TWI786185B - Curable composition - Google Patents

Abstract

The present invention provides a curable composition which comprises: a multifunctional (meth) acrylate monomer (A) containing at least two kinds selected from the group consisting of trifunctional (meth) acrylate monomer, tetrafunctional (meth) acrylate monomer and octafunctional (meth) acrylate monomer, and a cationic polymerizable monomer (B), wherein the total mass of the trifunctional (meth) acrylate monomer, the tetrafunctional (meth) acrylate monomer and the octafunctional (meth) acrylate monomer is 50 parts by mass or more based on 100 parts by mass of the polyfunctional (meth) acrylate monomer (A).

Description

hardening composition

This patent application is based on Japanese Patent Application No. 2017-178243 (filing date: September 15, 2017) claiming priority under the Treaty of Paris, and the entire content is hereby incorporated by reference into this specification .

The present invention relates to a curable composition capable of forming a laminate used as a front panel of an image display device, a cured film obtained by curing the curable composition, and a laminate including the cured film.

Image display devices such as liquid crystal display devices and organic EL display devices are widely used in various applications such as mobile phones and smart phones. The front panel of an image display device uses a laminate including a cured film obtained by curing a curable composition (for example, Patent Document 1).

[Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2009-202456

The front panel of such an image display device is required to have high surface hardness due to the direct contact of the user or the surrounding objects. Furthermore, when using the front panel of a flexible display, high bendability is also required. However, according to the research of the present inventors, it is known that the front panel of the conventional image display device cannot satisfy these characteristics simultaneously and sufficiently.

Therefore, an object of the present invention is to provide a curable composition capable of forming a laminate excellent in surface hardness and flexibility, a cured film obtained by curing the curable composition, and a laminate including the cured film.

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and found that if a compound containing a trifunctional (meth)acrylate monomer, a tetrafunctional (meth)acrylate monomer, and an octafunctional (meth)acrylic acid Trifunctional (methyl) When the total mass of an acrylate monomer, a tetrafunctional (meth)acrylate monomer, and an octafunctional (meth)acrylate monomer is more than a predetermined amount, the said subject can be solved, and this invention was completed further. That is, the present invention includes the following.

[1] A curable composition comprising: a composition selected from trifunctional (meth)acrylate monomers, tetrafunctional (meth)acrylate monomers and octafunctional (meth)acrylate monomers A curable composition of at least two kinds of multifunctional (meth)acrylate monomers (A) and cationically polymerizable monomers (B) in the group, wherein, relative to the multifunctional (meth)acrylate monomer 100 parts by mass of the body (A), the total mass of the trifunctional (meth)acrylate monomer, the tetrafunctional (meth)acrylate monomer, and the octafunctional (meth)acrylate monomer is 50 parts by mass or more.

[2] The curable composition according to [1], wherein the cationically polymerizable monomer (B) contains a cyclic ether compound having one or more epoxy groups and/or one or more oxetanyl groups (B-1).

[3] The curable composition according to [2], wherein the cyclic ether compound (B-1) contains a bicyclic ether compound having two or more epoxy groups and/or two or more oxetanyl groups. Ether compound (B-1-1).

[4] The curable composition according to any one of [1] to [3], wherein the cationically polymerizable monomer (B) further contains an ethylene oxide compound (B-2).

[5] The curable composition as described in [4], wherein the content of the polyfunctional (meth)acrylate monomer (A) is 5 to 80 parts by mass with respect to 100 parts by mass of the curable composition, and the cyclo The content of the ether compound (B-1) is 5 to 80 parts by mass, and the content of the vinyloxy compound (B-2) is 3 to 60 parts by mass.

[6] The curable composition according to [4] or [5], wherein 100% by mass of the total amount of the polyfunctional (meth)acrylate monomer (A) and the cationically polymerizable monomer (B) The content of the ethylene oxide compound (B-2) is 3 to 50 parts by mass.

[7] The curable composition according to any one of [2] to [6], wherein the cyclic ether compound (B-1) contains a radical polymerizable functional group having one or more radical polymerizable functional groups. Cyclic ether compound (B-1-2).

[8] The curable composition as described in [7], wherein the content of the polyfunctional (meth)acrylate monomer (A) is 5 to 50 parts by mass with respect to 100 parts by mass of the curable composition. The content of the cyclic ether compound (B-1-1) is 3 to 30 parts by mass, and the content of the radically polymerizable cyclic ether compound (B-1-2) is 5 to 40 parts by mass.

[9] The curable composition according to [7] or [8], wherein the radical polymerizable cyclic ether compound (B-1-1) is 1 part by mass of the bicyclic ether compound (B-1-1) The content of 1-2) is 0.1 to 10 parts by mass.

[10] The curable composition according to any one of [1] to [9], further comprising a radical polymerization initiator (C) and a cationic polymerization initiator (D).

[11] The curable composition according to [10], wherein the content of the radical polymerization initiator (C) is 1 to 100 parts by mass of the polyfunctional (meth)acrylate monomer (A). 15 parts by mass; the content of the cationic polymerization initiator (D) is 1 to 15 parts by mass relative to 100 parts by mass of the cationic polymerizable monomer (B).

[12] The curable composition according to any one of [1] to [11], which further contains inorganic particles.

[13] The curable composition according to [12], wherein when the inorganic particles are reactive silica particles, the content of the reactive silica particles is 1 to 70% by mass relative to the mass of the curable composition.

[14] A cured film obtained by curing the curable composition described in any one of [1] to [13].

[15] A laminate comprising the cured film described in [14] on at least one surface layer of a base film.

[16] The laminate according to [15], wherein the base film contains a polyimide-based polymer.

[17] The laminate according to [15] or [16], wherein the oxygen permeability is 800 cc/(m ² ·24h·atm) or less.

[18] A flexible display comprising the laminate according to any one of [15] to [17].

The curable composition of the present invention can form a laminate having excellent surface hardness and flexibility.

[1] Hardening composition

The curable composition of the present invention contains polyfunctional (meth)acrylate monomer (A) and cationic polymerizable monomer (B).

(1) Multifunctional (meth)acrylate monomer (A)

The so-called multifunctional (meth)acrylate monomer (A) means a compound having more than 2 (meth)acryloxy groups in the molecule. The multifunctional (meth)acrylate monomer (A) of the present invention ) includes at least two kinds selected from the group consisting of trifunctional (meth)acrylate monomers, tetrafunctional (meth)acrylate monomers, and octafunctional (meth)acrylate monomers. In addition, in this specification, the term "(meth)acrylate" means "acrylate" or "methacrylate", and the term "(meth)acryl" also means "acryl" or " Methacryl".

Trifunctional (meth)acrylate monomers are monomers having three (meth)acryloxy groups in the molecule, examples of which include: glyceryl tri(meth)acrylate, tri(meth)acrylate Methylolpropane, Di(trimethylol)propane Tri(Meth)acrylate, Neopentylthritol Tri(meth)acrylate, Reactant of Neopentylthritol Tri(meth)acrylate and Anhydride , Trimethylolpropane tri(meth)acrylate modified by caprolactone, Neopentylthritol tri(meth)acrylate modified by caprolactone, Tri(methyl)isocyanurate Acrylic ester, reactant of neopentylthritol tri(meth)acrylate modified by caprolactone and acid anhydride, etc. Among them, from the viewpoints of surface hardness, flexibility, oxygen barrier properties, and warpage resistance of a laminate having a cured film formed by curing a curable composition (sometimes referred to simply as a laminate), Trimethylolpropane tri(meth)acrylate is preferred. These trifunctional (meth)acrylate monomers can be used individually or in combination of 2 or more types.

In this specification, surface hardness means the surface hardness of the cured film side in the laminated body of this invention. The term "flexibility" refers to the property of suppressing the occurrence of cracks or the like when the laminate of the present invention is bent. The so-called oxygen barrier property refers to the property that oxygen is not easy to penetrate. The higher the oxygen barrier property, the lower the oxygen permeability or oxygen permeability. The so-called warpage resistance refers to the characteristic that it is not easy to cause warpage, and the higher the warpage resistance is, the less likely it is to cause warpage.

A 4-functional (meth)acrylate monomer is a monomer having 4 (meth)acryloxy groups in the molecule, examples of which include: di(trimethylol)propane tetra(meth)acrylate, Neopentylthritol tetra(meth)acrylate, dipentylthritol tetra(meth)acrylate, trineopentylthritol tetra(meth)acrylate, tetra(methyl)tetra(meth)acrylate modified by caprolactone Neopentylthritol acrylate, trineopentylthritol tetra(meth)acrylate modified by caprolactone, etc. Among these, neopentylthritol tetra(meth)acrylate is preferable from the viewpoint of the surface hardness, flexibility, oxygen barrier properties and warpage resistance of the laminate. These tetrafunctional (meth)acrylate monomers can be used individually or in combination of 2 or more types.

The 8-functional (meth)acrylate monomer is a monomer having 8 (meth)acryloxy groups in the molecule, examples of which include: octa(meth)acrylic acid trineopentyl glycolate, hexanol Ester-modified octa(meth)acrylate tri-neopentylthritol ester, etc. Among them, trineopentylthritol (meth)acrylate is preferable from the viewpoint of the surface hardness, flexibility, and oxygen barrier properties of the laminate. These 8 functional (meth)acrylate monomers can be used individually or in combination of 2 or more types.

The curable composition of the present invention contains a compound selected from the group consisting of 3-functional (meth)acrylate monomers, 4-functional (meth)acrylate monomers and 8-functional (meth)acrylate monomers. At least 2 kinds, and relative to 100 parts by mass of the polyfunctional (meth)acrylate monomer (A), a trifunctional (meth)acrylate monomer, a tetrafunctional (meth)acrylate monomer, and an octafunctional (meth)acrylate monomer Since the total mass of the acrylate monomers is 50 parts by mass or more, a laminate having excellent surface hardness and flexibility can be formed. Furthermore, the curable composition of the present invention can also form a laminate having excellent oxygen barrier properties and warpage resistance. The total mass of 3-functional (meth)acrylate monomers, 4-functional (meth)acrylate monomers and 8-functional (meth)acrylate monomers in 100 parts by mass of the curable composition of the present invention is preferably It is at least 60 parts by mass, particularly preferably at least 70 parts by mass, more preferably at least 80 parts by mass, particularly preferably at least 90 parts by mass, most preferably at least 100 parts by mass. When the total mass of the 3-functional (meth)acrylate monomer, the 4-functional (meth)acrylate monomer and the 8-functional (meth)acrylate monomer is within the above range, the surface hardness of the laminate can be further improved, Flexibility, oxygen barrier and warpage resistance.

In a preferred aspect of the present invention, the polyfunctional (meth)acrylate monomer in the curable composition of the present invention is composed of a trifunctional (meth)acrylate monomer and a tetrafunctional (meth)acrylate composed of monomers. Combining a trifunctional (meth)acrylate monomer and a tetrafunctional (meth)acrylate monomer is often advantageous from the viewpoint of surface hardness, flexibility, oxygen barrier properties, and warpage resistance. In addition, when an octafunctional (meth)acrylate monomer is contained, it may be advantageous from the viewpoint of flexibility.

The content of the tetrafunctional (meth)acrylate monomer is preferably 0.5 to 5 parts by mass, particularly preferably 1 to 3 parts by mass, relative to 1 part by mass of the trifunctional (meth)acrylate monomer. When the content of the tetrafunctional (meth)acrylate monomer is within the above range, it is easy to improve the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate.

The polyfunctional (meth)acrylate monomer (A) may contain other than trifunctional (meth)acrylate monomer, tetrafunctional (meth)acrylate monomer and octafunctional (meth)acrylate monomer (meth)acrylate monomer. The types of other (meth)acrylate monomers are not particularly limited, and examples thereof include: bifunctional (meth)acrylate monomers, pentafunctional (meth)acrylate monomers, hexafunctional (meth)acrylic acid monomers Ester monomers, 7-functional (meth)acrylate monomers, etc.

Bifunctional (meth)acrylate monomers include, for example, ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene di(meth)acrylate, Butylene glycol ester, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate and neopentyl glycol di(meth)acrylate, etc. base) alkylene glycol acrylate; diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate Di(meth)acrylate polyoxyalkylene glycols such as ester, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate esters; di(meth)acrylates such as tetrafluoroethylene glycol di(meth)acrylates are halogen-substituted alkyl glycol esters; trimethylolpropane di(meth)acrylates, di(meth)acrylates di( Aliphatic polyol di(meth)acrylate such as trimethylol)propane ester and neopentylthritol di(meth)acrylate; hydrogenated dicyclopentadienyl di(meth)acrylate, di(methyl)acrylate ) Di(meth)acrylates of hydrogenated dicyclopentadiene or tricyclodecanedialkanol such as tricyclodecane dimethanol acrylate; 1,3-dioxane-2,5 di(meth)acrylate -Di(meth)acrylates of dioxane diols or dioxane dialkanols such as diyl esters [alias: dioxanediol di(meth)acrylate]; bisphenol A ethylene oxide plus Di(meth)acrylate of bisphenol A or alkylene oxide adduct of bisphenol F such as diacrylate, bisphenol F ethylene oxide adduct diacrylate; bisphenol A Di(meth)acrylate epoxy ester of bisphenol A or bisphenol F, such as acrylic acid adducts of diglycidyl ether and acrylic acid adducts of bisphenol F diglycidyl ether; di(meth)acrylic polysilicon oxyesters; di(meth)acrylates of neopentyl glycol hydroxytrimethylacetate; 2,2-bis[4-(meth)acryloxyethoxyethoxyphenyl]propane; 2 ,2-bis[4-(meth)acryloxyethoxyethoxycyclohexyl]propane; 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5 -di(meth)acrylate of hydroxyethyl-1,3-dioxane]; di(meth)acrylate tris(hydroxyethyl)isocyanurate, etc. These bifunctional (meth)acrylate monomers can be used alone or in combination of two or more.

Pentafunctional (meth)acrylate monomers include, for example, dipenteopentyl penta(meth)acrylate, trineopentyl penta(meth)acrylate, dipenteopentyl penta(meth)acrylate, The reactant of alcohol ester and acid anhydride, dipentyl penta(meth)acrylate modified by caprolactone, tri-neopentyl glycol penta(meth)acrylate modified by caprolactone, Lactone-modified pentapentyl (meth)acrylate reactant with acid anhydride, etc. These pentafunctional (meth)acrylate monomers can be used individually or in combination of 2 or more types.

The hexafunctional (meth)acrylate monomers include, for example, dipenteopentylthritol hexa(meth)acrylate, trineopentylthritol hexa(meth)acrylate, hexa(methyl)hexa(meth)acrylate modified with caprolactone, ) dipenteoerythritol acrylate, caprolactone modified hexa(meth)acrylate, etc. These hexafunctional (meth)acrylate monomers can be used alone or in combination of two or more.

The 7-functional (meth)acrylate monomers include, for example: trineopentylthritol hepta(meth)acrylate, the reactant of trineopentylthritol hepta(meth)acrylate and acid anhydride, Quality hepta(meth)acrylate tri-neopentylthritol, reactant of hepta(meth)acrylate modified with caprolactone and acid anhydride, etc. These seven functional (meth)acrylate monomers can be used individually or in combination of 2 or more types.

The curable composition of the present invention contains a cationically polymerizable monomer (B). The cation polymerizable monomer (B) means a compound having a cation polymerizable group in the molecule. From the viewpoint of the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate, it is preferable that the cationically polymerizable monomer (B) contains a compound selected from the group having one or more epoxy groups and/or one or more epoxy groups. At least one of oxetanyl cyclic ether compound (B-1) and vinyloxy compound (B-2).

(I) Cyclic ether compound (B-1)

Examples of the cyclic ether compound (B-1) include epoxy compounds having one or more epoxy groups in the molecule [referred to as epoxy compounds (b)], and oxetanes having one or more in the molecule. radical oxetane compound [referred to as oxetane compound (b)], radical polymerizable cyclic ether compound (B-1-2) having one or more radical polymerizable functional groups, and the like. An epoxy compound (b), an oxetane compound (b), and a radical polymerizable cyclic ether compound (B-1-2) can be used individually or in combination of 2 or more types.

The epoxy group in the epoxy compound (b) is preferably unsubstituted or modified with a hydrocarbon group having 6 or less, preferably 3 or less carbons, and is especially preferably unsubstituted. As the epoxy compound (b), it is preferable to use an aliphatic epoxy compound (b1), an alicyclic epoxy compound (b2), or an aromatic epoxy compound (b3). These epoxy compounds (b) can be used individually or in combination of 2 or more types.

The aliphatic epoxy compound (b1) is a compound having at least one, preferably at least two, epoxy groups bonded to an aliphatic carbon atom in the molecule. Aliphatic epoxy compounds (b1) include, for example: 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, neopentyl glycol Bifunctional epoxy compounds such as diglycidyl ether; trimethylolpropane triglycidyl ether, neopentylthritol tetraglycidyl ether, and other trifunctional or higher epoxy compounds. Among these, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether are preferably equal to those having 2 aliphatic carbon atoms in the molecule. Bifunctional epoxy compounds (aliphatic diepoxy compounds) with bonded epoxy groups. These aliphatic epoxy compounds (b1) can be used individually or in combination of 2 or more types.

式(a)中，m為2至5的整數。 The alicyclic epoxy compound (b2) is a compound having at least one epoxy group bonded to an alicyclic ring in the molecule, preferably a compound having two or more epoxy groups in the molecule, especially preferably It is a compound (alicyclic diepoxy compound (b2)) having two epoxy groups in the molecule. The so-called "epoxy group bonded to an alicyclic ring" means an oxygen atom -O- cross-linked in the structure represented by formula (a):

In formula (a), m is an integer of 2-5.

In formula (a), a compound formed by bonding two or more forms of one or more hydrogen atoms in (CH ₂ ) _m to other chemical structures can be an alicyclic epoxy compound (b2) . One or more hydrogen atoms in (CH ₂ ) _m may be appropriately substituted with a linear alkyl group such as a methyl group or an ethyl group.

Among them, an alicyclic ring having an epoxycyclopentane structure [where m=3 in the formula (a)] or an epoxycyclohexane structure [where m=4 in the formula (a)] is preferable. Oxygen compounds.

Alicyclic epoxy compounds (b2) include, for example: 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methyl 3,4-epoxy-6-methylcyclohexylmethyl cyclohexanecarboxylate, ethylene bis(3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxycyclohexane Hexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, diethylene glycol bis(3,4-epoxycyclohexyl methyl ether ), ethylene glycol bis(3,4-epoxycyclohexyl methyl ether), etc. Among them, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxy ring is particularly preferable from the viewpoint of surface hardness, flexibility, oxygen barrier property and warpage resistance of the laminate. Hexyl methyl ester. The alicyclic epoxy compound (b2) can be used individually or in combination of 2 or more types.

Aromatic epoxy compounds (b3) include, for example: monohydric phenols having at least one aromatic ring such as phenol, cresol, and butylphenol, or mono/polyglycidyl ethers of the alkylene oxide adducts, such as bis Glycidyl ether compounds or epoxy novolac resins of phenol A, bisphenol F or compounds further added with alkylene oxide; resorcinol or hydroquinone, catechol Glycidyl ethers of aromatic compounds with 2 or more phenolic hydroxyl groups, such as (catechol); mono/polyshrinkycids of aromatic compounds with 2 or more alcoholic hydroxyl groups, such as benzenedimethanol, benzenediethyl alcohol, and benzenedibutanol Glycerin ether compounds; glycidyl esters of phthalic acid, terephthalic acid, trimellitic acid and other polyprotic acid aromatic compounds with more than 2 carboxylic acids; benzoic acid or toluic acid, naphthoic acid, etc. Glycidyl esters of benzoic acids; epoxides of styrene oxide or divinylbenzene, etc. These aromatic epoxy compounds (b3) can be used individually or in combination of 2 or more types.

Among the epoxy compounds (b), an aliphatic epoxy compound (b1) is preferable, and when the aliphatic epoxy compound (b1) is contained, the surface hardness, flexibility, oxygen barrier property, and warpage resistance of the laminate are From a point of view it is beneficial.

The oxetane group in the oxetane compound (b) is preferably unsubstituted or modified with a carbon number of 6 or less, preferably 1 to 3 hydrocarbon groups, especially preferably 1 to 3 Hydrocarbyl modified base.

Oxetane compounds (b) include, for example: 3-ethyl-3-hydroxymethyl oxetane (sometimes called oxetanol), 2-ethylhexyl oxetane Butane, 1,4-bis[{3-ethyloxetan-3-yl}methoxy]methyl]benzene (sometimes called xylenebisoxetane), 3- Monofunctional oxetane compounds of ethyl-3-(phenoxymethyl)oxetane, 3-(cyclohexyloxy)methyl-3-ethyloxetane; 3- Ethyl-3[{(3-ethyloxetan-3-yl)methoxy}methyl]oxetane, xylenedioxetane, xylenedioxetane Bifunctional oxetane compounds such as mixtures of alkanes (for example, mixtures of xylenebisoxetanes having 1, 2 or 3 repeating units in the xylene skeleton) and the like. Among these oxetane compounds (b), from the viewpoints of surface hardness, flexibility, oxygen barrier properties, and warpage resistance, bifunctional oxetane compounds are preferred, and 3-functional oxetane compounds are particularly preferred. -Ethyl-3[{(3-ethyloxetan-3-yl)methoxy}methyl]oxetane, xylenebisoxetane or xylenebisoxetane Butane mixtures, etc. These oxetane compounds (b) can be used individually or in combination of 2 or more types.

The radical polymerizable cyclic ether compound (B-1-2) has one or more radical polymerizable functional groups in the molecule. The radical polymerizable functional group includes, for example, a vinyl group, a (meth)acryl group, etc., preferably a (meth)acryl group, particularly preferably a methacryl group. The free radical polymerizable cyclic ether compound can be an epoxy compound with a free radical polymerizable functional group, an oxetane compound with a free radical polymerizable functional group, etc., preferably one with a free radical polymerizable functional group. epoxy compound. The epoxy compound having a radically polymerizable functional group can be any of alicyclic, aliphatic, and aromatic, and is particularly preferably alicyclic. Since the radically polymerizable cyclic ether compound (B-1-2) has a radically polymerizable group and a cationic polymerizable group (such as an epoxy group, an oxetanyl group, etc.), it can produce radically polymerizable and cationic Aggregate both.

Specific examples of the radically polymerizable cyclic ether compound (B-1-2) include epoxy compounds having a vinyl group such as 1,2-epoxy-4-vinylcyclohexane; (meth)acrylic acid 3,4-epoxy cyclohexyl methyl ester, glycidyl (meth)acrylate and other epoxy compounds with (meth)acrylyl groups; (meth)acrylic acid (3-ethyl-3-oxoheterocycle Oxetane compounds having a (meth)acryloyl group, such as butyl)methyl ester, etc. These radical polymerizable cyclic ether compounds can be used individually or in combination of 2 or more types.

From the viewpoint of the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate, the cyclic ether compound (B-1) preferably contains a compound having two or more epoxy groups and/or two or more oxygen groups. A bicyclic ether compound (B-1-1) of a heterocyclobutanyl group. Bicyclic ether compound (B-1-1) Among the above epoxy compounds (b) and oxetane compounds (b), examples include epoxy compounds having two or more epoxy groups, and epoxy compounds having two or more epoxy groups. Oxetane compounds of the above oxetanyl groups, etc.

Furthermore, it is preferable that a cyclic ether compound (B-1) contains a radically polymerizable cyclic ether compound (B-1-2). By containing the radically polymerizable cyclic ether compound (B-1-2), the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate can be further improved.

In one embodiment of the present invention, when the curable composition of the present invention contains a radically polymerizable cyclic ether compound (B-1-2), relative to the bicyclic ether compound (B-1-1) 1 Parts by mass, the content of the radically polymerizable cyclic ether compound (B-1-2) is preferably 0.1 to 10 parts by mass, more preferably 0.15 to 7 parts by mass, more preferably 0.2 to 5 parts by mass. In other aspects, the content of the radically polymerizable cyclic ether compound (B-1-2) is preferably 1 to 10 parts by mass relative to 1 part by mass of the bicyclic ether compound (B-1-1), especially Preferably it is 1.5 to 7 parts by mass, more preferably 2 to 5 parts by mass. When the content of the radically polymerizable cyclic ether compound (B-1-2) is within the above range, a laminate having more excellent surface hardness, flexibility, oxygen barrier properties, and warpage resistance can be formed.

(II) Ethylene oxide compound (B-2)

The ethyleneoxy compound (B-2) means a compound having one or more ethyleneoxy groups in the molecule. In particular, the ethyleneoxy compound (B-2) is preferably a compound having two or more ethyleneoxy groups. These ethylene oxide compounds (B-2) can be used individually or in combination of 2 or more types. The ethylene oxide compound (B-2) may be a monomer or an oligomer, preferably a monomer.

Vinyloxy compounds (B-2) include, for example: 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether , divinyl adipate and other aliphatic vinyl ether compounds; aliphatic vinyl ether compounds such as cyclohexyl vinyl ether and cyclohexanedimethanol divinyl ether; aromatic vinyl ethers such as phenyl vinyl ether and benzenedimethanol divinyl ether ether compounds, etc. These ethylene oxide compounds (B-2) can be used individually or in combination of 2 or more types. Among the ethylene oxide compounds (B-2), alicyclic vinyl ether compounds are preferred from the viewpoints of surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate.

In the curable composition of the present invention, it is favorable that the cationically polymerizable monomer (B) contains ethyleneoxy Compound (B-2). When the curable composition of the present invention contains the ethylene oxide compound (B-2), 100 parts by mass relative to the total amount of the polyfunctional (meth)acrylate monomer (A) and the cationically polymerizable monomer (B) , The content of the ethylene oxide compound (B-2) is preferably 3 to 50 parts by mass, more preferably 10 to 40 parts by mass, more preferably 15 to 35 parts by mass. When the content of the ethylene oxide compound (B-2) is within the above range, the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate can be further improved.

Furthermore, in the curable composition of the present invention, the content of the vinyloxy compound (B-2) is preferably 0.1 to 3 parts by mass relative to 1 part by mass of the cyclic ether compound (B-1), especially preferably 0.1 to 3 parts by mass. 0.5 to 2 parts by mass, more preferably 0.5 to 1.5 parts by mass. When the content of the ethylene oxide compound (B-2) is within the above range, the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate can be further improved.

The content of the cationic polymerizable monomer (B) is preferably 0.1 to 5 parts by mass relative to 1 part by mass of the multifunctional (meth)acrylate monomer (A), more preferably 0.5 to 3 parts by mass, more preferably 0.5 to 1.5 parts by mass, particularly preferably 0.8 to 1.2 parts by mass. When the content of the cationically polymerizable monomer (B) is within the above range, it is advantageous from the viewpoint of the surface hardness, flexibility, oxygen barrier properties, and warpage resistance of the laminate.

In a preferred embodiment of the present invention, the content of the polyfunctional (meth)acrylate monomer (A) is preferably 5 to 80 parts by mass, particularly preferably 10 parts by mass, relative to 100 parts by mass of the curable composition. to 60 parts by mass, more preferably 20 to 50 parts by mass, particularly preferably 25 to 40 parts by mass, the content of the cyclic ether compound (B-1) is preferably 5 to 80 parts by mass, especially preferably 7 to 60 parts by mass parts, more preferably 10 to 50 parts by mass, particularly preferably 20 to 40 parts by mass, the content of vinyloxy compound (B-2) is preferably 3 to 60 parts by mass, especially preferably 5 to 40 parts by mass, more preferably Preferably, it is 10 to 30 parts by mass. When the content of the polyfunctional (meth)acrylate monomer (A), cyclic ether compound (B-1) and vinyloxy compound (B-2) is within the above range, it is easy to form surface hardness, flexibility and oxygen barrier A laminate with excellent durability and warpage resistance.

In a preferred embodiment of the present invention, the content of the polyfunctional (meth)acrylate monomer (A) is preferably 5 to 50 parts by mass, particularly preferably 10 parts by mass, relative to 100 parts by mass of the curable composition. to 45 parts by mass, more preferably 20 to 40 parts by mass, the content of the bicyclic ether compound (B-1-1) is preferably 3 to 30 parts by mass, especially preferably 5 to 25 parts by mass, and the radical polymerizability The content of the cyclic ether compound (B-1-2) is preferably from 5 to 40 parts by mass, particularly preferably from 10 to 35 parts by mass. In other preferred embodiments of the present invention, the content of the polyfunctional (meth)acrylate monomer (A) is preferably 5 to 50 parts by mass, particularly preferably 10 parts by mass, relative to 100 parts by mass of the curable composition. to 45 parts by mass, more preferably 20 to 40 parts by mass, the content of the bicyclic ether compound (B-1-1) is preferably 3 to 20 parts by mass, especially preferably 5 to 15 parts by mass, and the radical polymerizability The content of the cyclic ether compound (B-1-2) is preferably 15 to 40 parts by mass, particularly preferably 20 to 35 parts by mass. It is easy to Forms a laminate with excellent surface hardness, flexibility, oxygen barrier properties and warpage resistance.

(3) Additives

The curable composition of the present invention may contain a radical polymerization initiator (C) and a cationic polymerization initiator (D). It is preferable to contain a photoradical polymerization initiator (C) and a photocation polymerization initiator (D) from a viewpoint of easy and rapid hardening. When a photoradical polymerization initiator is contained in a curable composition, the polyfunctional (meth)acrylate monomer (A) which is a radical polymerizable compound can be hardened rapidly. The photoradical polymerization initiator is not particularly limited as long as it can start the hardening of the radical polymerizable compound by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams. The specific example can be Examples: acetophenone, 3-methylacetophenone, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2- Acetophenones such as methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-hydroxy-2-methyl-1-phenylpropan-1-one It is an initiator; diphenyl ketone, 4-chlorodiphenyl ketone and 4,4'-diaminodiphenyl ketone and other diphenyl ketone-based initiators; 2,2-dimethoxy-1 , 2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone and other alkyl phenone initiators; benzoin ether-based initiators such as benzoin propyl ether and benzoin ethyl ether; 4- Thioxanthone-based initiators such as isopropylthioxanthone; acylphosphine oxide-based initiators such as bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; others, Xanthone, fluorenone, camphorquinone, benzaldehyde, anthraquinone, etc. Among these photoradical polymerization initiators, alkylphenone-based initiators, acylphosphine oxide-based initiators, and the like are preferable.

Moreover, when a photocationic polymerization initiator is contained in a curable composition, the cationically polymerizable monomer (B) which is a cationically polymerizable compound can be hardened rapidly. The photocationic polymerization initiator is not particularly limited as long as it can generate cationic species or Lewis acid by irradiation of active energy rays and start hardening of the cationic polymerizable monomer. Specific examples include: aromatic diazo Salts, for example, benzene diazonium hexafluoroantimonate, benzene diazonium hexafluorophosphate, benzene diazonium hexafluoroborate; aromatic iodonium salts, for example, diphenyl iodonium tetrakis(pentafluorophenyl) borate, (4-methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, hexafluorophosphoric acid Bis(4-nonylphenyl)iodonium salts; aromatic percited salts, such as triphenylconium hexafluorophosphate, triphenylconium hexafluoroantimonate, triphenylconium tetrakis(pentafluorophenyl)borate salt, bis(hexafluoro)phosphate 4,4'-bis(diphenylcondyl)diphenyl sulfide, bis(hexafluoro)antimonate 4,4'-bis[bis(β-hydroxyethoxy) Phenylpermeyl]diphenyl sulfide, bis(hexafluoro)phosphate 4,4'-bis[bis(β-hydroxyethoxy)phenylpermeyl]diphenyl sulfide, hexafluoroantimonic acid 7- [Di(p-tolyl) peridyl]-2-isopropylthioxanthone, tetrakis(pentafluorophenyl)boronic acid 7-[di(p-tolyl)peridyl]-2-isopropylthioxanthone ( thioxanthone), 4-phenylcarbonyl-4'-diphenylpermedium hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylpermedium hexafluoroantimonate yl diphenyl sulfide, tetrakis(pentafluorophenyl)boronic acid 4-(p-tert-butylphenylcarbonyl)-4'-bis(p-tolyl)condolyl diphenyl sulfide; Compounds, such as xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene hexafluorophosphate-cyclopentadienyl iron (II), xylene-cyclopentadienyl iron (II)-tri (Trifluoromethylsulfonyl)methanide, etc. These photocationic polymerization initiators can be used individually or in combination of 2 or more types. Among these photocationic polymerization initiators, aromatic odonium salts and aromatic permeic acid salts are preferred. Since the radically polymerizable cyclic ether compound (B-1-2) has a radically polymerizable group and a cationic polymerizable group (such as an epoxy group, an oxetanyl group, etc.), it can produce radically polymerizable and cationic Aggregate both. Therefore, when a photoradical polymerization initiator and a photocationic polymerization initiator are used together, it can harden|cure more easily and rapidly.

The curable composition of the present invention is preferably contained in a curable composition because it contains a polyfunctional (meth)acrylate monomer that is a radical polymerizable compound and a cation polymerizable monomer that is a cationic polymerizable compound. Contains a photocationic polymerization initiator and a radical polymerization initiator. By using a photocationic polymerization initiator and a photoradical polymerization initiator together, it is possible to form a surface hardness, flexibility, oxygen barrier property, and warpage resistance. Excellent laminate.

When the curable composition contains a radical polymerization initiator, the content of the radical polymerization initiator (C) is preferably 1 to 15 parts by mass relative to 100 parts by mass of the polyfunctional (meth)acrylate monomer (A). parts, preferably 3 to 12 parts by mass; relative to 100 parts by mass of the cationic polymerizable monomer (B), the content of the cationic polymerization initiator (D) is preferably 1 to 15 parts by mass, especially preferably 3 to 10 parts by mass parts by mass. When the content of the radical polymerization initiator or the cationic polymerization initiator is within the above range, the curability can be further improved, and the surface hardness, flexibility, oxygen barrier property and warpage resistance can be further improved.

The curable composition of the present invention may contain inorganic particles from the viewpoint of increasing the surface hardness of the laminate. Inorganic particles include, for example, silica particles, reactive silica particles, alumina particles, reactive alumina particles, talc particles, clay particles, calcium carbonate particles, magnesium carbonate particles, barium sulfate particles, aluminum hydroxide particles, titanium dioxide particles, zirconia particles, etc. The inorganic particles can be used alone or in combination of two or more. In a preferred mode, the curable composition of the present invention further contains reactive silicon oxide particles. When the curable composition contains reactive silicon oxide particles, a cross-linked structure can be formed with compounds having reactive groups or reactive sites contained in the curable composition, and a film with excellent oxygen barrier properties can be obtained especially. Examples of reactive groups include acryl, hydroxyl, alkoxy (eg, methoxy, ethoxy, etc.), carboxyl, thiol, amine, nitro, acyl, epoxy, and the like. Among them, crosslinking is formed by reacting with the acryl group of the polyfunctional (meth)acrylate monomer (A) or the radical polymerizable group of the radical polymerizable cyclic ether compound (B-1-2). From the viewpoint of the structure, especially the improvement of the oxygen permeability of the laminate, an acryl group is most preferable. The inorganic particles can be used alone or in combination of two or more.

The particle size of the reactive silica particles is preferably from 1 to 100 nm, particularly preferably from 3 to 50 nm, and more preferably from 5 to 30 nm, from the viewpoint of the oxygen barrier properties of the laminate, transparency, and inhibition of particle aggregation. The particle size can be measured as an average primary particle size using a conventional method, for example, using a laser diffraction method or the like.

When the curable composition contains reactive silica particles, the content of the reactive silica particles is preferably 1 to 70 parts by mass relative to 100 parts by mass of the curable composition from the viewpoint of oxygen barrier properties and flexibility , preferably 5 to 65 parts by mass, more preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, and particularly preferably 15 to 45 parts by mass.

(triazine)系、丙烯腈系、二苯基酮系、胺基丁二烯系、柳酸酯系等。此等紫外線吸收劑中，從紫外線吸收性高，即使使用在影像顯示裝置時亦可顯現高紫外線截止能力之觀點而言，較佳為苯并三唑系或三

系紫外線吸收劑。為了擴展紫外線吸收寬，可單獨或組合使用兩種以上之最大吸收波長相異的紫外線吸收劑。 The curable composition of the present invention may further contain an ultraviolet absorber. Examples thereof include organic ultraviolet absorbers and fine powder-based ultraviolet blocking agents. Examples of organic ultraviolet absorbers include: benzotriazole (benzotriazole) series, three

(triazine) series, acrylonitrile series, benzophenone series, aminobutadiene series, salicylate series, etc. Among these ultraviolet absorbers, benzotriazole-based or triazole-based ones are preferred from the standpoint of high ultraviolet absorbing properties and high ultraviolet cutoff ability even when used in image display devices.

Department of ultraviolet absorbers. In order to expand the ultraviolet absorption width, two or more ultraviolet absorbers having different maximum absorption wavelengths may be used alone or in combination.

Examples of benzotriazoles include: 2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6[(2H-benzotriazol-2-yl) Phenol]], 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-[5-chloro(2H)-benzo Triazol-2-yl]-4-methyl-6-(tert-butyl)phenol and the like.

Representative commercial products of benzotriazole-based organic ultraviolet absorbers include: Sumika Chemtex Co., Ltd. Sumisorb (registered trademark) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350, Sumisorb 400, BASF Corporation TINUVIN (registered trademark) PS, TINUVIN 99-2, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, Adekastab (registered trademark) LA-24, Adekastab LA-29, Adekastab LA manufactured by ADEKA Co., Ltd. -31, Adekastab LA-32, Adekastab LA-36, etc.

系可列舉例如：2-(4,6-二苯基-1,3,5-三

-2-基)-5-[(己基)氧基]-酚等。 three

For example: 2-(4,6-diphenyl-1,3,5-tri

-2-yl)-5-[(hexyl)oxy]-phenol and the like.

系有機紫外線吸收劑的代表性市售品，可列舉出BASF公司製之TINUVIN 400、TINUVIN 405、TINUVIN 460、TINUVIN 477、TINUVIN 479、ADEKA股份有限公司製之Adekastab LA-46、Adekastab LA-F70 等。 three

Typical commercial products of organic ultraviolet absorbers include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 479 manufactured by BASF Corporation, Adekastab LA-46 and Adekastab LA-F70 manufactured by ADEKA Co., Ltd. .

-2,4-二基][(2,2,6,6-四甲基-4-哌啶基)亞胺基]六亞甲基[(2,2,6,6-四甲基-4-哌啶基)亞胺]]、二丁基胺-1,3,5-三

-N,N-雙(2,2,6,6-四甲基-4-哌啶基-1,6-六亞甲二胺N-(2,2,6,6-四甲基-4-哌啶基)丁基胺的聚縮合物等。 Furthermore, HALS agents can also be used, for example: bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, poly[[6-(1,1,3, 3-tetramethylbutyl)amino-1,3,5-tri

-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene[(2,2,6,6-tetramethyl- 4-piperidinyl)imine]], dibutylamine-1,3,5-tri

-N,N-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamineN-(2,2,6,6-tetramethyl-4 -Piperidinyl) polycondensates of butylamine, etc.

Representative commercial products of HALS agents include: TINUVIN 111, TINUVIN 123, TINUVIN 144, TINUVIN 292, TINUVIN 5100 manufactured by BASF Corporation; Adekastab LA-52, Adekastab LA-57, Adekastab LA-5100 manufactured by ADEKA Co., Ltd. 63P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-77, Adekastab LA-81, Adekastab LA-82, Adekastab LA-87, Adekastab LA-402, Adekastab LA-502, etc.

The fine-powder ultraviolet blocking agent is preferably a fine-particle metal oxide, especially a fine-particle metal oxide having an average primary particle diameter in the range of 1 to 100 nm and having an ultraviolet protection effect. Examples of metal oxides include titanium oxide, zinc oxide, cerium oxide, iron oxide, and magnesium oxide. One or more of these fine particle metal oxides may be combined, preferably two or more. Furthermore, the shape of the fine particle metal oxide may be spherical, needle-like, rod-like, spindle-like, indeterminate, plate-like, etc., and is not particularly limited. Furthermore, regarding the crystal form, there are amorphous, rutile ( rutile) type, anatase type, etc., are not particularly limited.

The microparticle metal oxide is preferably treated by previously known surface treatment, such as fluorine compound treatment, silicone treatment, silicone resin treatment, suspension treatment, silane coupling agent treatment, titanium coupling agent treatment, oil treatment, N - Acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, amino acid treatment, inorganic compound treatment, plasma treatment, mechanochemical treatment and other surface treatment in advance, especially by selecting from polysiloxane, silane, One or more surface treatment agents of fluorine compounds, amino acid compounds, and metal soaps are used for water-repellent treatment.

As a typical commercial item of a fine particle metal oxide, HMZD-50 by Sumitomo Osaka Cement Co., Ltd. etc. are mentioned.

When the curable composition contains an ultraviolet absorber, the content of the ultraviolet absorber can be appropriately selected according to the ultraviolet transmittance or the absorbance of the ultraviolet absorber, for example, relative to the polyfunctional (meth)acrylate monomer (A) and The total amount of the cationically polymerizable monomer (B) is 100 parts by mass, preferably 1 to 10 parts by mass, particularly preferably 2 to 8 parts by mass. When the content of the ultraviolet absorber is not less than the above lower limit, the ultraviolet absorbing property of the obtained laminate can be effectively expressed, and when it is not more than the above upper limit, the decrease in the curability of the curable composition can be suppressed.

The curable composition of the present invention may further contain a leveling agent. The leveling agent has the function of adjusting the fluidity of the curable composition so that the cured film obtained by coating the curable composition becomes flatter. Examples of this include: polysiloxane such as polydimethylsiloxane, polysiloxane, etc. Acrylic and perfluoroalkyl surfactants, etc. The content of the leveling agent is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass relative to 100 parts by mass of the hardening composition.

From the viewpoint of imparting antistatic capability to the laminate, an antistatic agent may be contained in the curable composition. The antistatic agent is preferably metal oxide and metal salt. Examples of the metal oxide include ITO (indium-tin composite oxide), ATO (antimony-tin composite oxide), tin oxide, antimony pentoxide, zinc oxide, zirconium oxide, titanium oxide, aluminum oxide, and the like. Zinc antimonate etc. are mentioned as a metal salt. When an antistatic agent is contained in the curable composition, the content of the antistatic agent varies depending on the required antistatic performance, but relative to the polyfunctional (meth)acrylate monomer (A) and cationic polymerizable monomer The total amount of (B) is 100 parts by mass, preferably 0.1 to 20 parts by mass, particularly preferably 1 to 10 parts by mass.

The curable composition of the present invention may further contain other additives within the range of not impairing the surface hardness and flexibility. Examples of other additives include antioxidants, release agents, stabilizers, bluing agents, flame retardants, pH adjusters, lubricants, and thickeners. These other additives may be used alone or in combination of two or more. When other additives are contained in the curable composition, the content of other additives is preferably 0.01 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the curable composition.

The curable composition of the present invention is preferably a curable composition for a hard coat layer of a front panel of an image display device.

The curable composition of the present invention can initiate radical polymerization of the components contained in the composition, the polyfunctional (meth)acrylate monomer (A), the cationic polymerizable monomer (B) and, if necessary, Agents, cationic polymerization initiators, inorganic particles, ultraviolet absorbers, and other additives are obtained by conventional methods, such as mixing, and the order of mixing is not particularly limited.

[2] Cured film, laminate and manufacturing method thereof

(1) Cured film, laminated body

The present invention includes a cured film obtained by curing the aforementioned curable composition. This cured film is a cured product of the aforementioned curable composition. The cured film of the present invention is composed of the curable composition of the present invention, so it has excellent surface hardness and flexibility. Furthermore, the cured film of the present invention also has excellent oxygen barrier properties and warpage resistance.

The present invention also includes a laminate in which the cured film of the present invention is layered on at least one surface of a base film. In the laminate of the present invention, the polymer contained in the base film is preferably transparent, and examples thereof include polyester-based polymers such as polyethylene terephthalate, polycarbonate-based polymers, polycarbonate-based polymers, and the like. Aryl ester-based polymers, polyether-based polymers, polyimide-based polymers, polyamide-based polymers, etc. Among them, polyimide-based polymers are preferable because they are excellent in heat resistance, flexibility, and rigidity. The laminate having a base film made of a polyimide-based polymer is useful as a front panel of an image display device, especially a front panel (touch film) of a flexible display. The base film may be a single layer or a plurality of layers. When the base film has multiple layers, each layer may be composed of the same or different compositions.

The so-called polyimide-based macromolecule refers to a polymer containing polyimide and repeating structural units including both imide groups and amido groups. The so-called polyimide means a polymer containing repeating structural units comprising imide groups.

Polyimide-based polymers can be produced, for example, using tetracarboxylic acid compounds and diamine compounds as main raw materials. In one embodiment of the present invention, the polyimide-based polymer has a repeating structural unit represented by formula (10). Here, G is a tetravalent organic group, and A is a divalent organic group. The polyimide-based polymer may contain two or more structures represented by formula (10) with different G and/or A.

Furthermore, within the range of not impairing the various physical properties of the substrate film, the polyimide-based polymer may contain a group selected from the structures represented by formula (11), formula (12) and formula (13). One or more kinds of groups. When the polyimide-based polymer contains a structure represented by formula (13), it tends to exhibit good surface hardness, which is preferable. In addition, a polyimide-based polymer containing a repeating structural unit represented by formula (10) and a repeating structural unit represented by formula (13) is called polyamideimide.

G and G ¹ are each independently a tetravalent organic group, preferably an organic group that may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. Examples of G and ^G1 include groups represented by formula (20) to formula (29), and tetravalent chain hydrocarbon groups having 6 or less carbon atoms.

In formula (20) to formula (29), * represents the bond, Z represents a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C( CH ₃ ) ₂ -, -Ar-, -SO ₂ -, -CO-, -O-Ar-O-, -Ar-CH ₂ -Ar-, -Ar-C(CH ₃ ) ₂ -Ar- or Ar _-SO2 -Ar-. Ar represents an arylylene group having 6 to 20 carbon atoms which may be substituted by a fluorine atom, and specific examples thereof include a phenylene group.

G ² is a trivalent organic group, preferably an organic group that may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. G ² can exemplify a group in which any one of the bonds of the groups represented by formula (20) to formula (29) is substituted with a hydrogen atom, and a trivalent chain hydrocarbon group having 6 or less carbon atoms.

G ³ is a divalent organic group, preferably an organic group that may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. G ³ can be exemplified by two non-adjacent groups substituted with hydrogen atoms among the bonding positions of the groups represented by the formula (20) to the formula (29), and a chain hydrocarbon group having 6 or less carbon atoms. Specific examples include phenylene groups.

A, A ¹ , A ² and A ³ are each independently a divalent organic group, preferably an organic group which may be substituted by a hydrocarbon group or a fluorine-substituted hydrocarbon group. A, A ¹ , A ² and A ³ can exemplify the groups shown in formula (30) to formula (38); these groups substituted by methyl, fluorine, chlorine or trifluoromethyl; and carbon number 6 The following chain hydrocarbon groups.

In formula (30) to formula (38), * represents the bond, Z ¹ , Z ² and Z ³ independently represent a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, - CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, or -CO-.

One example is that Z ¹ and Z ³ are -O- and Z ² is -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or -SO ₂ -. The bonding positions of Z ¹ and Z ² relative to the respective rings and the bonding positions of Z ² and Z ³ relative to the respective rings are preferably meta-position or para-position relative to the respective rings.

The base film may use the aforementioned polyimide-based polymers and polyamide-based polymers in combination. The so-called polyamide-based polymers are polymers containing repeating structural units including amide groups. The polyamide-based polymer in this embodiment is a polymer mainly composed of repeating structural units represented by formula (13). Preferable examples and specific examples are the same as G3 and ^A3 in polyimide ^- based polymers. It may contain two or more structures represented by formula (13) in which G ³ and/or A ³ are different.

[式(3)中，R¹至R⁸分別獨立地表示氫原子、碳數1至6的烷基或碳數6至12的芳基，R¹至R⁸所含有之氫原子可分別獨立地經鹵素原子取代，B表示單鍵、-O-、-CH₂-、-CH₂-CH₂-、-CH(CH₃)-、-C(CH₃)₂-、-C(CF₃)₂-、-SO₂-、-S-、-CO-或-NR⁹-，R⁹表示氫原子、可經鹵素原子取代之碳數1至12的烴基，n為0至4的整數，＊表示鍵結處]。 In one embodiment of the present invention, the polyimide-based polymer contained in the substrate film may contain multiple types of G ³ , and the multiple types of G ³ may be the same or different from each other. In particular, it is preferable that at least a part of G3 is a structural unit represented by formula ( ³ ) from the viewpoint of improving the surface hardness and flexibility of a laminate containing a polyimide-based polymer as a base film :

[In formula (3), R ¹ to R ⁸ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, or an aryl group with 6 to 12 carbons, and the hydrogen atoms contained in R ¹ to R ⁸ can be independently is substituted by a halogen atom, B represents a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, -S-, -CO- or -NR ⁹ -, R ⁹ represents a hydrogen atom, a hydrocarbon group with 1 to 12 carbons which may be substituted by a halogen atom, n is an integer from 0 to 4, ＊ means a bond].

In formula (3), B independently represents a single bond, -O-, -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, -C (CF ₃ ) ₂ -, -SO ₂ -, -S-, -CO-, or -NR ⁹ - preferably represents -O- or -S- from the viewpoint of improving the flexibility of the laminate, especially Good means -O-. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbons, or an aryl group having 6 to 12 carbons. Examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second-butyl, third-butyl, n-pentyl, and 2-methylbutyl , 3-methylbutyl, 2-ethylpropyl, n-hexyl, etc. In addition, examples of the aryl group having 6 to 12 carbon atoms include phenyl, tolyl, xylyl, naphthyl, biphenyl and the like. From the viewpoint of the surface hardness and flexibility of the laminate, R ¹ to R ⁸ preferably independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and particularly preferably represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. An alkyl group, more preferably represents a hydrogen atom. Here, the hydrogen atoms contained in R ¹ to R ⁸ may be independently replaced by halogen atoms. R ⁹ represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may be substituted by a halogen atom.

In formula (3), n is an integer ranging from 0 to 4, and when n is within this range, the bendability or elastic modulus of the laminate is good. Furthermore, in formula (3), n is preferably an integer in the range of 0 to 3, especially an integer in the range of 0 to 2, more preferably 0 or 1, and when n is in this range, the curvature of the laminate Good flexibility or elastic modulus, and relatively good availability of raw materials. Furthermore, G3 may contain one or more structural units represented by the formula ( ³ ). From the viewpoint of improving the elastic modulus and flexibility of the laminate and reducing the yellowness (YI value), especially It may contain 2 or more types of structural units with different n values, but preferably contains 2 types of structural units with different n values. At this time, it is preferable that n contains both constituent units of 0 and 1 from the viewpoint of easily exhibiting high elastic modulus, flexibility, and low yellowness (YI value) of the laminate.

亦即複數個G³的至少一部分是式(3’)所示之構成單元。此時，積層體可發揮高表面硬度，同時具有高彎曲性，並可降低黃色度。 In a preferred implementation mode of the present invention, formula (3) is a constituent unit represented by formula (3'):

That is, at least a part of the plurality of G ³ is a structural unit represented by formula (3'). In this case, the laminate exhibits high surface hardness, has high bendability, and can reduce yellowness.

In a preferred embodiment of the present invention, the composition represented by formula (3) is equal to the sum of the constituent units represented by formula (10) and the constituent units represented by formula (13) of the polyimide-based polymer. The unit is preferably more than 20 mole%, especially preferably more than 30 mole%, more preferably more than 40 mole%, especially preferably more than 50 mole%, most preferably more than 60 mole%, preferably 90% Mole % or less, preferably less than 85 mole %, more preferably less than 80 mole %. When the structural unit represented by the formula (3) is equal to or greater than the above lower limit relative to the total of the structural units represented by the formula (10) and the structural unit represented by the formula (13) of the polyimide-based polymer, the laminate can be It exhibits high surface hardness and is excellent in bendability and modulus of elasticity. When the structural unit represented by the formula (3) is below the above-mentioned upper limit with respect to the total of the structural units represented by the formula (10) and the structural unit represented by the formula (13) of the polyimide-based polymer, by suppressing The thickening caused by the hydrogen bond between the amide bonds in the formula (3) can suppress the viscosity of the resin varnish and facilitate the processing of the substrate film. Furthermore, in a preferred embodiment of the present invention, the sum of the structural units represented by the formula (10) and the structural units represented by the formula (13) of the polyimide-based polymer is equal to that of the formula (3). The constituent unit represented by n being 1 to 4 is preferably at least 3 mol%, especially preferably at least 5 mol%, more preferably at least 7 mol%, particularly preferably at least 9 mol%, more preferably at least 9 mol%. 90 mole % or less, preferably less than 70 mole %, more preferably less than 50 mole %, especially preferably less than 30 mole %. With respect to the total of the structural units represented by the formula (10) and the structural units represented by the formula (13) of the polyimide-based polymer, the structural units represented by n in the formula (3) being 1 to 4 are the above-mentioned When it is more than the lower limit, the laminate can exhibit high surface hardness and further improve bendability. With respect to the total of the structural units represented by the formula (10) and the structural units represented by the formula (13) of the polyimide-based polymer, the structural units represented by n in the formula (3) being 1 to 4 are the above-mentioned When it is below the upper limit, the viscosity of the resin varnish can be suppressed by suppressing the thickening due to the hydrogen bond between the amide bonds of the formula (3), and the processing of the base film is facilitated. The content of the structural unit represented by formula (3) can be measured using ¹ H-NMR, or calculated from the input ratio of raw materials, for example.

In a preferred embodiment of the present invention, G3 in the polyimide ^- based macromolecule is preferably more than 5 mol%, more preferably more than 8 mol%, more preferably more than 10 mol%, Most preferably, it is 12 mol% or more, which is represented by formula (3) when n is 1 to 4. When the above-mentioned lower limit of G3 of the polyimide-based polymer is represented by formula ( ³ ) when n is 1 to 4, the laminate exhibits high surface hardness and has high flexibility. Furthermore, G3 in the polyimide ^- based macromolecule is preferably less than 90 mol%, especially preferably less than 70 mol%, more preferably less than 50 mol%, and particularly preferably less than 30 mol%. , preferably represented by formula (3) when n is 1 to 4. When the above-mentioned upper limit of G3 of the polyimide-based polymer is represented by formula ( ³ ) when n is 1 to 4, by suppressing the amide from formula (3) when n is 1 to 4 The viscosity increase caused by the hydrogen bond between the bonds can suppress the viscosity of the resin varnish and facilitate the processing of the laminate. The ratio of the structural unit represented by the formula (3) when n is 1 to 4 in the polyimide-based polymer can be measured using ¹ H-NMR or calculated from the input ratio of raw materials, for example.

[式(4)中，R¹⁰至R¹⁷分別獨立地表示氫原子、碳數1至6的烷基或碳數6至12的芳基，R¹⁰至R¹⁷所含有之氫原子可分別獨立地經鹵素原子取代，＊表示鍵結處]。當式(10)及式(13)中之複數個A及A³的至少一部分為式(4)所示之基時，積層體可顯現高表面硬度，同時可具有高透明性。 In a preferred embodiment of the present invention, at least a part of the plurality of A and ^A in formula (10) and formula (13) is a constituent unit represented by formula (4):

[In formula (4), R ¹⁰ to R ¹⁷ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, or an aryl group with 6 to 12 carbons, and the hydrogen atoms contained in R ¹⁰ to R ¹⁷ can be independently Substituted by halogen atoms, * indicates the bond]. When at least a part of the plurality of A and A ³ in formula (10) and formula (13) is the group represented by formula (4), the laminate can exhibit high surface hardness and at the same time have high transparency.

In formula (4), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , and R ¹⁷ each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, or an alkyl group with 6 to 12 carbons the aryl. Examples of the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms include those exemplified as the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms in formula (3). R ¹⁰ to R ¹⁷ preferably independently represent a hydrogen atom or an alkyl group with 1 to 6 carbons, especially a hydrogen atom or an alkyl group with 1 to 3 carbons. Here, the hydrogen contained in R ¹⁰ to R ¹⁷ Atoms may each independently be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of the surface hardness, transparency and flexibility of the laminate, R ¹⁰ to R ¹⁷ are more preferably hydrogen atoms, methyl groups, fluorine groups, chlorine groups or trifluoromethyl groups independently, especially R ¹⁰ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen atoms, R ¹¹ and R ¹⁷ are hydrogen atoms, methyl, fluoro, chloro or trifluoromethyl, especially R ¹¹ and R ¹⁷ is methyl or trifluoromethyl.

亦即複數個A及A³的至少一部分是式(4’)所示之構成單元。此時積層體可顯現高透明性，同時可藉由含氟元素骨架來提升該聚醯亞胺系高分子對溶劑之溶解性，可將樹脂清漆的黏度抑制地較低，而容易進行基材膜的加工。 In a preferred embodiment of the present invention, the constituent unit shown in formula (4) is the constituent unit represented by formula (4'):

That is, at least a part of the plurality of A and A ³ is a structural unit represented by formula (4'). At this time, the laminate can show high transparency, and at the same time, the solubility of the polyimide polymer to the solvent can be improved by the fluorine-containing element skeleton, and the viscosity of the resin varnish can be suppressed to be low, so that it is easy to carry out the substrate Membrane processing.

In a preferred embodiment of the present invention, the ratio of ^A and A3 in the above-mentioned polyimide-based macromolecule is preferably 30 mole % or more, more preferably 50 mole % or more, more preferably 70 mole % The above is represented by formula (4), especially formula (4'). When ^A and A3 in the above-mentioned range in the polyimide-based macromolecule are represented by formula (4), especially formula (4'), the laminate can exhibit high transparency, and at the same time, the fluorine-containing element can Using a skeleton to improve the solubility of the polyimide-based polymer to solvents can suppress the viscosity of the resin varnish to a low level and facilitate the processing of the substrate film. Preferably, less than 100 mole % of ^A and A3 in the polyimide-based polymer is represented by formula (4), especially formula (4′). A and A ³ in the above-mentioned polyimide-based polymer can be formula (4), especially formula (4'). The ratio of the constituent units represented by the formula ( ⁴ ) of A and A3 in the polyimide-based polymer can be measured, for example, using ¹ H-NMR or calculated from the input ratio of raw materials.

[式(5)中，R¹⁸至R²⁵分別獨立地表示氫原子、碳數1至6的烷基或碳數6至12的芳基，R¹⁸至R²⁵所含有之氫原子可分別獨立地經鹵素原子取代，＊表示鍵結處]。當式(10)中之複數個G的至少一部分為式(5)所示之基時，積層體可顯現高透明性，同時可提升聚醯亞胺系高分子對溶劑之溶解性，可將樹脂清漆的黏度抑制地較低，並且容易進行基材膜的加工。 In a preferred embodiment of the present invention, at least a part of the plurality of G in formula (10) is a constituent unit represented by formula (5):

[In formula (5), R ¹⁸ to R ²⁵ independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, or an aryl group with 6 to 12 carbons, and the hydrogen atoms contained in R ¹⁸ to R ²⁵ can be independently Substituted by halogen atoms, * indicates the bond]. When at least a part of the plurality of G in the formula (10) is the group shown in the formula (5), the laminate can show high transparency, and at the same time, the solubility of the polyimide-based polymer to the solvent can be improved, and the The viscosity of the resin varnish is suppressively low, and the processing of the base film is easy.

In formula (5), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ , and R ²⁵ each independently represent a hydrogen atom, an alkyl group with 1 to 6 carbons, or an alkyl group with 6 to 12 carbons the aryl. Examples of the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms include those exemplified as the alkyl group having 1 to 6 carbon atoms or the aryl group having 6 to 12 carbon atoms in formula (3). R ¹⁸ to R ²⁵ preferably independently represent a hydrogen atom or an alkyl group with 1 to 6 carbons, especially a hydrogen atom or an alkyl group with 1 to 3 carbons, and here, the hydrogen contained in R ¹⁸ to R ²⁵ Atoms may each independently be substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. From the viewpoint of easily improving the surface hardness, flexibility and transparency of the laminate, ^R18 to ^R25 are more preferably independently hydrogen atoms, methyl groups, fluorine groups, chlorine groups or trifluoromethyl groups, more preferably R ¹⁸ , R ¹⁹ , R ²⁰ , R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms, R ²¹ and R ²² are hydrogen atoms, methyl, fluoro, chloro or trifluoromethyl, especially R ²¹ And R ²² is methyl or trifluoromethyl.

亦即複數個G的至少一部分是式(5’)所表示之構成單元。此時積層體可具有高透明性。 In a preferred embodiment of the present invention, the structural unit represented by formula (5) is the structural unit represented by formula (5'):

That is, at least a part of the plurality of G is a structural unit represented by formula (5'). In this case, the laminate can have high transparency.

In a preferred embodiment of the present invention, the G in the above-mentioned polyimide-based polymer is preferably more than 50 mole%, especially more than 60 mole%, more preferably more than 70 mole%. Formula (5), especially formula (5'). When G in the above-mentioned range in the above-mentioned polyimide-based macromolecule is represented by formula (5), especially formula (5'), the laminate can have high transparency, and can be separated by the fluorine-containing element skeleton. Increasing the solubility of the polyimide-based polymer to solvents can suppress the viscosity of the resin varnish to a low level, making it easier to manufacture laminates. Preferably, less than 100 mol% of G in the polyimide-based polymer is represented by formula (5), especially formula (5′). G in the above-mentioned polyimide-based polymer can be represented by formula (5), especially formula (5′). The ratio of the structural unit represented by the formula (5) of G in the polyimide-based polymer can be measured, for example, using ¹ H-NMR or calculated from the input ratio of raw materials.

Polyimide-based polymers can be obtained, for example, by polycondensation of diamine compounds and tetracarboxylic acid compounds (tetracarboxylic dianhydrides, etc.), for example, according to JP-A-2006-199945 or JP-A-2008- No. 163107 bulletin to record the method to synthesize. Commercially available polyimide products include Neopulim (registered trademark) manufactured by Mitsubishi Gas Chemical Co., Ltd., KPI-MX300F manufactured by Kawamura Sangyo Co., Ltd., and the like. The polyimide-based polymer having the structure represented by formula (13) can be synthesized, for example, according to the method described in JP 2014-528490 A.

In a preferred aspect of the present invention, the polyimide-based polymer (polyimide) having a repeating structural unit represented by formula (10) can be obtained by reacting a diamine compound with a tetracarboxylic acid compound. , the polyimide-based macromolecule (polyamide imide) having the repeating structural unit shown in formula (10) and the repeating structural unit shown in formula (13) can be obtained by making diamine compound and four After the reaction of the carboxylic acid compound, it is obtained by further reacting the dicarboxylic acid compound. The polyamide-based polymer having the repeating structural unit represented by formula (13) can be obtained by reacting the diamine compound and the dicarboxylic acid compound. .

As a tetracarboxylic-acid compound, aromatic tetracarboxylic-acid compounds, such as aromatic tetracarboxylic dianhydride, and aliphatic tetracarboxylic-acid compounds, such as aliphatic tetracarboxylic dianhydride, etc. are mentioned. The tetracarboxylic acid compound can be used individually or in combination of 2 or more types. The tetracarboxylic acid compound may be a tetracarboxylic acid compound analog such as an acid chloride compound other than the dianhydride.

Specific examples of aromatic tetracarboxylic dianhydrides include non-condensed polycyclic aromatic tetracarboxylic dianhydrides, monocyclic aromatic tetracarboxylic dianhydrides, and condensed polycyclic aromatic tetracarboxylic acids. Dianhydride. Examples of non-condensed polycyclic aromatic tetracarboxylic dianhydrides include 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic acid di anhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3'- Biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2 -Bis(2,3-dicarboxyphenyl)propane dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (sometimes described as 6FDA), 1,2-bis (2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,2-bis(3,4-dicarboxyphenyl) Ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl) ) methane dianhydride, 4,4'-(terephenylenedioxy)diphthalic dianhydride, 4,4'-(m-phenylenedioxy)diphthalic dianhydride, etc. Furthermore, monocyclic aromatic tetracarboxylic dianhydrides include, for example, 1,2,4,5-benzenetetracarboxylic dianhydrides, and condensed polycyclic aromatic tetracarboxylic dianhydrides include, for example, 2,3 ,6,7-Naphthalene tetracarboxylic dianhydride.

Among them, preferable examples include: 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,2',3 ,3'-Diphenylketonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-Diphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-bis Carboxyphenyl)propane dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA), 1,2-bis(2,3-dicarboxyphenyl)ethane di anhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,2-bis(3,4-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3, 4-dicarboxyphenyl)ethanedianhydride, bis(3,4-dicarboxyphenyl)methanedianhydride, bis(2,3-dicarboxyphenyl)methanedianhydride, 4,4'-(p-phenylene Dioxy)diphthalic dianhydride and 4,4'-(isophthalic dioxy)diphthalic dianhydride, especially 4,4'-oxydiphthalic acid diphthalic acid anhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene ) diphthalic dianhydride (6FDA), bis(3,4-dicarboxyphenyl)methane dianhydride and 4,4'-(terephthalic dioxy)diphthalic dianhydride. These can be used individually or in combination of 2 or more types.

As aliphatic tetracarboxylic dianhydride, a cyclic or acyclic aliphatic tetracarboxylic dianhydride is mentioned. The so-called cycloaliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride with an alicyclic hydrocarbon structure. The specific examples include: 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1, 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, etc.; bicyclo[2.2.2]-octane-7 -ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl 3,3'-4,4'-tetracarboxylic dianhydride and positional isomers thereof. These can be used individually or in combination of 2 or more types. Specific examples of acyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butane tetracarboxylic dianhydride and 1,2,3,4-pentane tetracarboxylic dianhydride, etc. These can be used individually or in combination of 2 or more types. Furthermore, a cycloaliphatic tetracarboxylic dianhydride and a noncyclic aliphatic tetracarboxylic dianhydride can be used in combination.

Among the above-mentioned tetracarboxylic dianhydrides, 4,4'-oxydiphthalate is preferred from the viewpoint of high surface hardness, high transparency, high flexibility, high flexibility and low colorability of the laminate. Formic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2',3,3 '-Biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4 ,4'-(hexafluoroisopropylidene)diphthalic dianhydride and mixtures thereof, especially 3,3',4,4'-biphenyltetracarboxylic dianhydride and 4,4' -(hexafluoroisopropylidene)diphthalic dianhydride and mixtures thereof, more preferably 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride (6FDA).

As the dicarboxylic acid compound, 4,4'-oxybisbenzoic acid and/or its acid chloride compound can be preferably used. In addition to 4,4'-oxybisbenzoic acid or the acid chloride, other dicarboxylic acid compounds can also be used. Examples of other dicarboxylic acid compounds include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, and similar acyl chloride compounds, acid anhydrides, and the like, and two or more of them may be used in combination. Specific examples include: terephthalic acid; isophthalic acid; naphthalene dicarboxylic acid; 4,4'-biphenyl dicarboxylic acid; 3,3'-biphenyl dicarboxylic acid; chain hydrocarbons with 8 or less carbon atoms The dicarboxylic acid compound and two benzoic acids are connected by a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ - or a phenylene group compounds, and such acid chloride compounds. Among these other dicarboxylic acid compounds, terephthalic acid is preferred. Specific examples are preferably 4,4'-oxybis(benzoyl chloride) and terephthalyl chloride, more preferably a combination of 4,4'-oxybis(benzoyl chloride) and p- Phthaloyl Chloride.

The above-mentioned polyimide-based polymers can be made of tetracarboxylic acid compounds in addition to the tetracarboxylic acid compounds used in the synthesis of the above-mentioned polyimide-based polymers within the range of not impairing the various physical properties of the laminate. And tricarboxylic acid and their anhydrides and derivatives reacted.

Examples of the tetracarboxylic acid include water adducts of anhydrides of the above-mentioned tetracarboxylic acid compounds.

Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, and similar acyl chloride compounds, acid anhydrides, and the like, and two or more of them may be used in combination. Specific examples include: 1,2,4-benzenetricarboxylic anhydride; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; phthalic anhydride and benzoic acid through a single bond, -O -, -CH ₂ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -SO ₂ -, or phenylene-linked compounds.

Examples of diamine compounds include aliphatic diamines, aromatic diamines, and mixtures thereof. The term "aromatic diamine" in this embodiment means a diamine in which an amine group is directly bonded to an aromatic ring, and a part of the structure may contain an aliphatic group or other substituents. The aromatic ring may be a single ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. Among these, a benzene ring is preferred. In addition, "aliphatic diamine" means a diamine in which an amine group and an aliphatic group are directly bonded, and may contain an aromatic ring or other substituents in a part of the structure.

Aliphatic diamines include, for example: acyclic aliphatic diamines such as hexamethylenediamine; and 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl) Cycloaliphatic diamines such as cyclohexane, norbornane diamine, and 4,4'-diaminodicyclohexylmethane, etc. These can be used individually or in combination of 2 or more types.

Examples of aromatic diamines include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylenediamine, p-xylenediamine, 1,5-diaminonaphthalene, 2,6 -Aromatic diamines with one aromatic ring, such as diaminonaphthalene; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diamine 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'- Diaminodiphenylphenoxide, 3,3'-diaminodiphenylphenoxide, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy ) benzene, bis[4-(4-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, 2,2-bis[4-(4- Aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, 2,2'-bis (Trifluoromethyl)-4,4'-diaminodiphenyl (sometimes described as TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, 9,9-bis (4-Aminophenyl) 9,9-bis(4-amino-3-methylphenyl) fluorene, 9,9-bis(4-amino-3-chlorophenyl) fluorine, 9, Aromatic diamines having two or more aromatic rings, such as 9-bis(4-amino-3-fluorophenyl) fluorine. These can be used individually or in combination of 2 or more types.

Aromatic diamines are preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 3,3' -Diaminodiphenylether, 4,4'-diaminodiphenylene, 3,3'-diaminodiphenylene, 1,4-bis(4-aminophenoxy)benzene , bis[4-(4-aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, 2,2-bis[4-(4-amino phenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2'-dimethylbenzidine, 2,2'-bis(tri Fluoromethyl)-4,4'-diaminobiphenyl (TFMB), 4,4'-bis(4-aminophenoxy)biphenyl, especially 4,4'-diaminobiphenyl Phenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 4,4'-diaminodiphenylene, 1,4-bis(4 -aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]pyridine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2 ,2'-Dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (TFMB), 4,4'-bis(4-aminobenzene Oxy)biphenyl. These can be used alone or in combination of two or more.

Among the above-mentioned diamine compounds, from the viewpoint of high surface hardness, high transparency, high flexibility, high flexibility, and low colorability of the laminate, it is preferable to use a compound selected from aromatic diamines having a biphenyl structure. One or more types of groups formed. It is especially preferred to use a compound selected from the group consisting of 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)benzidine, 4,4'-bis(4-aminophenoxy)biphenyl and 4 , one or more of the group consisting of 4'-diaminodiphenyl ethers, more preferably 2,2'-bis(trifluoromethyl)-4,4'-diaminodiphenyl( TFMB).

In one embodiment of the present invention, an imidization catalyst may exist in the synthesis reaction of polyimide-based polymers. Examples of imidization catalysts include aliphatic amines such as tripropylamine, dibutylpropylamine, and ethyldibutylamine; N-ethylpiperidine, N-propylpiperidine, N-butyl Alicyclic amines (monocyclic type) such as pyrrolidine, N-butylpiperidine and N-propylhexahydro azepine; azabicyclo[2.2.1]heptane, azabicyclo [3.2.1] Octane, azabicyclo[2.2.2]octane and azabicyclo[3.2.2]nonane and other alicyclic amines (polycyclic); and pyridine, 2-picoline (2 -picoline (2-picoline)), 3-picoline (3-picoline), 4-picoline (4-picoline), 2-ethylpyridine, 3-ethylpyridine, 4-ethyl Pyridine, 2,4-lutidine, 2,4,6-collidine, 3,4-cyclopentenylpyridine, 5,6,7,8-tetrahydroisoquinoline and isoquinoline, etc. Aromatic amines. Furthermore, it is preferable to use an acid anhydride together with an imidization catalyst from a viewpoint of facilitating imidization. As the acid anhydride, common acid anhydrides used in imidization reaction may be mentioned, and specific examples thereof include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride; aromatic acid anhydrides such as phthalic acid, and the like.

The reaction temperature of a diamine compound, a tetracarboxylic acid compound, and a dicarboxylic acid compound is not specifically limited, For example, it is 50-350 degreeC. The reaction time is also not particularly limited, for example, about 30 minutes to about 10 hours. The reaction can be carried out in an inert environment or under reduced pressure as required. In addition, reaction can be performed in a solvent, and a solvent mentioned later used for preparation of a resin varnish is mentioned.

In one embodiment of the present invention, the weight average molecular weight of the polyimide-based polymer or the polyamide-based polymer is preferably 200,000 or more, more preferably 250,000 or more, more preferably 300,000 or more, and most preferably 400,000 or more , preferably less than 600,000, especially less than 500,000. In other embodiments of the present invention, the weight average molecular weight of the polyimide-based polymer or the polyamide-based polymer is preferably 10,000 to 500,000, more preferably 50,000 to 480,000, more preferably 70,000 to 450,000, and most preferably 100,000 to 400,000. When the weight-average molecular weight is within the above range, the polyimide-based polymer can obtain high flexibility, and the viscosity of the resin varnish can be suppressed to be low, and it is easier to extend the polyimide-based polymer, so processing sex is good. The weight-average molecular weight can be determined by GPC and converted to standard polystyrene.

In a preferred embodiment of the present invention, the polyimide-based polymer and the polyamide-based polymer contained in the base film may contain halogen atoms such as fluorine atoms that can be introduced through the above-mentioned fluorine-based substituents and the like. . Specific examples of the fluorine-containing substituent include a fluorine group and a trifluoromethyl group. By making polyimide-based macromolecules and polyamide-based macromolecules contain halogen atoms, the elastic modulus of the base film can be improved, and the yellowness (YI value) can be reduced at the same time, so it is preferable to use polyimide-based high Molecules and polyamide-based polymers contain halogen atoms in the molecules. Furthermore, the halogen atom is preferably a fluorine atom from the viewpoint of reduction of yellowness (improvement of transparency), reduction of water absorption, and suppression of deformation of the base film. In addition, when the halogen atom is a fluorine atom, the laminate can be used particularly usefully when bending the laminate is difficult to leave a bending line, causing deformation such as bending in a flexible display.

From the standpoint of improvement in hardness, improvement in modulus of elasticity, reduction in yellowness (improvement in transparency), reduction in water absorption, and suppression of deformation of the base film, relative to 100 parts by mass of the polyimide-based polymer, The polyimide-based polymer and the content of halogen atoms in the polyamide-based polymer are preferably 1 to 40 parts by mass, particularly preferably 3 to 35 parts by mass, and more preferably 5 to 32 parts by mass.

In a preferred embodiment of the present invention, the substrate film contains the aforementioned polyimide-based polymer. With respect to 100 parts by mass of the substrate film, the content of the polyimide-based polymer in the substrate film is preferably at least 40 parts by mass, particularly preferably at least 50 parts by mass, more preferably at least 70 parts by mass, and more preferably at least 70 parts by mass. More than 90 parts by mass, preferably 100 parts by mass. When the content of the polyimide-based polymer is 40 parts by mass or more, the base film has good flexibility.

The base film may contain additives. As an additive, an inorganic material, the said ultraviolet absorber, said other additive etc. are mentioned, for example. These additives can be used individually or in combination of 2 or more types. Examples of the inorganic material include silicon compounds such as quaternary alkoxysilanes such as tetraethoxysilane (TEOS) in addition to the aforementioned inorganic particles. The resin varnish used to manufacture the substrate film is preferably an inorganic particle, particularly preferably a silicon oxide particle, from the viewpoint of the stability of the polyimide resin varnish. Inorganic particles can be bonded by molecules having siloxane bonds.

The average particle size of silicon oxide particles is preferably at least 10nm, more preferably at least 15nm, more preferably at least 20nm, more preferably at most 100nm, especially at most 90nm, more preferably at most 80nm, more preferably at most 70nm, especially Preferably, it is 60 nm or less, particularly preferably, it is 50 nm or less, and most preferably, it is 40 nm or less. When the average particle diameter of the silicon oxide particles is within the above range, it is easy to improve the flexibility and transparency of the laminate. The average particle diameter of the laminate can be measured by the BET method. The average particle diameter can also be measured by image analysis of a transmission electron microscope (TEM) or a scanning electron microscope (SEM).

When the substrate film contains silicon oxide particles, the content of the silicon oxide particles is preferably at least 1 part by mass, more preferably at least 5 parts by mass, more preferably at least 10 parts by mass, and particularly preferably at least 100 parts by mass of the substrate film. It is 20 mass parts or more, Preferably it is 60 mass parts or less, Most preferably, it is 50 mass parts or less. When the content of the silicon oxide particles is within the above range, it is easy to improve the modulus of elasticity and flexibility of the base film.

When the substrate film contains additives, the content of the additives can be appropriately selected according to the type of additives, such as 0.01 to 60 parts by mass, preferably 0.1 to 60 parts by mass, and especially preferably 0.1 to 60 parts by mass, relative to 100 parts by mass of the substrate film. 1 to 50 parts by mass.

The thickness of the substrate film can be appropriately adjusted depending on the application, and is usually 10 to 1,000 μm, preferably 15 to 500 μm, particularly preferably 20 to 400 μm, more preferably 25 to 300 μm, more preferably 25 to 100 μm, and most preferably 25 to 75 μm. When the thickness of the base film is in the above range, the flexibility is good, and it is also beneficial to the thinning of the image display device. In addition, it tends to be easy to ensure the mechanical strength as the base material and the surface hardness during the production of the laminate.

In the present invention, the production method of the base film is not particularly limited, and can be produced, for example, by a method including the following steps: (a) a step of preparing a liquid containing the aforementioned resin (sometimes called a resin varnish) (varnish preparation) step), (b) a step of applying a resin varnish to a support to form a coating film (coating step), and (c) a step of drying the coated liquid (coating film) to form a substrate film (base material film forming step).

In the varnish preparation step, the aforementioned resin is dissolved in a solvent, and the aforementioned additives such as the aforementioned silicon oxide particles are stirred and mixed as needed to prepare a resin varnish. In addition, when using silicon oxide particles as an additive, the silicon oxide sol can be obtained by substituting the dispersion of silicon oxide sol containing silicon oxide particles with a solvent that can dissolve the aforementioned resin, such as the solvent used in the preparation of the following varnish , and add this silica sol to the resin.

The solvent used for preparing the resin varnish is not particularly limited as long as it can dissolve the aforementioned polymer. Examples of such solvents include amide solvents such as N,N-dimethylacetamide and N,N-dimethylformamide; lactones such as γ-butyrolactone (GBL) and γ-valerolactone; solvents; sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and cyclobutylene; carbonate-based solvents such as ethylene carbonate and propylene carbonate; and combinations thereof (mixed solvents). Among these, amide-based solvents or lactone-based solvents are preferable. These solvents may be used alone or in combination of two or more. Furthermore, the varnish may contain water, alcohol solvents, ketone solvents, acyclic ester solvents, ether solvents, and the like. The solid content concentration of the varnish is preferably 1 to 25% by mass, particularly preferably 5 to 15% by mass.

In the coating step, the varnish can be applied to the substrate by a generally known coating method to form a coating film. Commonly known coating methods include, for example, roll coating methods such as wire rod coating, reverse coating, and gravure coating, die coating, knife coating, and lip coating. , Spin coating method, screen coating method, curtain coating method, soaking method, spray method, fluid casting method, etc.

In the base film forming step, the base film can be formed by drying the coating film and peeling it from the base material. After peeling, a drying step of drying the substrate film may be performed. Drying of the coating film can generally be performed at a temperature of 50 to 350°C. The coating film can be dried in an inert environment or under reduced pressure as required.

Examples of the support material include PET films, PEN films, other polyimide-based polymers, polyamide-based polymer films, and the like. Among them, PET films, PEN films, etc. are preferred from the viewpoint of excellent heat resistance, and particularly preferred from the viewpoints of adhesion, ease of peeling, and cost when forming a film with a base material. PET film. Other metal strips such as stainless steel or glass plates can also be used.

In the laminate of the present invention, the cured film may have a single-layer structure or a multi-layer structure. The thickness of the cured film can be appropriately selected according to the application of the image display device to which the laminate is applied, and is, for example, 1 to 50 μm, preferably 2 to 30 μm. In terms of excellent surface hardness and bendability, the thickness of the cured film is particularly preferably 3 to 20 μm, more preferably 6 to 18 μm, particularly preferably 8 to 16 μm. The thickness of the cured film can be measured using a contact digital gauge.

In one embodiment of the present invention, in the laminate of the present invention, a primer layer may be disposed between the base film and the cured film. When a cured film is arranged on both surfaces of the base film, the primer layer can be arranged only between the base film and a cured film, or between the base film and a cured film and between the base film and another cured film. Both are provided with a primer layer between the films.

The primer layer is a layer formed by a primer, which can improve the adhesion between the substrate film and the hardened film. The compound contained in the primer layer can form a chemical bond with the polymer contained in the substrate film, preferably a polyimide-based polymer, on the interface.

The primer is, for example, an epoxy-based compound primer of an ultraviolet curing type, a thermosetting type, or a two-component curing type. The primer can be polyamic acid. These are suitable for improving the adhesion between the base film and the cured film when the base film contains polyimide-based polymers.

The primer may contain a silane coupling agent. The silane coupling agent can also chemically bond with a silicon compound that can be contained in the base film by a condensation reaction. A silane coupling agent can be preferably used especially when the compounding ratio of the silicon compound which can be contained in a base film is high.

The silane coupling agent is preferably a compound having a silicon atom and an alkoxysilyl group having 1 to 3 alkoxy groups covalently bonded to the silicon atom. Especially preferred is a compound comprising a structure in which a silicon atom is covalently bonded to two or more alkoxy groups, more preferably a compound comprising a structure in which a silicon atom is covalently bonded to three alkoxy groups. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy and the like. Among them, a methoxy group and an ethoxy group are preferable because they increase the reactivity with silicon compounds.

The silane coupling agent preferably has a substituent having high affinity with the base film and the cured film. The substituent of the silane coupling agent is preferably an epoxy group, an amine group, a urea group, or an isocyanate group from the viewpoint of affinity with the polyimide-based polymer that may be contained in the base film. When the cured film contains (meth)acrylates, if the silane coupling agent that can be used in the primer layer has epoxy, methacrylic, acrylic, amine or styrene groups, the affinity can be improved, so better. Among them, when the base film is made of a polyimide-based polymer, a silane coupling agent having a substituent selected from a methacryl group, an acryl group, and an amine group exhibits compatibility with the base film and the cured film. The affinity tends to be excellent, so it is preferable.

The thickness of the primer layer can be appropriately selected according to the cured film, for example, it is 0.01 nm to 20 μm. When using an epoxy compound primer, the thickness of the primer layer is preferably 0.01 to 20 μm, particularly preferably 0.1 to 10 μm. When a silane coupling agent is used, the thickness of the primer layer is preferably from 0.1 nm to 1 μm, especially preferably from 0.5 nm to 0.1 μm.

In an embodiment of the present invention, the laminate of the present invention may further include a functional layer in addition to the base film and the cured film. Examples of the functional layer include those having various functions such as an ultraviolet absorbing layer, an adhesive layer, a hue adjusting layer, and a refractive index adjusting layer. The laminate of the present invention may have a single layer or a plurality of functional layers. In addition, one functional layer may have plural functions.

The ultraviolet absorbing layer is a layer having the function of absorbing ultraviolet rays, for example, it is composed of a main material selected from ultraviolet curable transparent resin, electron beam curable transparent resin, and thermosetting transparent resin, and an ultraviolet absorber dispersed in the main material. constituted. By providing an ultraviolet absorbing layer as a functional layer, it is possible to easily suppress a change in yellowness due to light irradiation.

The adhesive layer is a layer having an adhesive function, and has the function of bonding the base film or laminate to other members. As the material of the adhesive layer, known ones can be used. For example, a thermosetting resin composition or a photosetting resin composition can be used.

The adhesive layer may also be composed of a resin composition containing a component having a polymerizable functional group. At this time, after the laminate is adhered to other members, the resin composition constituting the adhesive layer is further polymerized to achieve firm bonding. The bonding strength between other members and the adhesive layer included in the laminate may be 0.1 N/cm or more or 0.5 N/cm or more.

The adhesive layer may also contain a thermosetting resin composition or a photosetting resin composition as a material. At this time, the resin composition can be cured by supplying energy afterwards to polymerize the resin composition.

The adhesive layer may also be a layer called pressure sensitive adhesive (PSA), which is attached to the object by pressing. The pressure-sensitive adhesive can be an adhesive that is "adhesive at room temperature and adheres to the material to be bonded under light pressure" (JIS K6800), or it can be an adhesive that "contains specific components in the protective film (microcapsules) ), and can maintain stability until the film is destroyed by appropriate means (pressure, heat, etc.)" (JIS K6800) capsule adhesive.

The hue adjustment layer is a layer having a hue adjustment function, and can adjust the layered body to a desired hue. The hue adjustment layer is, for example, a layer containing a resin and a colorant. Examples of coloring agents include inorganic pigments such as titanium oxide, zinc oxide, red iron oxide, titanium dioxide-based fired pigments, ultramarine blue, cobalt aluminate, and carbon black; azo-based compounds, quinacridone-based compounds, anthracene Anthraquinone-based compounds, perylene-based compounds, isoindolinone-based compounds, phthalocyanine-based compounds, quinophthalone-based compounds, indanthrene-based compounds Organic pigments such as compounds and diketo pyrrolo pyrrole (diketo pyrrolo pyrrole) compounds; extender pigments such as barium sulfate and calcium carbonate; and basic dyes, acid dyes, and mordant dyes.

The refractive index adjustment layer is a layer having a refractive index adjustment function, which has a different refractive index from the base film and can impart a predetermined refractive index to the laminate. The refractive index adjustment layer may be, for example, a resin layer containing an appropriately selected resin and, if necessary, a pigment, or a metal thin film.

Pigments for adjusting the refractive index include, for example, silicon oxide, aluminum oxide, antimony oxide, tin oxide, titanium oxide, zirconium oxide, and tantalum oxide. The average primary particle size of the pigment may be 0.1 μm or less. By setting the average primary particle diameter of the pigment to 0.1 μm or less, scattering of light passing through the refractive index adjustment layer can be prevented, thereby preventing a decrease in transparency.

Metals used in the refractive index adjustment layer include, for example, metals such as titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, and silicon nitride. oxides, metal nitrides, etc.

The above-mentioned primer layer may also be arranged between the base film and the functional layer.

The laminate of the present invention is excellent in surface hardness and flexibility because it contains a cured film obtained by curing the aforementioned curable composition. The laminate of the present invention also has excellent oxygen barrier properties and warpage resistance. Therefore, it is used as a front panel of an image display device and the like.

In a preferred mode, the laminated system of the present invention is laminated (or laminated) on the optical film directly or through a resin layer or the like. Optical films (films with optical properties) can be single-layer structures (such as optical functional films such as polarizers, retardation films, brightness enhancement films, anti-glare films, anti-reflection films, diffusion films, and light-concentrating films, etc.) or Multi-layer structure (such as polarizing plate, retardation plate, etc.). The optical film is preferably a polarizing plate, a polarizer, a phase difference plate or a phase difference film, and is particularly preferably a polarizing plate. The resin layer is not particularly limited, for example, it can be made of acrylic resin, polycarbonate resin, polyester resin, norbornene resin, cellulose ester resin, cyclic olefin resin, styrene resin, methacrylic acid It is composed of methyl ester-styrene resin, acrylonitrile-styrene resin and acrylonitrile-butadiene-styrene resin. These resins can be used alone or in combination of two or more. Furthermore, in the optical film laminated (or bonded) with the laminate of the present invention, a separation film (release film) may be laminated (or bonded) on the surface opposite to the laminate (surface on the optical film side). This separation film is usually peeled and removed when using a laminate including an optical film. Examples of the separation film include polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, etc., and the surface facing the optical film side may be used on the side of the optical film and the side of the separation film. Apply mold release treatment.

In the laminate of the present invention, the oxygen permeability is preferably 800cc/(m ² ‧24h‧atm), more preferably 600cc/(m ² ‧24h‧atm), more preferably 400cc/(m ² ‧ 24h‧atm), preferably 300cc/(m ² ‧24h‧atm). When the oxygen permeability is in the above range, when the laminate is applied to an image display device or the like, deterioration of a display element, a polarizing plate, or the like can be effectively suppressed. In addition, oxygen permeability can be measured by the method described in an Example.

The laminated body of the present invention preferably does not break when it is continuously bent 10 times with a bending radius of 3 mm in a mandrel test. In the best form, even if it is bent 10 times continuously with a bending radius of 2 mm, no cracks will occur. Since the laminate of the present invention has such excellent flexibility, it can be preferably used in flexible displays. The spindle test can be measured by the method described in the examples.

The pencil hardness of the laminate of the present invention is preferably at least H, particularly preferably at least 2H, more preferably at least 3H, still more preferably at least 4H, and particularly preferably at least 5H. Since the laminate of the present invention has such excellent pencil hardness, when used as a front panel of an image display device or the like, damage to the surface of the image display device can be effectively suppressed.

The laminate of the present invention has a small amount of warping even after the laminate is cut to a predetermined size and left for a long time, and has excellent warpage resistance. The amount of warpage is preferably at most ±8 mm, more preferably at most ±6 mm, more preferably at most ±5 mm, more preferably at most ±4 mm, and most preferably at most ±3 mm. This amount of warping can be measured by the method described in the examples.

(2) Manufacturing method of laminated body

The laminate of the present invention can be produced, for example, by a method comprising: (d) a step of applying the curable composition of the present invention on a substrate film to form a coating film (coating film forming step), (e ) The step of irradiating high-energy rays to the coating film to harden the coating film to form a cured film (hardening step).

In the coating film forming step, a curable composition dissolved in a solvent can be applied to the base film. The solvent is sufficient as long as it can dissolve the curable composition, for example, methanol, ethanol, 1-propanol, 2-propanol (isopropanol), 1-butanol, 2-butanol (second butanol) , 2-methyl-1-propanol (isobutanol), 2-methyl-2-propanol (tertiary butanol) and other alcohol solvents; 2-ethoxyethanol, 2-butoxyethanol, 3 -Methoxy-1-propanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and other alkoxy alcohol solvents; diacetone alcohol and other ketal solvents; acetone, butanone Ketone solvents such as , methyl isobutyl ketone; aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate, etc. These solvents can be used alone or in combination of two or more.

Drying of the coating film formed on the base film may also be performed. Drying of the coating film can be performed by evaporating the solvent at a temperature of 50 to 150° C., and the drying time is usually 30 to 180 seconds. Drying can also be carried out under atmospheric conditions, under an inert environment or under reduced pressure.

Furthermore, after the coating film forming step, an extending step of extending the base film may be provided. The stretching may be uniaxial stretching or biaxial stretching, but it is preferable to stretch the substrate film by uniaxial stretching from the viewpoint of the uniformity of in-plane retardation distribution. When biaxial extension is performed, the biaxial extension can be simultaneous biaxial extension or sequential biaxial extension.

In the curing step, the coating film is irradiated with high-energy rays (for example, active energy rays) to cure the coating film to form a cured film. The intensity of irradiation can be appropriately determined depending on the composition of the curable composition, and is not particularly limited, but irradiation in a wavelength region effective for activation of photocationic polymerization initiators and photoradical polymerization initiators is preferable. The irradiation intensity is preferably 0.1 to 6,000 mW/cm ² , more preferably 10 to 1,000 mW/cm ² , more preferably 20 to 500 mW/cm ² . When the irradiation intensity is within the above range, an appropriate reaction time can be ensured, and yellowing or deterioration due to heat radiated from the light source and heat during curing reaction can be suppressed. The irradiation time can be appropriately determined in accordance with the composition of the curable composition, and is not particularly limited. It can be set so that the cumulative light quantity represented by the product of the aforementioned irradiation intensity and irradiation time is preferably 10 to 10,000 mJ/cm ² , and is especially preferred It is 50 to 1,000 mJ/cm ² , more preferably 80 to 500 mJ/cm ² . When the cumulative amount of light is within the aforementioned range, a sufficient amount of activated species from the photocationic polymerization initiator or photoradical polymerization initiator can be generated, and the hardening reaction can be carried out more reliably. Furthermore, the irradiation time will not be too long, Good productivity can be maintained. Moreover, since the hardness of a cured film can be improved more by performing an irradiation process in this range, it is useful.

[3] Image display device

The laminated system of the present invention is useful as a front panel of an image display device, especially a front panel (touch film) of a flexible display. In the present invention, an image display device including the laminate of the present invention, especially a flexible display, can also be provided. The flexible display of this embodiment includes, for example, a flexible functional layer and a laminate (functioning as a front panel) of the present invention laminated on the flexible functional layer. That is, the front panel of the flexible display is arranged on the viewing side of the flexible functional layer. The front panel has the function of protecting the flexible functional layer.

Examples of image display devices include wearable devices such as televisions, smart phones, mobile phones, car navigation, tablet PCs, portable game consoles, electronic paper, indicators, billboards, clocks, and smart watches. The term "flexible display" includes all image display devices with flexible characteristics.

[Example]

Although Examples and Comparative Examples are shown below and this invention is demonstrated more concretely, this invention is not limited to these examples. In the following, the usage amount, parts and % of content are indicated, and it is the quality standard when there is no special statement.

[1-1] Production Example 1: Production of Base Film 1

DMAc was added to polyimide powder (“KPI-MX300F(100)”, manufactured by Kawamura Sangyo Co., Ltd., polystyrene-equivalent weight average molecular weight (Mw) = 280,000) and dissolved, and the dispersion medium was added to GBL's silicon oxide sol is used to prepare a polyimide varnish with a mass ratio of polyimide to silicon oxide of 1:1 on a pure basis. The total mass of the polyimide resin and silicon oxide in the polyimide varnish was 17% by mass. This polyimide varnish was fluid-cast and dried to obtain a substrate film 1 with a thickness of 50 μm.

[1-2] Production Example 2: Production of Base Film 2

(Preparation of silica sol A)

Using the amorphous silica sol with a BET diameter (average particle diameter measured by the BET method) of 27nm produced by the sol-gel method as a raw material, GBL-substituted silica sol A was prepared by solvent replacement .

(Synthesis of polyamideimide A)

Under a nitrogen atmosphere, 45 parts by mass of 2,2'-bis(trifluoromethyl)benzidine (TFMB) and 768.55 parts by mass of dimethylacetamide (DMAc) were added to a reaction vessel equipped with a stirrer, and the TFMB was dissolved in DMAc while stirring at warm temperature. Next, 18.92 parts by mass (0.3 mole times [relative to TFMB]) of 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) was added to the reaction container, and stirred at room temperature 3 hours. Then, 4.19 parts by mass (0.1 mole times [relative to TFMB]) of 4,4'-oxybis(benzoyl chloride) (OBBC) was added to the reaction vessel, followed by adding terephthaloyl chloride (TPC ) 17.29 parts by mass (0.6 mole times [relative to TFMB]) was added to the reaction container, and stirred at room temperature for 1 hour. Next, 4.63 parts by mass of 4-picoline (0.35 molar times [relative to TFMB]) and 13.04 parts by mass of acetic anhydride (0.9 molar times [relative to TFMB]) were added to the reaction vessel, and stirred at room temperature for 30 Minutes, the temperature was raised to 70° C. and stirred for 3.5 hours to obtain a reaction solution.

The obtained reaction solution was cooled to room temperature, and thrown into a large amount of methanol in the form of filaments, and the deposited precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100° C., and polyamide imide A was obtained. The weight average molecular weight of polyamide imide A was 455,000.

(production of polyamideimide varnish A)

After dissolving polyamideimide A in GBL, silicon oxide sol A is added in such a way that polyamideimide A: silicon oxide particles = 60:40 (mass ratio) to produce polyamideimide Varnish A. It prepared so that the solid content concentration in polyamideimide varnish A might become 10 mass %.

After the polyamideimide varnish A was filtered through a filter with a mesh opening of 10 μm, the film thickness of the self-supporting film was 55 μm, and applied to a polyester substrate (manufactured by Toyobo Co., Ltd., (trade name "A4100") was dried at 50°C for 30 minutes and then at 140°C for 15 minutes, and then the obtained coating film was peeled off from the polyester substrate to obtain a self-supporting film. The self-supporting film was fixed to a metal frame, and it dried at 200 degreeC for 40 minutes under air|atmosphere, and obtained the base material film 2 which has a thickness of 50 micrometers.

[2-1] Examples 1 to 25 and Comparative Example 1

After weighing the components shown in Table 1 and Table 2, a curable composition was prepared by stirring. The curable composition was applied to the substrate film 1 obtained in Production Example 1 using a bar coater, dried at 80° C. for 3 minutes, and then UV irradiation equipment “6KWI lamp conveyor belt manufactured by Eye Graphics Co., Ltd. was used under a nitrogen atmosphere. ", UV curing was carried out under the following curing conditions, whereby a laminated body with a cured film laminated on one surface of the base film 1 was obtained. The thickness of the cured film was 9 μm. When the product used contains solvents, etc., the compounding amount of each compounded component shown in Table 1 and Table 2 is the mass part of the active ingredient contained in the product.

(hardening condition)

Light source lamp: high pressure mercury lamp

Cumulative light quantity: 500mJ/cm ²

Peak intensity: 200mW/cm ²

In addition, the integrated light quantity is the value measured using the laminated light meter (365 nm) of the said UV irradiation apparatus.

[2-2] Examples 26 to 29

After weighing the ingredients shown in Table 3, a curable composition was prepared by stirring. Except that the substrate film 2 obtained in Production Example 2 was used instead of the substrate film 1 obtained in Production Example 1, and the thickness of the cured film was adjusted to be 16 μm, the others were the same as in Examples 1 to 25. A laminate in which a cured film is layered on one surface of the base film 2 is obtained. The thickness of the cured film was 16 μm. When the product used contains solvents, etc., the compounding amount of each compounded ingredient shown in Table 3 is the mass part of the active ingredient contained in the product.

[2-3] Example 30

After weighing the components shown in Table 3, a curable composition was prepared by stirring. Except that the substrate film 2 obtained in Manufacturing Example 2 was used instead of the substrate film 1 obtained in Manufacturing Example 1, other operations were performed in the same manner as in Examples 1 to 25 to obtain an area layer on the substrate film 2. Laminated body with hardened film. The thickness of the cured film was 9 μm. When the product used contains solvents, etc., the compounding amount of each compounded ingredient shown in Table 3 is the mass part of the active ingredient contained in the product.

[Measurement of Pencil Hardness]

The pencil hardness of the cured film surface was measured about the laminate obtained in Examples 1-30 and the comparative example 1 based on JISK5600-5-4:1999. The load was set to 750g. The measurement results are shown in Table 1 to Table 3.

[mandrel test]

The laminates obtained in Examples 1 to 30 and Comparative Example 1 were subjected to a bending test according to JIS K 5600-5-1:1999, and evaluated by the following evaluation methods. The evaluation results are shown in Table 1 to Table 3.

The laminates obtained in Examples 1 to 30 and Comparative Example 1 were cut into 1 cm×8 cm to obtain measurement samples. The operation of winding the measurement sample around a roller of 6 mm (radius R=3 mm) or 4 mm (radius R=2 mm) was performed continuously 10 times so that the cured film faced outward.

The flexibility was judged as follows based on the presence or absence of cracks (cracks) in the cured film. Judgment results are shown in Table 1 to Table 3.

(judgment of flexibility)

⊚: No cracks, good appearance.

○: 1 to 4 cracks were generated.

Δ: Five or more cracks occurred.

[Measurement of oxygen permeability]

According to JIS K 7126-1 (differential pressure method), the laminates obtained in Examples 1 to 30 and Comparative Example 1 were laminated using a differential pressure gas permeability measuring device "GTR-30AS type" manufactured by GTR TEC Co., Ltd. Body to measure oxygen permeability. The measurement results are shown in Table 1 to Table 3.

[Warpage measurement]

The laminates obtained in Examples 1 to 30 and Comparative Example 1 were cut into 3.5 cm x 4.0 cm, and were adjusted for 24 hours under constant temperature and humidity conditions of 23°C/50%RH to obtain measurement samples. The measurement sample is placed on a flat surface so that the lower side becomes convex, and the heights from the flat surface to the four corners of the measurement sample are measured using a digital dimension measuring device LS-7600 (manufactured by KEYENCE Co., Ltd.). The average value of the values obtained at 4 points was set as the amount of warping.

The details of each compounded component shown in Table 1 to Table 3 are as follows.

<Trifunctional A (acrylate) monomer>

Trimethylolpropane triacrylate ("A-TMPT", manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Tetrafunctional A (acrylate) monomer>

Neopentylthritol tetraacrylate ("A-TMMT", manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

<6-functional A (acrylate) monomer>

Dineopentyl hexaacrylate ("A-DPH", manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

<8-functional A (acrylate) monomer>

Tri-neopentylthritol octaacrylate ("A-TPE-H-NS", manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)

<Bicyclic ether compound 1>

3,4-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (“Celloxide (registered trademark) 2021P”, manufactured by Daicel Chemical Co., Ltd.)

<Bicyclic ether compound 2>

3-Ethyl-3[{(3-ethyloxetan-3-yl)methoxy}methyl]oxetane (“OXT-221”, manufactured by Toagosei Co., Ltd.)

<Bicyclic ether compound 3>

Mixture of xylene bisoxetane (mixture with 1, 2 or 3 repeating units in the xylene skeleton) ("OXT-121", manufactured by Toagosei Co., Ltd.)

<Radical polymerizable cyclic ether compound>

3,4-Epoxycyclohexylmethyl methacrylate ("Cyclomer (registered trademark) M100", manufactured by Daicel Chemical Co., Ltd.)

<Ethylene oxide compound>

Cyclohexanedimethanol divinyl ether (manufactured by SIGMA-ALDRICH)

〈Inorganic particles〉

Acryl group-modified silica particles ("PGM-AC-2140Y", manufactured by Nissan Chemical Co., Ltd., particle size 10 to 15 nm)

<Cationic polymerization initiator>

A 3:1 (mass ratio) mixture of iodonium salt (4-methylphenyl)[4-(2-methylpropyl)phenyl]-hexafluorophosphate and propylene carbonate ("IRGACURE (registered trademark) 250", manufactured by BASF Japan Co., Ltd.)

<Radical polymerization initiator>

1-Hydroxy-cyclohexyl-phenyl-ketone ("IRGACURE 184", manufactured by BASF Japan Co., Ltd.)

<Leveling agent>

Silicone-based leveling agent (“BYK(registered trademark)-307”, manufactured by BYK Chemie Japan Co., Ltd.)

Compared with the laminate of Comparative Example 1, it was confirmed that the laminates of Examples 1 to 30 had higher pencil hardness and no appearance defects occurred in the mandrel test of R=3. Further, it was confirmed that the oxygen permeability was low and the amount of warpage was small. The laminates obtained in Examples 1 to 30 thus have excellent surface hardness and bendability. Furthermore, it also has excellent oxygen barrier properties and warpage resistance.

Regarding the flexibility, the laminates obtained in Examples 4, 8, 9, 10, 14, 16, 17, 22, and 25 had cracks of only 1 to 4 mm even in the mandrel test with R=2. . Furthermore, the laminates obtained in Examples 6, 12, 15, 18 to 21, 23, 24, and 26 to 30 had good appearance even in the mandrel test conducted at R=2.

Claims (16)

A curable composition comprising: a group selected from the group consisting of 3-functional (meth)acrylate monomers, 4-functional (meth)acrylate monomers and 8-functional (meth)acrylate monomers The multifunctional (meth)acrylate monomer (A) of at least two kinds of (meth)acrylate monomers, and the cationic polymerizable monomer (B), wherein, relative to the multifunctional (meth)acrylate monomer Body (A) 100 parts by mass, the total mass of 3-functional (meth)acrylate monomers, 4-functional (meth)acrylate monomers and 8-functional (meth)acrylate monomers is 50 parts by mass or more, cationic The polymerizable monomer (B) contains a cyclic ether compound (B-1) having one or more epoxy groups and/or one or more oxetanyl groups, and the cyclic ether compound (B-1) contains a cyclic ether compound (B-1) having 1 A radically polymerizable cyclic ether compound (B-1-2) having more than one radically polymerizable functional group. The curable composition as described in claim 1, wherein the cyclic ether compound (B-1) contains a bicyclic compound having two or more epoxy groups and/or two or more oxetanyl groups. Ether compound (B-1-1). The curable composition according to claim 1, wherein the cationically polymerizable monomer (B) further contains an ethylene oxide compound (B-2). The curable composition as described in item 3 of the scope of application, wherein, relative to 100 parts by mass of the curable composition, the content of the multifunctional (meth)acrylate monomer (A) is 5 to 80 parts by mass, and the ring The content of the ether compound (B-1) is 5 to 80 parts by mass, and the content of the vinyloxy compound (B-2) is 3 to 60 parts by mass. The curable composition as described in item 3 of the scope of the patent application, wherein, the relative The content of the vinyloxy compound (B-2) is 3 to 50 parts by mass with respect to 100 parts by mass of the total amount of the polyfunctional (meth)acrylate monomer (A) and the cationically polymerizable monomer (B). The curable composition as described in item 1 of the scope of the patent application, wherein, relative to 100 parts by mass of the curable composition, the content of the multifunctional (meth)acrylate monomer (A) is 5 to 50 parts by mass. The content of the cyclic ether compound (B-1-1) is 3 to 30 parts by mass, and the content of the radically polymerizable cyclic ether compound (B-1-2) is 5 to 40 parts by mass. The curable composition according to claim 6, wherein the radically polymerizable cyclic ether compound (B-1-2) is added to 1 part by mass of the bicyclic ether compound (B-1-1) The content is 0.1 to 10 parts by mass. The curable composition as described in any one of claims 1 to 7 of the patent claims further contains a radical polymerization initiator (C) and a cationic polymerization initiator (D). The curable composition as described in claim 8 of the patent application, wherein, relative to 100 parts by mass of the polyfunctional (meth)acrylate monomer (A), the content of the radical polymerization initiator (C) is 1 to 15 parts by mass; the content of the cationic polymerization initiator (D) is 1 to 15 parts by mass relative to 100 parts by mass of the cationic polymerizable monomer (B). The curable composition as described in any one of claims 1 to 7 further contains inorganic particles. The curable composition described in claim 10, wherein when the inorganic particles are reactive silicon oxide particles, the content of the reactive silicon oxide particles is 1 to 70% by mass relative to the mass of the curable composition. A cured film obtained by curing the curable composition described in any one of Claims 1 to 11. A laminate, which has the cured film described in item 12 of the scope of application on at least one surface layer of the base film. The laminated body as described in claim 13, wherein the base film is made of a polyimide-based polymer. The laminate described in Claim 13 or Claim 14, wherein the oxygen permeability is 800cc/(m ² ‧24h‧atm) or less. A flexible display comprising the laminate described in any one of items 13 to 15 of the scope of the patent application.