is a cross-sectional view showing an example of the cured resin layer of the present invention. The cured resin layer 1 may be a single layer or multiple layers.
The method for forming the cured resin layer will be described in detail in the method for manufacturing a laminate, which will be described later.

Reduction rate R of the storage elastic modulus (E' ₁₅₀ ) at 150° C. to the storage elastic modulus (E' ₃₀ ) at 30° C. of the cured resin layer (<(E' ₃₀ −E' ₁₅₀ )/E' ₀ >×100) is preferably 45% or less, more preferably 38% or less, still more preferably 30% or less. When the rate of decrease R is within this range, the heat resistance of the cured resin layer becomes higher. When a manufacturing process involving heating is performed after formation, the rate of decrease in storage elastic modulus at high temperatures is suppressed, and mechanical damage (for example, fine cracks, peeling, etc.) to the functional layer is less likely to occur, and the functional layer It is possible to sufficiently exhibit the predetermined function that is originally possessed by
The storage elastic modulus was measured by the method described in Examples below.

The coefficient of linear expansion of the cured resin layer at 30° C. to 150° C. is preferably 95 ppm/K or less, more preferably 90 ppm/K or less, still more preferably 87 ppm/K or less. When the coefficient of linear expansion is within this range, the heat resistance of the cured resin layer becomes higher. For example, as described above, a functional layer, which will be described later, is formed on the cured resin layer by coating and heat drying to form a laminate. For example, when a manufacturing process involving heating is performed after forming the cured resin layer, an increase in dimensions at high temperatures is suppressed, and mechanical deformation (e.g., warping, etc.) of the functional layer is less likely to occur, and the functional layer is originally It is possible to sufficiently exhibit the predetermined functions that it has.
The coefficient of linear expansion was measured by the method described in Examples below.

The total light transmittance of the cured resin layer is preferably 85% or higher, more preferably 90% or higher, still more preferably 95% or higher. When the total light transmittance is in this range, for example, when a functional layer to be described later is formed to form a laminate, the transparency of the entire laminate can be easily maintained, and for example, it can be used for optical purposes. can.

The haze value of the cured resin layer is preferably 1.0% or less, more preferably 0.5% or less, and even more preferably 0.1% or less. When 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 for example, it can be used for optical purposes. .

The thickness of the cured resin layer is not particularly limited, and may be appropriately adjusted, for example, according to the purpose of the laminate having a functional layer, which will be described later. The thickness of the cured resin layer is usually 50 μm or less, preferably 20 μm or less, more preferably 0.1 to 20 μm, even more preferably 0.1 to 10 μm, particularly preferably 0.2 to 10 μm.
When the thickness of the cured resin layer is within this range, it is possible to prevent the thickness of the laminate to be described later from becoming large, and it is possible to obtain a thin laminate. 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. Moreover, if the laminate is thin, flexibility after mounting of the laminate can be secured.

The cured resin layer of the present invention is excellent in solvent resistance. Because of its excellent solvent resistance, even when an organic solvent is used to form another layer on the surface of the cured resin layer, the surface of the cured resin layer is hardly dissolved. Therefore, for example, even when the functional layer is formed on the surface of the cured resin layer using a resin solution containing an organic solvent, the components of the cured resin layer are less likely to penetrate into the functional layer. is difficult to decrease.
From the above viewpoint, the gel fraction of the cured resin layer is preferably 90% or more, more preferably 93% or more, still more preferably 98% or more, and particularly preferably 100%. A cured resin layer having a gel fraction of 93% or more has excellent solvent resistance. It is possible to easily obtain a layered product in which the layer surface is hardly dissolved and which is excellent in solvent resistance.
The gel fraction was measured by the method described in Examples below.

(Laminate)
As one aspect of the present invention, it is preferable to provide a functional layer on the cured resin layer.
FIG. 2 is a schematic cross-sectional view showing an example of a laminate using the cured resin layer of the present invention. In FIG. 2, a laminate 11 is, for example, a laminate of a functional layer 2 on a cured resin layer 1, and the cured resin layer 1 can be used as a layer or a substrate on which the functional layer 2 is provided.
Moreover, as another aspect of the present invention, the laminate may include a process film, a cured resin layer, and a functional layer in this order. When the laminate is actually used, the process film is peeled off from the laminate, and the laminate is attached to an electronic device such as a predetermined display.
Since the cured resin layer of the present invention exhibits a small decrease in storage elastic modulus at high temperatures and an excellent coefficient of linear expansion, it is more preferably used in a manufacturing process including a heat treatment step at high temperatures.
The functional layer is not particularly limited, and examples thereof include 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. In addition, the arrangement position of the functional layer is not particularly limited.

For example, 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. In 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 μm, preferably 20 nm to 20 μm.

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 be used. Epoxy-based adhesive is preferable as the material constituting the .
Similarly, the pressure-sensitive adhesive layer is a layer used, for example, when attaching the laminate to an adherend or the like. Examples of 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. Also, 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 adhesive layer may be appropriately selected according to its use. It is usually 1 μm to 50 μm, preferably 5 μm to 25 μm.

The thickness of the laminate can be determined as appropriate depending on the intended use, such as an adherend or an electronic device. A substantial thickness of the laminate is preferably 0.3 to 50 μm, more preferably 0.5 to 25 μm, and more preferably 0.7 to 12 μm from the viewpoint of handleability.
In addition, "substantial thickness" means the thickness in the state of use. That is, the laminate may have a process film, etc. as described above, but the thickness of the portion (process film, etc.) that is removed during use is not included in the "substantial thickness". do not have.

(Laminate manufacturing method)
The laminate of the present invention can be produced using a process film as one aspect. By using the process film, the laminate can be produced efficiently and easily.

The method for producing a laminate of the present invention includes the following (Step 1) to (Step 3).
(Step 1): A curable resin layer is formed on a process film using a curable resin composition containing a polymer component (A) and a curable monomer (B) having three or more curable functional groups. Step of forming (Step 2): Step of forming a cured resin layer by curing the curable resin layer obtained in Step 1 (Step 3): On the cured resin layer obtained in Step 2, a functional layer the process of forming

The method of applying the curable resin composition onto the process film is not particularly limited, and may be spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, or gravure coating. A known coating method such as a 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 80 to 130°C.

The curable resin layer obtained in step 1 is cured to form a cured resin layer.
A method for curing the curable resin layer is not particularly limited, and a known method can be employed. For example, when the curable resin layer is formed using a curable resin composition containing a thermal polymerization initiator, the curable resin layer can be cured by heating the curable resin layer. . The heating temperature is usually 30 to 150°C, preferably 50 to 130°C.
Further, when the curable resin layer is formed using a curable resin composition containing a photopolymerization initiator, the curable resin layer is cured by irradiating the curable resin layer with an active energy ray. can be made 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 irradiation dose is usually in the range of illuminance of 50 to 1,000 mW/cm ² and light intensity of 50 to 5,000 mJ/cm ² , preferably 1,000 to 5,000 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.

In this case, in order to prevent deterioration of the polymer component (A) and coloration of the curable resin layer due to irradiation of the active energy ray, a filter that absorbs light of a wavelength unnecessary for the curing reaction is interposed, and the active energy ray may be applied to the curable resin composition. According to this method, the filter absorbs light of a wavelength that is unnecessary for the curing reaction and degrades the polymer component (A). It becomes easy to obtain a resin.
A resin film such as a polyethylene terephthalate film can be used as the filter. When using a resin film, it is preferable to provide a step of laminating a resin film such as a polyethylene terephthalate film on the curable resin layer between

steps

1 and 2 . The resin film is usually peeled off after step 2.

The curable resin layer can also be cured by irradiating the curable resin layer with an electron beam. When electron beams are applied, the curable resin layer can be cured usually without using a photopolymerization initiator. When irradiating with an electron beam, 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.

The curing of the curable resin layer 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.

A desired functional layer is formed on the cured resin layer obtained in step 2.
As a method for forming the functional layer, the method described above can be appropriately adopted.

When the laminate has a process film, the laminate may have the process film on one side or both sides. In the latter case, it is preferable to use two types of process films and make the process film to be peeled off first easier to peel.
The process film is preferably sheet-like or film-like. The term "sheet-like" or "film-like" includes not only a long one but also a short flat plate-like one.
Process films include paper base materials such as glassine paper, coated paper, and fine paper; laminated paper obtained by laminating these paper base materials with thermoplastic resins such as polyethylene and polypropylene; Those subjected to filling treatment with alcohol, acrylic-styrene resin, etc.; plastic films such as polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, and polyolefin films such as polyethylene and polypropylene; and glass.
Further, the process film may be a paper substrate or a plastic film having a release agent layer provided thereon from the viewpoint of ease of handling. The release layer can be formed using conventionally known release agents such as silicone release agents, fluorine release agents, alkyd release agents, and olefin release agents.
The thickness of the release agent layer is not particularly limited, but is usually 0.02 to 2.0 μm, more preferably 0.05 to 1.5 μm.
The thickness of the process film is preferably 1 to 500 μm, more preferably 5 to 300 μm, from the viewpoint of ease of handling.
Incidentally, the process film is usually peeled off in a predetermined process depending on the use of the laminate.

Thus, the manufacturing method including the above (Step 1) to (Step 3) forms a cured resin layer using a process film, and the laminate obtained by this method has a process film. may or may not have.
According to the above-described method for manufacturing a laminate, the laminate according to one aspect of the present invention can be efficiently, continuously, and easily produced.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

The storage modulus, coefficient of linear expansion, total light transmittance, haze value, and solvent resistance (molar fraction) of the cured resin layers prepared in Examples and Comparative Examples were evaluated by the following methods.

(1) Storage modulus A laminate having a thickness of 40 μm was obtained by laminating four cured resin layers obtained by peeling and removing polyethylene terephthalate (PET) films as process films on both sides obtained in Examples and Comparative Examples. did. Next, cut into a test piece of 5 mm × 30 mm, set the distance between chucks to 15 mm using a thermomechanical analyzer (manufactured by NETZSCH Japan, product name "DMA242"), and hold the laminate of the cured resin layers. did. Next, the laminate of the cured resin layers was heated from 30° C. to 280° C. at a frequency of 10 Hz, an amplitude of 15 μm, and a heating rate of 3° C./min to measure the viscoelasticity. The modulus E' ₃₀ (MPa) and the storage modulus E' ₁₅₀ (MPa) at 150 ° C. are obtained, and the storage modulus decrease rate R [<(E' ₃₀ -E' ₁₅₀ )/E' ₃₀ > x 100 (% )] was calculated.
(2) Coefficient of Linear Expansion In the same manner as in (1) above, four cured resin layers from which polyethylene terephthalate (PET) films as process films on both sides were peeled off were laminated to form a laminate having a thickness of 40 μm. Next, a test piece of 5 mm × 30 mm is cut, and a thermomechanical analyzer (manufactured by NETZSCH Japan, product name “TMA4030SE”) is used to set the distance between chucks to 10 mm, and the laminate of the cured resin layers is obtained. grasped. Then, the laminate of the cured resin layer was heated from 30° C. to 150° C. at a load of 3 g and a temperature increase rate of 5° C./min. /K) was calculated.
(3) Light transmittance, haze value The cured resin layers obtained in Examples and Comparative Examples were cut into test pieces of 50 mm x 50 mm, and the test pieces were measured using a haze meter ( The total light transmittance (%) was measured using a product name “SH-7000” manufactured by Nippon Denshoku Industries Co., Ltd.).
Similarly, the haze value (%) was measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "SH-7000") according to JIS K7136:2000.
(4) Solvent resistance (gel fraction)
The cured resin layer obtained in Examples and Comparative Examples, obtained by peeling and removing polyethylene terephthalate (PET) films as process films on both sides, was wrapped with a mesh (α_UX SCREEN 150-035/380TW manufactured by NBC Meshtec Co., Ltd.), A stapled construction was taken and the weight of the construction was measured. Next, the structure was immersed in a bottle filled with a methyl ethyl ketone (MEK) solvent, sealed, and left at 25° C. for 36 hours. After that, the structure was taken out from the solvent, dried at 100° C. for 60 minutes, and the weight of the structure after drying was measured. The gel fraction was calculated as a percentage (%) after dividing the weight of the structure after drying by the weight of the structure before being immersed in MEK (methyl ethyl ketone) solvent.

(Example 1)
- Formation of cured resin layer A curable resin composition was prepared as follows.
As the polymer component (A), polyimide resin (PI) powder (manufactured by Kawamura Sangyo Co., Ltd., product name “KPI-MX300F”, Tg = 354 ° C., weight average molecular weight 280,000) 100 parts by weight of methyl ethyl ketone (MEK) and A 15% by mass solution of PI was prepared by dissolving in toluene (MEK:toluene=1:1). Next, in this solution, trifunctional tris-(2-acryloxyethyl) isocyanurate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-9300, molecular weight: 423.4) 122 mass as a curable monomer (B) and 5 parts by mass of (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (OMNIRAD TPO, manufactured by IGM Resins) as a polymerization initiator. A flexible resin composition was prepared. The curable monomers and polymerization initiators used in Example 1 and other experimental examples do not contain solvents and are all raw materials with a solid content of 100%.
Next, as a process film, a polyethylene terephthalate (PET) film (manufactured by Toyobo Co., Ltd., PET100A-4100, thickness 50 μm) having an easy-adhesion layer on one side was used. A curable resin composition was applied to the surface, and the resulting coating film was dried by heating at 100° C. for 2 minutes.
Furthermore, a PET film (manufactured by Toyobo Co., Ltd., Cosmo Shine A4100, thickness 50 μm) is laminated on the dried coating film so that the surface opposite to the easy-adhesion surface faces each other, and a conveyor type ultraviolet irradiation device (Heraus company, device name “CV-100Q-G”), UV lamp height 85 mm, UV lamp output 100%, line speed 3.7 m/min, light wavelength 365 nm, illuminance 400 mW/cm ² , light amount Under the condition of 800 mJ/cm ² (measured with UV Power Puck (registered trademark) II manufactured by Heraus), a curing reaction was performed by irradiating ultraviolet rays through a PET film to form a cured resin layer with a thickness of 10 μm.
The storage elastic modulus, linear expansion coefficient, total light transmittance, haze value and solvent resistance (molar fraction) of the obtained cured resin layer were evaluated. Table 1 shows the results.

(Example 2)
Instead of the curable monomer (B) in the curable resin composition of Example 1, tetrafunctional pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT, molecular weight: 352.3) was used. A cured resin layer having a thickness of 10 μm was formed in the same manner as in Example 1 except for the above.
The storage elastic modulus, linear expansion coefficient, total light transmittance, haze value and solvent resistance (molar fraction) of the obtained cured resin layer were evaluated. Table 1 shows the results.

(Example 3)
Instead of the curable monomer (B) in the curable resin composition of Example 1, hexafunctional dipentaerythritol polyacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DPH, molecular weight: 578.6) is used. A cured resin layer having a thickness of 10 μm was formed in the same manner as in Example 1, except for the addition.
The storage elastic modulus, linear expansion coefficient, total light transmittance, haze value and solvent resistance (molar fraction) of the obtained cured resin layer were evaluated. Table 1 shows the results.

(Comparative example 1)
Instead of the curable monomer (B) in the curable resin composition of Example 1, bifunctional tricyclodecanol acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., A-DCP, molecular weight 304.4) was used. A cured resin layer having a thickness of 10 μm was formed in the same manner as in Example 1 except for the above.
The storage elastic modulus, linear expansion coefficient, total light transmittance, haze value and solvent resistance (molar fraction) of the obtained cured resin layer were evaluated. Table 1 shows the results.

(Comparative example 2)
Instead of the curable monomer (B) in the curable resin composition of Example 1, bifunctional ethoxylated bisphenol A diacrylate (Shin-Nakamura Chemical Co., Ltd., ABE-300, molecular weight 468.6) is used. A cured resin layer having a thickness of 10 μm was formed in the same manner as in Example 1, except for the addition.
The storage elastic modulus, linear expansion coefficient, total light transmittance, haze value and solvent resistance (molar fraction) of the obtained cured resin layer were evaluated. Table 1 shows the results.

The chemical structural formula of the curable monomer (B) used in Examples and Comparative Examples is shown below.

The cured resin layer of Examples 1, 2 or 3 using a curable monomer having 3, 4 or 6 curable functional groups in the curable resin composition has two curable functional groups in the curable resin composition. Compared to the cured resin layers of Comparative Examples 1 and 2 using a curable monomer having a group, the rate of decrease in storage elastic modulus is small even at high temperatures, the coefficient of linear expansion is small, and the layer has solvent resistance. Furthermore, it was found that the total light transmittance and haze value were maintained.

According to the curable resin composition of the present invention, the cured resin layer made of the cured product has a small decrease rate of storage elastic modulus and a small linear expansion coefficient even at high temperatures, and furthermore has a total light transmittance and a haze value. is maintained, and since it is thin and flexible, members such as electronic devices and optical films that are required to be manufactured at high temperatures, for example, as a hard coat layer for antireflection films, It is also expected to be applied to members such as flexible organic EL elements and flexible thermoelectric conversion elements.

1: Cured resin layer 2: Functional layer 11: Laminate

Claims

A curable resin composition containing a polymer component (A) and a curable monomer (B) having three or more curable functional groups.
The curable resin composition according to claim 1, wherein the polymer component (A) has a glass transition temperature of 250°C or higher.
The curable resin composition according to claim 1 or 2, wherein the polymer component (A) has a weight average molecular weight of 100,000 or more.
The curable resin composition according to any one of claims 1 to 3, wherein the polymer component (A) is a polyimide resin.
The cured resin layer according to any one of claims 1 to 4, wherein the cured resin layer comprises a cured product of the curable resin composition and has a thickness of 20 µm or less.
Reduction rate R of storage elastic modulus (E' 150 ) at 150° C. to storage elastic modulus (E' 30 ) at 30° C. of the cured resin layer (<(E' 30 −E' 150 )/E' 30 >×100 ) is 45% or less, the cured resin layer according to claim 5.
The cured resin layer according to claim 5 or 6, wherein the cured resin layer has a linear expansion coefficient of 95 ppm/K or less at 30°C to 150°C.
The cured resin layer according to any one of claims 5 to 7, wherein the cured resin layer has a total light transmittance of 85% or more.
The cured resin layer according to any one of claims 5 to 7, wherein the cured resin layer has a haze value of 1.0% or less.
The laminate according to any one of claims 5 to 9, comprising a functional layer on the cured resin layer.