WO2015133535A1

WO2015133535A1 - Laminate body

Info

Publication number: WO2015133535A1
Application number: PCT/JP2015/056398
Authority: WO
Inventors: 倫仁大石; 和人御宿; 夕佳高橋; 伊藤　賢哉; 山廣　幹夫; 真範石川
Original assignee: グンゼ株式会社; Jnc株式会社
Priority date: 2014-03-05
Filing date: 2015-03-04
Publication date: 2015-09-11
Also published as: JP2015168095A

Abstract

The present invention addresses the problem of providing a laminate body that can be suitably used in a display device or the like, that has excellent optical properties, and that resists breakage during production. The present invention is a laminate body wherein at least a curable resin layer (A), an olefin optical film (B), and a curable resin layer (C) are laminated in said order, the laminate body being characterized in that the curable resin layer (A) contains a urethane acrylate (a) that has a urethane skeleton and a methacryloyl group that has two or more functional groups, and in that the laminate body bends 15 or more times in an MIT folding endurance test that conforms to JIS P8115 and has a tear propagation strength of 110 mN or more as measured by a measurement method that conforms to JIS P8116.

Description

Laminated body

The present invention relates to a laminate.

In recent years, base substrates used for display devices such as flexible devices, transparent electrode films for touch panels, gas barrier films, etc. have not only high optical transmittance and low haze, but also low retardation. Therefore, characteristics such as high heat resistance are required.

An optical transparent film using an olefin resin such as a cyclic olefin resin is used as the base substrate having the above-mentioned characteristics. An optical transparent film using such an olefin resin is promising as a base substrate for thin film transistors and next-generation transparent electrode films because it exhibits characteristics close to glass.

Since the optically transparent film using the above cyclic olefin resin or the like is likely to be broken or damaged when forming a circuit of a thin film transistor or forming a transparent electrode film, in order to improve the scratch resistance of the film surface, A surface protective layer is provided on the surface of the olefin resin layer. Such an optical transparent film has a problem in that it is cracked by stress applied during bending or cutting.

As an optically transparent film that has solved the above-mentioned problems, it has a hard coat layer formed of an ionizing radiation curable resin on at least one surface of a cyclic olefin-based film having a thickness of 10 to 250 μm. There has been proposed a hard coat film in which an elastomer layer formed of a thermoplastic elastomer is provided between the cyclic olefin-based film (see, for example, Patent Document 1).

However, in Patent Document 1, the composition of the surface protective layer and the characteristics of the hard coat film have not been sufficiently studied, and the hard coat film is sent in a so-called roll-to-roll process in which the film is sent through a roll during production. There is a problem of breaking. If the film breaks during production, it causes a decrease in yield, which is a major obstacle to commercialization.

Therefore, it is desired to develop a laminate that can be suitably used for a display device or the like that has excellent optical characteristics and is prevented from being broken during the manufacturing process.

JP 2002-254561 A

An object of the present invention is to provide a laminate that can be suitably used for a display device or the like, has excellent optical characteristics, and is prevented from being broken during the manufacturing process.

As a result of intensive studies to achieve the above object, the present inventor has at least a curable resin layer A, an olefinic optical film B, and a curable resin layer C laminated in this order in the above curable property. The resin layer A contains a specific urethane acrylate, and the laminate exhibits the number of bendings in a specific range of MIT bending fatigue tests, and exhibits a specific range of tear propagation strength. Has been found to be able to be achieved, and the present invention has been completed.

That is, this invention relates to the following laminated body.
1. At least a curable resin layer A, an olefin-based optical film B, and a curable resin layer C are laminated in this order,
The curable resin layer A contains (a) a urethane acrylate having a urethane skeleton and a bi- or higher functional (meth) acryloyl group,
The laminate has a bending number of 15 or more in the MIT bending fatigue test in accordance with JIS P8115, and the tear propagation strength measured by a measuring method in accordance with JIS P8116 is 110 mN or more.
A laminate characterized by the above.
2. Item 2. The laminate according to Item 1, wherein the curable resin layer A further contains (b) a polyfunctional acrylate having a trifunctional or higher functional group that does not have a urethane skeleton in the main chain.
3. Item 3. The laminate according to

Item

1 or 2, wherein the curable resin layer C contains a urethane acrylate having (a) a urethane skeleton and a bifunctional or higher functional (meth) acryloyl group.
4). Item 4. The curable resin layer C according to any one of Items 1 to 3, further comprising (b) a polyfunctional acrylate having a trifunctional or higher functional group having no urethane skeleton in the main chain. The laminated body of description.
5. Item 5. The laminate according to any one of Items 1 to 4, wherein at least one layer selected from the curable resin layer A and the curable resin layer C contains a surface modifier.
6). Item 6. The laminate according to Item 5, wherein the surface modifier is a fluorine-modified silicon compound.
7). Item 7. The laminate according to Item 6, wherein the fluorine-modified silicon compound is a fluorosilsesquioxane compound or a polymer containing fluorosilsesquioxane.
8). Item 8. The laminate according to any one of Items 1 to 7, wherein the olefin-based optical film B contains a cyclic olefin polymer.

In the laminate of the present invention, since the curable resin layer A contains a urethane acrylate having (a) a urethane skeleton and a bifunctional or higher (meth) acryloyl group, the curable resin layer A has an appropriate hardness. It is difficult to break when the curable resin layer A is laminated on the olefin-based optical film B, and breakage of the laminate of the present invention is suppressed.

In addition, the laminate of the present invention has a bending number of times of 15 or more in the MIT bending fatigue test according to JIS P8115, and a tear propagation strength measured by a measuring method according to JIS P8116 is 110 mN or more. In a roll-to-roll process in the manufacturing process, when a film is fed through a roll in a state where tension is applied to the laminate, the laminate is bent or friction is generated between the roll and the roll. Body breakage is suppressed.

That is, in the laminate of the present invention, the curable resin layer A contains (a) a urethane acrylate having a urethane skeleton and a bifunctional or higher (meth) acryloyl group, and the MIT resistance of the laminate in accordance with JIS P8115. By providing a configuration in which the number of flexing in the bending fatigue test is 15 times or more and the tear propagation strength measured by a measuring method based on JIS P8116 is 110 mN or more, the optical characteristics are excellent, and the manufacturing process Breakage at is suppressed. Since the laminated body of the present invention is prevented from being broken during the production process, it has a good yield and is very advantageous when commercialized. For this reason, the laminated body of this invention can be used suitably for a display display apparatus etc.

It is a schematic diagram which shows an example of the layer structure of the laminated body of this invention. It is a cross-sectional schematic diagram which shows the measuring method of loop breaking strength.

Hereinafter, the present invention will be described in detail.

The laminate of the present invention is a laminate in which at least the curable resin layer A, the olefin-based optical film B, and the curable resin layer C are laminated in this order, and the curable resin layer A includes (a) It contains a urethane acrylate having a urethane skeleton and a bi- or higher functional (meth) acryloyl group, and the laminate has a flex number of 15 or more in a MIT folding fatigue test in accordance with JIS P8115, and JIS The tear propagation strength measured by the measurement method based on P8116 is 110 mN or more.

In the laminate of the present invention, the curable resin layer A contains urethane acrylate having (a) a urethane skeleton and a bifunctional or higher functional (meth) acryloyl group. When the curable resin layer A is laminated on the olefin optical film B, it is difficult to break, and the breakage of the laminate of the present invention is suppressed.

That is, in the laminate of the present invention, the curable resin layer A contains (a) a urethane acrylate having a urethane skeleton and a bifunctional or higher (meth) acryloyl group, and the MIT resistance of the laminate in accordance with JIS P8115. By providing a configuration in which the number of flexing in the bending fatigue test is 15 times or more and the tear propagation strength measured by a measuring method based on JIS P8116 is 110 mN or more, the optical characteristics are excellent, and the manufacturing process Breakage at is suppressed. Since the laminated body of the present invention is prevented from being broken during the production process, it has a good yield and is very advantageous when commercialized. Such a laminate of the present invention can be suitably used for a display device or the like.

(Curable resin layer A)
The curable resin layer A contains (a) a urethane acrylate having a urethane skeleton and a bifunctional or higher-functional (meth) acryloyl group (hereinafter also simply referred to as “component (a)”).

The urethane acrylate having the (a) urethane skeleton and the bifunctional or higher (meth) acryloyl group is not particularly limited. For example, the urethane acrylate has a bifunctional or higher (meth) acryloyl group and has a urethane skeleton. And active energy ray-curable resins such as ultraviolet curable resins. The component (a) imparts flexibility to the curable resin layer A.

Examples of the component (a) include urethane (meth) acrylate resins. The urethane (meth) acrylate resin is a radically polymerizable unsaturated group that can be obtained by reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol and then further reacting with a hydroxyl group-containing (meth) acrylic compound. Examples thereof include oligomers, prepolymers and polymers. In particular, polycarbonate urethane acrylates using polycarbonate polyols as polyhydric alcohols are preferred. By using polycarbonate urethane acrylate, the formed curable resin layer A can exhibit excellent stretchability and toughness.

Specific examples of the polyisocyanate include 2,4-tolylene diisocyanate and its isomer, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, Phenylmethane triisocyanate is mentioned.

Commercially available products of the above polyisocyanates include Banoc D-750, Crisbon NK (trade name; manufactured by DIC Corporation), Death Module L (trade name; manufactured by Sumitomo Bayer Urethane Co., Ltd.), Coronate L (trade name; Nippon Polyurethane Industry) Co., Ltd.), Takenate D102 (trade name; manufactured by Mitsui Takeda Chemical Co., Ltd.), Isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation), and the like can be used.

Examples of the polyhydroxy compound include polyester polyol, polyether polyol, and the like. Specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, Trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide Adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-e Ren'okishido - propylene oxide adduct and the like.

Specific examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, 1,3- Butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4 -Cyclohexane glycol, para-xylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2,7-decalin glycol and the like.

The hydroxyl group-containing (meth) acrylic compound is not particularly limited, but a hydroxyl group-containing (meth) acrylic acid ester is preferable, and specifically, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, di (meth) acrylate of tris (hydroxyethyl) isocyanuric acid, pentaerythritol tri (meth) acrylate, etc. Can be mentioned.

The method for synthesizing the component (a), for example, urethane (meth) acrylate resin, is not particularly limited, and it can be synthesized by a conventionally known synthesis method. As such a synthesis method, for example, a predetermined amount of an organic polyisocyanate and a polycarbonate polyol are reacted under a condition of 70 to 80 ° C. until the residual isocyanate concentration reaches a predetermined amount, and then, further, a predetermined amount of the molecule is introduced into the molecule. (Meth) acrylate containing one or more hydroxyl groups is added, and the residual isocyanate concentration is 0.1% by weight or less at a temperature of 70 to 80 ° C. in the presence of a polymerization inhibitor (for example, hydroquinone monomethyl ether). A synthesis method in which the reaction is carried out until is obtained.

The content of the component (a) is preferably 10 to 90% by weight, more preferably 30 to 70% by weight, based on 100% by weight of the resin composition forming the curable resin layer A. By setting the content of the component (a) within the above range, the curable resin layer A is more excellent in extensibility and flexibility.

The weight average molecular weight (Mw) of the component (a) is preferably 3000 to 500,000, more preferably 5000 to 200,000. By setting the weight average molecular weight of the component (a) within the above range, flexibility can be imparted to the curable resin layer A. It can suppress that the crosslinking density in the curable resin layer A becomes it too high that the weight average molecular weight of (a) component is 3000 or more.

The curable resin layer A further includes (b) a polyfunctional acrylate having a trifunctional or higher polymerizable functional group not having a urethane skeleton in the main chain (hereinafter sometimes simply referred to as “component (b)”). It is preferable to contain. The component (b) is not required to have a urethane skeleton in the main chain, and may include a urethane bond in the side chain. The component (b) does not have a urethane skeleton in the main chain and has a trifunctional or higher polymerizable functional group to form a crosslinked structure in the curable resin layer A. For this reason, by setting it as the structure containing the said (b) component, the abrasion resistance of the curable resin layer A and abrasion resistance can be improved more.

Although it does not specifically limit as said (b) component, For example, the active energy ray curable acrylate resin which has a trifunctional or more functional group which does not have a urethane skeleton in a principal chain is mentioned, Especially, a urethane skeleton is in a principal chain. An ultraviolet curable resin having a trifunctional or higher functional (meth) acryloyl group that does not contain benzene can be suitably used.

As the polyfunctional acrylate (b) having a trifunctional or higher polymerizable functional group having no urethane skeleton in the main chain, a polymer obtained by polymerizing a (meth) acrylic monomer may be used.

The method for synthesizing the “polymer obtained by polymerizing the (meth) acrylic monomer” is not particularly limited, and can be synthesized by a conventionally known method. For example, a polymer precursor is first obtained by addition polymerization of single or different (meth) acrylic monomers. As the (meth) acrylic monomer, a (meth) acrylic monomer having a reactive group is used.

Next, the polymer precursor is reacted with a reactive group on the side chain of the polymer precursor (for example, an epoxy group, a carboxylic acid, a hydroxyl group, a glycidyl group, etc.) and the compound having an acryloyl group is reacted with the polymer precursor. By making it, the polymer obtained by superposing | polymerizing the said (meth) acrylic-type monomer can be obtained.

The compound that reacts with a reactive group on the side chain of the polymer precursor and has an acryloyl group can react with the above-mentioned reactive group and has one or more (meth) acryloyl groups. Monomers can be used.

Examples of the (meth) acrylic monomer having a reactive group for preparing the polymer precursor include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and glycidyl methacrylate. Etc. Examples of these commercially available products include light ester P-2M (2-methacryloyloxyethyl acid phosphate / manufactured by Kyoeisha Chemical Co., Ltd.), light ester HO-MS (N) (2-methacryloyloxyethyl succinic acid). / Product name: manufactured by Kyoeisha Chemical Co., Ltd., Light Ester HO-HH (N) (2-Metalliloyloxyethyl hexahydrophthalic acid / Product name: manufactured by Kyoeisha Chemical Co., Ltd.), Light Ester EG (ethylene glycol dimethacrylate / Product name: manufactured by Kyoeisha Chemical Co., Ltd.), light ester 9EG (PEG # 400 dimethacrylate / product name: manufactured by Kyoeisha Chemical Co., Ltd.), light ester G-101P (glycerin dimethacrylate / product name: manufactured by Kyoeisha Chemical Co., Ltd.), LIGHT ESTER M-3F (Trifluoroethyl methacrylate / quotient Name: manufactured by Kyoeisha Chemical Co., Ltd.), HEA (trade name; manufactured by Toa Gosei Co., Ltd.), ATBS (2-acrylamido-2-methylpropanesulfonic acid / trade name; manufactured by Toa Gosei Co., Ltd.), A-SA (2- And acryloyloxyethylene succinate / trade name; manufactured by Shin-Nakamura Chemical Co., Ltd.).

The (meth) acrylic monomer for preparing the polymer precursor may contain a (meth) acrylic monomer having no reactive group. Examples of the (meth) acrylic monomer having no reactive group for preparing the polymer precursor include methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, isobutyl acrylate, etc. Is mentioned. These commercially available products include, for example, Acrix C-1 (trade name; manufactured by Toa Gosei Co., Ltd.), Acrix CHA (trade name; produced by Toa Gosei Co., Ltd.), Aron DA (trade name; produced by Toa Gosei Co., Ltd.) ), A-LEN-10 (ethoxylated phenylphenol acrylate / trade name; manufactured by Shin-Nakamura Chemical Co., Ltd.), AM90-G (methoxy polyethylene acrylate / trade name; manufactured by Shin-Nakamura Chemical Co., Ltd.), S-1800A ( Isosteric acrylate / trade name; Shin-Nakamura Scientific Co., Ltd.), AMP-20GY (phenoxypolyethylene glycol acrylate / trade name; Shin-Nakamura Chemical Co., Ltd.), light ester CH (cyclohexyl methacrylate / trade name; Kyoeisha Chemical Co., Ltd.) Co., Ltd., light ester BZ (benzyl methacrylate / trade name) Manufactured by Kyoeisha Chemical Co., Ltd.), Light Ester IB-X (isobornyl methacrylate / trade name; manufactured by Kyoeisha Chemical Co., Ltd.) and the like.

Examples of the (meth) acrylic monomer having no reactive group for preparing the polymer precursor include fluorosilsesquioxane having one (meth) acryloyl group. Examples of the fluorosilsesquioxane having the (meth) acryloyl group include compounds represented by the following formula (1).

R _f in formula (1) is each independently 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6. , 6,6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrodecyl, henicosafluoro-1,1,2, 2-tetrahydrododecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl, pentafluorophenylpropyl, pentafluorophenyl or α, α, α-trifluoromethylphenyl Etc. are included.

Examples of the monomer that can react with the reactive group on the side chain of the polymer precursor and has one or more (meth) acryloyl groups include a carboxylic acid compound, a carboxylic acid ester compound, and an epoxy compound. It is done.

Examples of the carboxylic acid compound having a (meth) acryloyl group include acrylic acid, methacrylic acid, and vinyl benzoic acid. In order to obtain the component (b) having a polymerizable unsaturated bond in the side chain using a carboxylic acid compound having a (meth) acryloyl group, a known esterification reaction can be used. Here, the esterification reaction is a dehydration condensation reaction between a carboxylic acid compound and a group having active hydrogen (preferably a hydroxyl group).

Examples of the carboxylic acid ester compound having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, 1-propyl (meth) acrylate, 1-butyl (meth) acrylate, and t-butyl (meth). Examples thereof include acrylate and 2-ethylhexyl (meth) acrylate. In order to obtain the component (b) having a polymerizable unsaturated bond in the side chain using a carboxylic acid ester compound having a (meth) acryloyl group, a known esterification reaction can be used. Here, the esterification reaction is a transesterification reaction between a carboxylic acid ester compound and a group having active hydrogen (preferably a hydroxyl group).

Examples of the epoxy compound having a (meth) acryloyl group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like. In order to obtain the component (b) having a polymerizable unsaturated bond in the side chain using a compound having a (meth) acryloyl group, a known epoxy ring-opening reaction between a cyclic ether and a hydroxyl group can be used. .

Further, a part of the isocyanate group of a compound having a plurality of isocyanate groups such as isophorone diisocyanate is urethanated with a hydroxyl group-containing addition polymerizable monomer such as 2-hydroxyethyl acrylate to obtain an isocyanate compound having a polymerizable unsaturated bond. Furthermore, the component (b) having a polymerizable unsaturated bond in the side chain can be obtained by utilizing a urethanization reaction between the isocyanate compound and a group having active hydrogen (preferably a hydroxyl group).

As the component (b), various known polymerizable compounds can also be used. For example, trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and isocyanuric acid-modified tri (meth) acrylate as a polyfunctional acrylate compound having no hydroxyl group in the molecule; pentaerythritol tetra (meth) Examples include tetrafunctional (meth) acrylates such as acrylate; hexafunctional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate.

As the component (b), prepolymers and oligomers can also be used. Examples of these include polyester (meth) acrylate, silicone (meth) acrylate, epoxy (meth) acrylate, and the like.

As the polyfunctional polyester (meth) acrylate used for the component (b), commercially available products include M-8030 (manufactured by Toa Gosei Co., Ltd.).

Furthermore, as a polyfunctional acrylic polymer used for the component (b), commercially available products include Hitaroid 7975D (Mw 15000 / trade name; Hitachi Chemical), Hitaroid 7988 (Mw 60000 / trade name; Hitachi Chemical), and Hitaroid (Mw 78000 / trade name). Hitachi Chemical), ACRYT 8kx-01 (trade name; manufactured by Taisei Fine Chemical Co., Ltd.), and the like.

The content of the component (b) is preferably 5 to 60% by weight, more preferably 5 to 30% by weight, based on 100% by weight of the resin composition forming the curable resin layer A. By making content of (b) component into the above-mentioned range, the curable resin layer A is more excellent in extensibility and flexibility.

The weight average molecular weight (Mw) of the component (b) is preferably 1000 to 500,000, more preferably 2000 to 100,000. When the weight average molecular weight of the component (b) is 1000 or more, the curable resin layer A exhibits good flexibility, and the crosslink density in the curable resin layer A increases, which is favorable for the curable resin layer A. Abrasion resistance, abrasion resistance, and tack resistance can be imparted.

The curable resin layer A may further contain a surface modifier. The surface modifier is preferably contained in at least one layer selected from the curable resin layer A and the curable resin layer C described later. When at least one layer selected from the curable resin layer A and the curable resin layer C contains a surface modifier, the anti-blocking property is excellent when the laminate of the present invention is rolled up. Indicates.

As the surface modifier, for example, a silicon compound can be used, and a general surface modifier having a silicone compound as a main component can be used. Among these, it is preferable to use a fluorine-modified silicon compound.

Examples of commercially available silicone compounds include BYK-UV3500, BYK-UV-3570 (both trade names; manufactured by Big Chemie Japan Co., Ltd.), TEGO Rad2100, 2200N, 2250, 2500, 2600, 2700 (both trade names; Manufactured by Evonik Degussa Japan Co., Ltd.), X-22-2445, X-22-2455, X-22-2457, X-22-2458, X-22-2459, X-22-1602, X-22-1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22-2404, X-22-2474, X-22-174DX, X-22-8201, X- 22-2426, X-22-164A, X-22-164C (all trade names; Shin-Etsu Chemical Co., Ltd.) ), And the like.

As the silicon compound, one or more compounds selected from the group consisting of fluorosilsesquioxane compounds, fluorosilsesquioxane polymers described in WO2008 / 072766 and WO2008 / 072765 may be used.

Examples of the fluorosilsesquioxane compound include a fluorosilsesquioxane compound having a molecular structure represented by the following formula (1).

Further, examples of the fluorosilsesquioxane polymer include a polymer (homopolymer or copolymer) containing a fluorosilsesquioxane compound represented by the following formula (1). Since the polymer polymerized using the compound represented by the following formula (1) is a fluorinated silicone compound, it can impart slip properties and anti-blocking properties to the surface of the cured film.

The fluorosilsesquioxane polymer is a structural unit a derived from fluorosilsesquioxane having one addition polymerizable functional group in the molecule, a structural unit b derived from organopolysiloxane having an addition polymerizable functional group. , A structural unit derived from an addition polymerizable monomer and having a group having a polymerizable unsaturated bond in the side chain, and optionally a fluorosilsesquioxy having one addition polymerizable functional group in the molecule A structural unit d derived from an addition polymerizable monomer other than Sun, an organopolysiloxane having an addition polymerizable functional group, and an addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond; It is a polymer containing. “Derived” means a polymerized residue when each monomer constitutes a fluorosilsesquioxane polymer.

The structural unit a is derived from fluorosilsesquioxane having a molecular structure represented by the above formula (1).

The structural unit b is derived from an organopolysiloxane having an addition polymerizable functional group having a molecular structure represented by the following formula (2).

The organopolysiloxane having an addition polymerizable functional group preferably has a molecular structure represented by the following formula (2).

In the organopolysiloxane, in the above formula (2), n is an integer of 1 to 1,000; R ¹ , R ² , R ³ , R ⁴ , and R ⁵ are each independently hydrogen, carbon number An arylalkyl composed of 1-30 alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted aryl and alkylene, in R ¹ , R ² , R ³ , R ⁴ , and R ⁵ , At least one hydrogen may be replaced by fluorine and at least one —CH ₂ — may be replaced by —O— or cycloalkylene; A ² is an addition polymerizable functional group.

Furthermore, in the organopolysiloxane having an addition polymerizable functional group, in the above formula (2), R ¹ , R ² , R ³ and R ⁴ are preferably methyl at the same time. Also preferably, A ² in the above formula (2) is a radical polymerizable functional group, more preferably the A ² contains a (meth) acrylic or styryl, A ² is represented by the following formula (3), (4 ) Or (5) is more preferred.

In the above formula (3), Y ¹ is alkylene having 2 to 10 carbons, and R ⁶ is hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons. In the above formula (4), R ⁷ is hydrogen, alkyl having 1 to 5 carbons, or aryl having 6 to 10 carbons, X ¹ is alkylene having 2 to 20 carbons, and Y is —OCH ₂ CH ₂ —, —OCH (CH ₃ ) CH ₂ —, or —OCH ₂ CH (CH ₃ ) —, and p is an integer of 0 to 3. In the above formula (5), Y ² is a single bond or alkylene having 1 to 10 carbon atoms. Here, the alkyl having 1 to 5 carbon atoms may be linear or branched.

Alternatively, in the above formula (3), Y ¹ is alkylene having 2 to 6 carbon atoms, and R ⁶ is hydrogen or methyl. In the above formula (4), X ¹ is —CH ₂ CH ₂ CH ₂ —, Y is —OCH ₂ CH ₂ —, p is 0 or 1, and R ⁷ is hydrogen or methyl. In the above formula (5), Y ² is preferably a single bond or alkylene having 1 or 2 carbon atoms.

Examples of organopolysiloxanes preferably used include Silaplane FM0711 (trade name; manufactured by JNC Corporation), Silaplane FM0721 (trade name; manufactured by JNC Corporation), Silaplane FM0725 (trade name; manufactured by JNC Corporation), Silaplane TM0701 (trade name; manufactured by JNC Corporation), Silaplane TM0701T (trade name; manufactured by JNC Corporation), and the like are included.

The structural unit c is a structural unit derived from an addition polymerizable monomer and derived from a monomer having a group having a polymerizable unsaturated bond in the side chain. For example, as a component of an addition polymerizable monomer containing a structural unit a, a structural unit b, and a monovalent functional group containing a group having active hydrogen described below, a precursor obtained using a hydroxyl group-containing vinyl monomer, By reacting with an isocyanate compound having a polymerizable unsaturated bond, a polymer containing a structural unit c (fluorosilsesquioxane polymer) is obtained.

As described above, the structural unit c is obtained from an addition polymerizable monomer having a functional group capable of introducing a group having a polymerizable unsaturated bond.

That is, the fluorosilsesquioxane polymer containing a group having a polymerizable unsaturated bond in the side chain can obtain a polymer having a functional group capable of introducing a group having a polymerizable unsaturated bond as a precursor. Examples of the functional group into which such a group having a polymerizable unsaturated bond can be introduced include a group having active hydrogen and a monovalent functional group containing a cyclic ether. Active hydrogen is hydrogen bonded to an atom (eg, nitrogen atom, sulfur atom, oxygen atom) whose electronegativity value is greater than or equal to carbon among hydrogen atoms existing in the molecule of an organic compound. It is. Therefore, a preferred precursor for obtaining a fluorosilsesquioxane polymer is a polymer containing a group having active hydrogen, and a fluorosilsesquioxane having one addition polymerizable functional group in the molecule, addition polymerization. A fluorosilsesquioxane polymer precursor is obtained using an addition-polymerizable monomer containing an active hydrogen-containing group and a monovalent functional group containing a cyclic ether together with an organopolysiloxane having a functional functional group. be able to.

Examples of the group having active hydrogen include —OH, —SH, —COOH, —NH, —NH ₂ , —CONH ₂ , —NHCONH—, —NHCOO—, Na ⁺ [CH (COOC ₂ H ₅ )], — CH ₂ NO ₂ , OOH, —SiOH, —B (OH) ₂ , —PH ₃ , —SH and the like can be mentioned. Carboxyl, amino and hydroxyl are preferred, and hydroxyl is more preferred. The addition polymerizable monomer c containing a group having active hydrogen may be a compound having a group having active hydrogen and an addition polymerizable double bond in the molecule, and is a vinyl containing a group having active hydrogen. Any of a compound, a vinylidene compound, and a vinylene compound may be sufficient. An acrylic acid derivative or a styrene derivative containing a group having active hydrogen is preferable.

Examples of the addition polymerizable monomer containing a group having active hydrogen include monomers disclosed in JP-A-9-208681, JP-A-2002-348344, and JP-A-2006-158961. Specific examples include the following monomers.

Examples of the carboxyl group-containing vinyl monomer include (meth) acrylic acid, (anhydrous) maleic acid, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, and itacone. Examples include acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, hexamethan (meth) acrylate and cinnamic acid.

Examples of the hydroxyl group-containing vinyl monomer include a hydroxyl group-containing monofunctional vinyl monomer and a hydroxyl group-containing polyfunctional vinyl monomer. As the hydroxyl group-containing monofunctional vinyl monomer, a vinyl monomer having one vinyl group is used. For example, hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4- Hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-butene- 1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether (2-propenoxyethanol), 16-hydroxyhexadecane methacrylate Such as microcrystalline sucrose allyl ether.

As the addition polymerizable monomer containing an active hydrogen group, a hydroxyl group-containing monofunctional vinyl monomer is preferable, and hydroxyethyl (meth) acrylate is more preferable.

As described above, the group having a polymerizable unsaturated bond reacts with a precursor of a fluorosilsesquioxane polymer and a functional group (a group having active hydrogen) capable of introducing a group having a polymerizable unsaturated bond. It can be introduced by reacting a functional group with a compound having a polymerizable unsaturated bond in the same molecule.

Examples of the compound having a functional group that reacts with a group having active hydrogen and a group having a polymerizable unsaturated bond in the same molecule include, for example, an isocyanate compound having a polymerizable unsaturated bond, and a polymerizable unsaturated bond. The acid halide which has, the carboxylic acid compound which has a polymerizable unsaturated bond, the carboxylic acid ester compound which has a polymerizable unsaturated bond, and an epoxy compound can be mentioned. The group having such a polymerizable unsaturated bond is preferably a radical polymerizable group, and examples thereof include (meth) acryl, allyl, and styryl.

As the isocyanate compound having a (meth) acryl group, a compound having the following structure can be used.

In the formula, R ⁸ and R ⁹ are hydrogen or methyl, B is oxygen, alkylene having 1 to 3 carbon atoms, or —OR ¹⁰ —; R ¹⁰ is alkylene having 2 to 12 carbon atoms, carbon number 2 Represents an oxyalkylene having ˜12 or arylene having 6 to 12 carbon atoms.

The content of the silicon compound as the surface modifier is preferably 0.01 to 20% by weight with respect to 100% by weight of the resin composition forming the curable resin layer A. By the surface modifier, slip property can be imparted to the surface of the curable resin base layer A, and the tack resistance of the curable resin layer A can be improved. Therefore, adhesion between laminates (films) and adhesion to a metal roll can be suppressed during coating by roll-to-roll.

The above-mentioned fluorosilsesquioxane polymer can be synthesized by the method described in International Publication No. 2008/072765 or International Publication No. 2008/072766.

Surface modification to the curable resin layer A by adding a surface modifier to the resin composition forming the curable resin layer A (improving scratch resistance, blocking resistance, tackiness, leveling properties, etc.) The effect of can be provided.

The thickness of the curable resin layer A is not particularly limited, but is preferably 1 to 30 μm, and more preferably 3 to 10 μm. When the said thickness is too thick, manufacture may become difficult and there exists a possibility that it may be inferior to economical efficiency. If the thickness is too thin, the scratch resistance may be poor.

(Olefin optical film B)
The olefinic optical film B is not particularly limited as long as it contains an olefinic resin and is a film suitable for use in optical applications. Examples of the film suitable for use in the optical application include a film having high transparency. The total light transmittance of the olefin optical film B is preferably 90% or more. The haze of the olefinic optical film B is preferably 1% or less, and more preferably 0.5% or less.

The olefin-based resin contained in the olefin-based optical film B is not particularly limited as long as the olefin-based optical film B can be a film suitable for optical use, but is preferably a cyclic olefin polymer. Olefin-based resin film B By containing the cyclic olefin polymer, the olefin-based resin film B is excellent in optical properties and heat resistance.

Examples of the cyclic olefin polymer include polymers having an alicyclic structure in the main chain and / or side chain. From the viewpoint of weather resistance, moisture resistance, etc., the main chain preferably has an alicyclic structure.

Examples of the alicyclic structure of the cyclic olefin polymer include a saturated cyclic hydrocarbon (cycloalkane) structure and an unsaturated cyclic hydrocarbon (cycloalkene) structure. In terms of excellent mechanical strength, heat resistance, etc., Those having an alkane structure are preferred.

The cyclic olefin polymer may be a cyclic olefin homopolymer or a cyclic olefin copolymer. Among these, a cyclic olefin copolymer is preferable in terms of excellent heat resistance.

Examples of the cyclic olefin copolymer include a copolymer of norbornene and ethylene. The copolymer of norbornene and ethylene preferably has a copolymerization ratio in terms of mass of norbornene and ethylene of 80:20 to 90:10. If the copolymerization ratio is within this range, the glass transition temperature is 170 ° C to 200 ° C. When the ratio of norbornene is lower than this range, the glass transition temperature becomes less than 170 ° C., so that the heat resistance may be lowered. Moreover, when the ratio of ethylene is lower than this range, it may be difficult to process a film having a strength that can withstand necessary post-processes (coating process, thin film forming process, etc.).

As a commercial product of the film containing the copolymer of norbornene and ethylene as the cyclic olefin copolymer, “F1 film” (trade name, manufactured by Gunze Co., Ltd.) may be mentioned.

The above copolymer of norbornene and ethylene usually has a refractive index of about 1.49 to 1.55, and usually has a light transmittance of about 90.8% to 93.0%. Various known additives such as an ultraviolet absorber, an inorganic or organic antiblocking agent, a lubricant, an antistatic agent, and a stabilizer may be added to the copolymer of norbornene and ethylene for a proper purpose.

In addition, the olefin resin contained in the olefin optical film B is not limited to the above resin, and a known olefin resin can be used. Examples of such known olefin resins include those described in JP2013-202989A, JP2003-103718A, JP5-17776A, or JP2003-504523A. Can be mentioned.

The content of the olefinic resin in the olefinic optical film B is preferably 70% by weight or more, more preferably 80% by weight, even more preferably 90% by weight or more, with the olefinic optical film B being 100% by weight.

The thickness of the olefin-based optical film B is not particularly limited, but is preferably 20 to 300 μm, more preferably 50 to 200 μm. When the said thickness is too thick, there exists a possibility that a laminated body may be inferior to a softness | flexibility. When the said thickness is too thin, there exists a possibility that the intensity | strength of a laminated body may fall.

(Curable resin layer C)
The curable resin layer C is a layer that is laminated on the side of the olefin optical film B opposite to the surface on which the curable resin layer A is laminated.

The resin for forming the curable resin layer C is not particularly limited as long as it does not deteriorate the optical characteristics of the laminate of the present invention and does not prevent the breakage in the production process.

The curable resin layer C preferably contains a urethane acrylate having (a) a urethane skeleton and a bifunctional or higher functional (meth) acryloyl group. By setting it as the structure containing the said (a) component, the fracture | rupture of the curable resin layer C in the manufacturing process of a laminated body is suppressed, and, thereby, the fracture | rupture of the laminated body of this invention is suppressed more. As the (a) urethane acrylate, the same urethane acrylate (a) contained in the curable resin layer A can be used.

The curable resin layer C preferably further contains (b) a polyfunctional acrylate having a trifunctional or higher functional group. When the curable resin layer C is configured to contain the component (b), the curable resin layer C is more excellent in hardness, which can further improve the scratch resistance of the laminate of the present invention. The said polyfunctional acrylate (b) can use the same thing as the polyfunctional acrylate (b) which the said curable resin layer A contains.

The curable resin layer C may further contain a surface modifier. The surface modifier is preferably contained in at least one layer selected from the curable resin layer A and the curable resin layer C. When at least one layer selected from the curable resin layer A and the curable resin layer C contains a surface modifier, the anti-blocking property is excellent when the laminate of the present invention is rolled up. Indicates.

As the surface modifier, the same surface modifier as that contained in the curable resin layer A can be used.

The thickness of the curable resin layer C is not particularly limited, but is preferably 1 to 30 μm, and more preferably 3 to 10 μm. If the thickness is too thick, the laminate may be easily broken. If the thickness is too thin, the scratch resistance may be poor.

(Laminate)
In the laminate of the present invention, the number of bendings in the MIT bending fatigue test according to JIS P8115 is 15 or more. Due to the fact that the MIT bending fatigue test is in the above-mentioned range, in the roll-to-roll process in the manufacturing process, the laminate is bent when the laminate is fed through the roll in a tensioned state. Breakage of the laminate is suppressed. The number of bends in the MIT bending fatigue test is preferably 20 times or more.

The laminate of the present invention has a tear propagation strength of 110 mN or more measured by a measuring method based on JIS P8116. When the tear propagation strength is in the above-mentioned range, in the roll-to-roll process in the manufacturing process, when a film is fed through the roll in a state where tension is applied to the laminate, friction is generated between the roll and the roll. Breakage of the resulting laminate is suppressed.

In the laminate of the present invention, as long as at least the curable resin layer A, the olefin-based optical film B, and the curable resin layer C are laminated in this order, the layer configuration is not particularly limited, and other layers are used. You may have. For example, you may have an easily bonding layer between the curable resin layer A and the olefin type optical film B, and similarly, an easy bonding layer is provided between the curable resin layer C and the olefin type optical film B. You may have. It does not specifically limit as adhesive resin which forms the said easily bonding layer, For example, a silicone resin can be used.

The surface of the olefin optical film B may be subjected to a surface treatment such as plasma treatment or corona treatment. By subjecting the surface of the olefin-based optical film B to surface treatment, the interlayer adhesion of the laminate of the present invention can be further improved.

(Production method)
As a manufacturing method of the laminated body of this invention, if curable resin layer A, the olefin type optical film B, and curable resin layer C can be laminated | stacked in this order, it will not specifically limit, It manufactures by a conventionally well-known method. Can do. For example, the curable resin layer A forming composition is applied to one surface of the olefin-based optical film B, and the curable resin layer C forming composition is applied to the other surface. The laminate of the present invention can be produced by a method of forming the curable resin layers A and B by drying and irradiating and curing with ultraviolet rays using a UV irradiation apparatus.

The method for applying the curable resin layer A forming composition and B to the olefin optical film B is not particularly limited. For example, the olefin optical film B is drawn from the roll of the roll-shaped olefin optical film B. However, the method of apply | coating these compositions with a roll knife is mentioned.

The method for drying the curable resin layer A forming composition and the curable resin layer C forming composition is not particularly limited. For example, the curable resin layer A forming composition and the curable resin layer C forming composition are not limited. A method of passing the product through the dryer in a state where the product is applied onto the olefin-based optical film B is exemplified. The drying temperature for drying the curable resin layer A forming composition and the curable resin layer C forming composition is preferably 40 to 100 ° C.

The conditions for the ultraviolet irradiation when the dried composition for forming the curable resin layer A and the composition for forming the curable resin layer C are cured by irradiating with ultraviolet rays are preferably an integrated dose of 200 to 1000 mJ / cm ² . The conditions for ultraviolet irradiation are appropriately set depending on conditions such as the viscosity of the composition to be cured.

The laminate of the present invention can be produced by the production method described above.

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

(Synthesis Example 1)
Synthesis of component (a) (Synthesis example of polycarbonate urethane acrylate (a-1)) 4,4'-dicyclohexylmethane diisocyanate (trade name: Desmodur (registered trademark), manufactured by Sumika Bayer Urethane Co., Ltd.) 7 g (1.17 mol), polycarbonate polyol (trade name: ETERRNACOLL (registered trademark) UC-100, manufactured by Ube Industries, Ltd.) using 1,4-cyclohexanedimethanol, 1000 g (1 mol), 2-butanone ( (MEK, methyl ethyl ketone) 1699.2 g was charged, and the reaction was carried out at 70 ° C. to 80 ° C. until the predetermined residual isocyanate concentration was reached.

Subsequently, 2-hydroxyethyl acrylate (trade name: BHEA, manufactured by Nippon Shokubai Co., Ltd.) 255.2 g (2.2 mol) and hydroquinone monomethyl ether as a polymerization inhibitor (trade name: MQ, manufactured by Kawaguchi Chemical Industry Co., Ltd.) After adding 0.85 g, the reaction was continued under the conditions of 70 ° C. to 80 ° C. until the residual isocyanate concentration became 0.1% by weight to obtain a polycarbonate-based urethane acrylate (a-1). The obtained polymer (a-1) had a weight average molecular weight of 100,000 by GPC analysis.

(Synthesis Example 2)
(B) Synthesis of Component Into a 200 mL four-necked flask equipped with a reflux condenser, a thermometer and a dropping funnel, 25.00 g of methyl methacrylate (MMA), 25.00 g of glycidyl methacrylate (GMA), 2 -50.00 g of butanone (MEK) was introduced and sealed with nitrogen. It was set in an oil bath maintained at 80 ° C. and refluxed, and deoxygenated for 10 minutes. Subsequently, a solution prepared by dissolving 0.70 g of 2,2′-azobisisobutyronitrile (AIBN) and 0.08 g of mercaptoacetic acid (AcSH) in 7.00 g of MEK was introduced and kept at the reflux temperature. Polymerization was started as it was. After polymerization for 3 hours, a solution in which 0.70 g of AIBN was dissolved in 7.00 g of MEK was introduced, and the polymerization was further continued for 5 hours.

After completion of the polymerization, 65 mL of denatured alcohol (Solmix AP-1, manufactured by Nippon Alcohol Sales Co., Ltd.) was added to the polymerization solution and poured into 1300 mL of Solmix AP-1, to precipitate a polymer. The supernatant was removed and dried under reduced pressure (40 ° C., 3 hours, 70 ° C., 3 hours) to obtain 40 g of a polymer having a glycidyl group. The weight average molecular weight calculated | required by GPC analysis of the obtained polymer was 31,200, and molecular weight distribution was 1.43. The compositional mole fraction of the monomer component determined from ¹ H-NMR measurement of the polymer was MMA: GMA = 50: 50.

[Addition of acryloyl group to side chain (epoxy group reaction)]
Subsequently, 50.0 g of a polymer having a glycidyl group, 16.48 g of acrylic acid (AA), and MEHQ of 0.004 were added to a 200 mL internal flask having a reflux condenser, a thermometer, and a septum cap. 13 g, 1.25 g of tetramethylammonium chloride and 33.24 g of 2-butanone (MEK) were introduced and sealed with nitrogen. It set to the oil bath maintained at 80 degreeC, and it heated up and started reaction. After reacting for 10 hours, the reaction was terminated by cooling to room temperature and introducing 10.0 g of MeOH. After completion of the reaction, 65 mL of Solmix AP-1 was added to the reaction solution, and then poured into 1300 mL of Solmix AP-1 to precipitate the reaction product. The supernatant was removed, followed by drying under reduced pressure (drying at 40 ° C. for 3 hours and then drying at 70 ° C. for 3 hours) to obtain a polymer (b-1) having an acryloyl group. The weight average molecular weight determined by GPC analysis of the obtained polymer (b-1) was 47,000.

(Synthesis Example 3)
Synthesis of surface modifier (synthesis of fluorosilsesquioxane-containing compound (d-1) as silicon compound)
[Synthesis of polymer precursor having hydroxyl group]

In a 200 mL four-necked flask equipped with a reflux condenser, thermometer and dropping funnel, 36.65 g of the compound (d-1) represented by the above formula, 3.37 g of methyl methacrylate (MMA), 2- 0.97 g of hydroxyethyl methacrylate (HEMA), 24.00 g of dimethylsilicone modified with one end methacryloxy group (FM-0721, molecular weight of about 6,300) and 64.45 g of 2-butanone (MEK) were introduced and sealed with nitrogen. . It was set in an oil bath maintained at 95 ° C. and refluxed, and deoxygenated for 10 minutes. Next, a solution prepared by dissolving 0.35 g of 2,2′-azobisisobutyronitrile (AIBN) and 0.20 g of mercaptoacetic acid (AcSH) in 4.94 g of MEK was introduced and maintained at the reflux temperature. Polymerization was started as it was. After polymerization for 3 hours, a solution prepared by dissolving 0.35 g of AIBN in 3.16 g of MEK was introduced, and polymerization was further continued for 5 hours. After completion of the polymerization, 65 mL of denatured alcohol (Solmix AP-1, manufactured by Nippon Alcohol Sales Co., Ltd.) was added to the polymerization solution, and then poured into 1300 mL of Solmix AP-1, to precipitate a polymer. The supernatant was removed and dried under reduced pressure (after drying at 40 ° C. for 3 hours and then at 70 ° C. for 3 hours) to obtain 40 g of a polymer precursor having a hydroxyl group. The weight average molecular weight calculated | required by GPC analysis of the obtained polymer precursor was 31,200, and molecular weight distribution was 1.43. The compositional molar fraction of the monomer component determined from ¹ H-NMR measurement of the polymer precursor was as follows: Compound (d-1): MMA: HEMA: FM-0721 = 41.7: 42.8: 10.1: 5.4. Moreover, the hydroxyl group equivalent was 9,400 g / eq.

[Synthesis of polymer having acryloyl group in side chain (synthesis of fluorosilsesquioxane-containing compound (d-1))
Into a 200 mL four-necked flask equipped with a reflux condenser, a thermometer and a septum cap, 15.0 g of a polymer precursor having a hydroxyl group, 0.015 g of MEHQ, 0.0263 g of DBTDL, and ethyl acetate 130 g was introduced and sealed with nitrogen. It set to the oil bath maintained at 48 degreeC, and heated up. Next, when the liquid temperature reached 45 ° C., 2.35 g of acryloyloxyethyl isocyanate (AOI, manufactured by Showa Denko KK) was introduced to start the reaction. After reacting for 6 hours, the reaction was terminated by cooling to room temperature and introducing 10.0 g of MeOH. After completion of the reaction, 65 mL of Solmix AP-1 was added to the reaction solution and poured into 1300 mL of Solmix AP-1 to precipitate the reaction product. The supernatant was removed, followed by drying under reduced pressure (drying at 40 ° C. for 3 hours and then drying at 70 ° C. for 3 hours) to obtain 11.8 g of a polymer (d-1) having an acryloyl group. The weight average molecular weight determined by GPC analysis of the obtained polymer was 32,800. In addition, the acryloyl group equivalent determined from ¹ H-NMR measurement of the polymer (d-1) was 6,900 g / eq.

Example 1
(Preparation of olefin-based optical film B)
An ethylene-norbornene copolymer (trade name: “TOPAS” manufactured by TOPAS Advanced Polymers) having a copolymerization ratio of norbornene and ethylene of 82:18 was obtained by melt extrusion using a resin temperature of 300 ° C. and a take-up roll temperature of 130 ° C. The olefin-based optical film B having a thickness of 100 μm was prepared by extrusion molding under the above conditions.

[Preparation Example 1 (Preparation of Paint 1)]
11.4 g of the polycarbonate-based urethane acrylate (a-1) obtained in Synthesis Example 1 (solid content 100%), 25.4 g of the polymer (b-1) having an acryloyl group obtained in Synthesis Example 2 (solid content) 30 wt% MEK solution) and 62.2 g of 2-butanone (MEK) were introduced into a light-shielded plastic bottle and stirred and mixed. After confirming that the solution became transparent, 0.95 g of a photopolymerization initiator (c) (trade name: Irgacure 184, manufactured by BASF) was added, and the mixture was further stirred and mixed to prepare paint 1. .

[Preparation Example 2 (Preparation of Paint 2)]
11.4 g of the polycarbonate-based urethane acrylate (a-1) obtained in Synthesis Example 1 (100% solid content), 25.3 g of the polymer (b-1) having an acryloyl group obtained in Synthesis Example 2 (solid content) 30 wt% MEK solution) and 62.1 g of 2-butanone (MEK) were introduced into a light-shielded plastic bottle and stirred and mixed. After confirming that the solution became transparent, 0.95 g of the photopolymerization initiator (c) (trade name: Irgacure 184, manufactured by BASF) and 0.32 g of the fluorosilsesquioxane-containing compound (d-1) (Solid content 30 wt% MEK solution) was added, and further stirred and mixed to prepare paint 2 containing a surface modifier.

[Preparation Example 3 (Preparation of Paint 3)]
15.2 g of the polycarbonate-based urethane acrylate (a-1) obtained in Synthesis Example 1 (solid content: 100%), 12.7 g of the polymer (b-1) having an acryloyl group obtained in Synthesis Example 2 (solid content) 30 wt% MEK solution) and 71.1 g of 2-butanone (MEK) were introduced into a light-shielded plastic bottle and stirred and mixed. After confirming that the solution became transparent, 0.95 g of a photopolymerization initiator (c) (trade name: Irgacure 184, manufactured by BASF) was added, and the mixture was further stirred and mixed to prepare paint 3. .

<Manufacture of laminates>
The coating 1 prepared as described above was applied to one surface of the olefin-based optical film B using a wire bar. The olefin-based optical film B coated with the paint 1 is placed in an oven at 80 ° C. and dried for 2 minutes, irradiated with ultraviolet rays under the condition of an integrated light quantity of 500 mJ / cm ² , and the thickness of one surface of the olefin-based optical film B is increased. A curable resin layer A having a thickness of 5 μm was formed.

The coating 2 prepared as described above was applied to the surface of the olefin-based optical film B opposite to the surface on which the curable resin layer A was formed using a wire bar. Moreover, the coating material 2 was hardened by the same method as the said curable resin layer A was formed, the curable resin layer C with a thickness of 5 micrometers was formed, and the laminated body was prepared.

Example 2
As the olefin-based optical film B, a thermoplastic cyclic olefin-based film having a thickness of 100 μm and containing a norbornene homopolymer (trade name: ZENOR film ZF16 manufactured by Nippon Zeon Co., Ltd.) was used in the same manner as in Example 1, A laminate was prepared.

Example 3
A laminate was prepared in the same manner as in Example 1 except that paint 3 was used instead of paint 1 and paint 2.

Comparative Example 1
The curable resin layers A and C were not provided, and the olefin optical film B alone was used as Comparative Example 1.

Comparative Example 2
As a paint for forming the curable resin layer A and the curable resin layer C, an acrylic photocurable resin (trade name: NAB001 manufactured by Nippon Paint Co., Ltd.) is used, and the thickness of the curable resin layers A and C is 3 μm. A laminate was prepared in the same manner as in Example 1 except that.

Comparative Example 3
As the olefin-based optical film B, a thickness of 100 μm, a thermoplastic cyclic olefin-based film containing a norbornene homopolymer (trade name: ZENOR film ZF16, manufactured by Nippon Zeon Co., Ltd.) was used in the same manner as in Comparative Example 2, A laminate was prepared.

The following evaluations were performed on the above examples and comparative examples.

(Total light transmittance)
The total light transmittance of the laminate was measured using a haze meter NDH5000 (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.) by a measuring method based on JIS-K7361-1.

(Haze)
The haze of the laminate was measured using a haze meter NDH5000 (manufactured by Nippon Denshoku Industries Co., Ltd.) by a measuring method based on JIS-K7136.

(Number of flexing in MIT folding fatigue test)
The laminate was sampled to a size of 15 mm wide × 110 mm long to obtain a test piece. Using this test piece, a MIT folding fatigue tester D type (manufactured by Toyo Seiki Seisakusyo Co., Ltd.) was used in a measurement method in accordance with JIS-P8115, with a test speed of 90 cpm, a bending angle of 90 °, and a load of 0.25 kgf. The number of bends in the MIT folding fatigue test of the laminate was measured under the measurement conditions of R0.38 mm for the bending clamp and 0.25 mm for the opening of the bending clamp.

(Tear propagation strength)
The laminate was sampled to a size of 50 mm width × 63.5 mm length to obtain a test piece. Using this test piece, the tear propagation strength of the laminate was measured using a light load tear tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) by a measuring method based on JIS P8116. The measurement was performed after setting the sample in a testing machine and making a notch of about 10 mm in the length direction.

(Loop breaking strength)
The laminate was sampled to a size of 25 mm wide × 200 mm long to obtain a test piece. Using this test piece, the loop breaking strength of the laminate was measured using a peel strength measuring machine (trade name: Tribogear HEIDON17 manufactured by Shinto Kagaku Co., Ltd.). The measurement was performed by the following procedure according to the method shown in FIG. FIG. 2 is a schematic cross-sectional view showing a method for measuring the loop breaking strength. First, as shown in FIG. 2, the test piece 10 was folded back in the length direction, the

end portions

11 and 11 in the length direction were overlapped, and the folded portion 12 was formed in a loop shape. The

overlapped end portions

11 and 11 are passed between

rolls

13 and 13 having a roll gap of 1 mm, the

overlapped end portions

11 and 11 are pulled at a pulling speed of 200 mm / min, and the tension when the loop-shaped portion 12 passes through the roll gap is pulled. The strength was measured and used as the loop strength of the laminate. In addition, it has shown that the fracture | rupture of a laminated body is suppressed, so that the loop breaking strength is high, and the fracture | rupture of a laminated body in a manufacturing process is fully suppressed as it is 3.0 N / 25mm or more.

(Coefficient of friction)
Using a surface property measuring instrument (trade name: Tribogear HEIDON14FW, manufactured by Shinto Kagaku Co., Ltd.) by a measuring method based on ASTM-D-1894, a flat plate indenter 63.5 × 63.5 mm, load 200 gf, surface pressure 0.49 kPa The measurement was performed under the conditions of a speed of 5.0 mm / sec and a moving distance of 50 mm. Specifically, the test force (load) when the test piece was fixed to the moving table and the flat indenter plate (aluminum) was slid was measured, and the friction coefficient was calculated based on the following formula.
[Static friction coefficient (μs)] = [Peak test force (gf)] / [Load (gf)]
[Dynamic friction coefficient (μk)] = [Average test force (gf)] / [Load (gf)]

(Peeling force)
The laminate was sampled to a size of 50 mm width × 180 mm length to obtain a test piece. Using this test piece, the peel strength of the laminate was measured by Autograph AG-500NX (manufactured by Shimadzu Corporation). Specifically, two test pieces were overlapped and reciprocated 5 times with a 2 kg rubber roll. The pressure-bonded test piece is peeled off from the end and attached to the autograph, and the tensile strength is measured under the measurement conditions of a tensile speed of 200 mm / min, a load range of 500 mN, a measurement position of 30-100 mm, and a chuck distance of 7.5 cm, and the average value is calculated. The peel force was used.

Table 1 shows the measurement results. In addition, the numerical value of each evaluation of Table 1 is the average value of the measured value measured about 5 samples.

As is apparent from the results in Table 1, the curable resin layer A, the olefin-based optical film B, and the curable resin layer C are laminated in this order, and the curable resin layer A includes (a) a urethane skeleton, It contains a urethane acrylate having a bifunctional or higher functional (meth) acryloyl group, and the laminate has a flex number of 15 times or more in the MIT bending fatigue test based on JIS P8115, and conforms to JIS P8116. The laminates of Examples 1 to 3 having a tear propagation strength measured by the measurement method of 110 mN or more had high total light transmittance, low haze, and excellent optical characteristics. Further, it was found that the laminates of Examples 1 to 3 had high loop breaking strength, and the breaking during the manufacturing process was suppressed.

Furthermore, since the curable resin layers A and C included the surface modifier in the laminates of Examples 1 and 2, the friction coefficient and the peel force were low, and the laminate was wound up in a roll shape. Since the anti-blocking property at the time was also excellent, it was found that breakage in the production process was further suppressed.

On the other hand, Comparative Example 1 uses the olefin-based optical film B as a single layer, and in the laminates of Comparative Examples 2 and 3, the curable resin layers A and C are (a) urethane skeleton and bifunctional. Since it does not contain the above urethane acrylate having a (meth) acryloyl group, the number of flexing times in the MIT folding fatigue test is less than 15 times, and the tear propagation strength is less than 110 mN. It turned out that intensity | strength is low and the fracture | rupture in a manufacturing process is not suppressed.

DESCRIPTION OF SYMBOLS 1 ... Laminated body, 2 ... Curable resin layer A, 3 ... Olefin type optical film B, 4 ... Curable resin layer C, 10 ... Test piece, 11 ... End part of length direction of test piece, 12 ... Folded part , 13 ... roll

Claims

At least a curable resin layer A, an olefin-based optical film B, and a curable resin layer C are laminated in this order,
The curable resin layer A contains (a) a urethane acrylate having a urethane skeleton and a bi- or higher functional (meth) acryloyl group,
The laminate has a bending number of 15 or more in the MIT bending fatigue test in accordance with JIS P8115, and the tear propagation strength measured by a measuring method in accordance with JIS P8116 is 110 mN or more.
A laminate characterized by the above.
The laminate according to claim 1, wherein the curable resin layer A further contains (b) a polyfunctional acrylate having a trifunctional or higher functional group that does not have a urethane skeleton in the main chain.
The laminate according to claim 1 or 2, wherein the curable resin layer C contains (a) a urethane acrylate having a urethane skeleton and a bi- or higher functional (meth) acryloyl group.
4. The curable resin layer C according to any one of claims 1 to 3, further comprising (b) a polyfunctional acrylate having a trifunctional or higher functional group having no urethane skeleton in the main chain. The laminated body of description.
The laminate according to any one of claims 1 to 4, wherein at least one layer selected from the curable resin layer A and the curable resin layer C contains a surface modifier.
The laminate according to claim 5, wherein the surface modifier is a fluorine-modified silicon compound.
The laminate according to claim 6, wherein the fluorine-modified silicon compound is a fluorosilsesquioxane compound or a polymer containing fluorosilsesquioxane.
The laminate according to any one of claims 1 to 7, wherein the olefin-based optical film B contains a cyclic olefin polymer.