KR101959586B1 - Adamantane-containing polymer - Google Patents

Abstract

A polymer comprising a structure represented by the following formula (I).

Description

ADAMANTANE-CONTAINING POLYMER}

The present invention relates to a polymer, a resin composition containing the same, and a hard coat film having a cured layer obtained from the resin composition.

Various functional films are used in liquid crystal displays, plasma displays, organic EL displays, and the like. In particular, a touch panel type device typified by a smart phone has recently become popular, and a film that is harder and has less scratches is desired.

As a method of imparting hardness to a film, a method of hard coating an ultraviolet curable resin is generally used. However, there is a problem in that the film is curled due to the curing shrinkage of the ultraviolet-curing resin, resulting in deterioration of the productivity in the process of adhering the display surface to the display surface.

In order to solve the above problem, Patent Document 1 discloses a method of forming at least two hard coat layers on at least one surface of a plastic film. However, this method has a problem that the application process for forming the hard coat layer of two or more layers becomes complicated, and the production cost becomes high.

Patent Document 2 discloses the use of a reactive polymer obtained by addition reaction of an unsaturated monocarboxylic acid with an epoxy group-containing (meth) acrylic copolymer in a hard coat layer, but the balance of hardness and curl suppression of the hard coat layer is sufficient It was difficult to do.

Japanese Patent Application Laid-Open No. 2005-53152 Japanese Laid-Open Patent Publication No. 2008-69303

It is an object of the present invention to provide a polymer which is capable of producing a hardcoat film with a high hardness and curl suppression.

According to the present invention, the following polymers and the like are provided.

1. A polymer comprising a structure represented by the following formula (I).

[Chemical Formula 1]

(Wherein R ₁ , R ₄ and R ₆ are each a hydrogen atom or a methyl group.

R ₂ and R ₅ are each a divalent aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group or a single bond containing at least one selected from a hydroxyl group, a halogen atom and a hetero atom.

R ₃ is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or an oxo group.

and m represents an integer of 0 to 15.)

2. The polymer according to 1, wherein R ₂ in the polymer represented by the formula (I) is a single bond and m is 0.

3. A polymer obtained by reacting (meth) acrylic acid with an epoxy group of a copolymer of (meth) acrylate having adamantyl group and (meth) acrylate having epoxy group bonded thereto, or a polymer obtained by reacting an adamantyl group- ) Acrylate and (meth) acrylic acid with a (meth) acrylate having an epoxy group bonded to the carboxyl group of the copolymer.

4. A resin composition comprising the polymer according to any one of 1 to 3 and a photopolymerization initiator.

5. A hard-coated film having a cured layer obtained from the resin composition according to 5.4.

According to the present invention, a polymer capable of producing a hard coat film having a high hardness and suppressed curl can be provided.

The polymer of the present invention includes a structure represented by the following formula (I).

(2)

(Wherein R ₁ , R ₄ and R ₆ are each a hydrogen atom or a methyl group.

R ₂ and R ₅ are each a divalent aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group or a single bond containing at least one selected from a hydroxyl group, a halogen atom and a hetero atom.

R ₃ is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group or an oxo group (= O).

and m represents an integer of 0 to 15.)

Each group of the polymer represented by the formula (I) is as follows.

Examples of the divalent aliphatic hydrocarbon group containing at least one selected from the hydroxyl group, the halogen atom and the hetero atom of R ₂ and R ₅ include the following three structures.

(3)

(Wherein n is an integer of 0 or more).

Examples of the divalent aliphatic hydrocarbon group represented by R ₂ and R ₅ include a methylene group, an ethylene group and a butylene group.

Examples of the hydrocarbon group for R ₃ include a methyl group, an ethyl group, a butyl group, and a t-butyl group.

Examples of the cyclic hydrocarbon group of R ₃ include a cyclopentyl group and a cyclohexyl group.

The halogen-substituted hydrocarbon group of R ₃ is a group in which the hydrogen atom of the hydrocarbon group is substituted with a halogen atom. Likewise, the halogen-substituted cyclic hydrocarbon group of R ₃ is a group in which the hydrogen atom of the cyclic hydrocarbon group is substituted with a halogen atom.

In addition, the oxo group R _3, a case where the two R ₃ is an adamantyl, and are bonded to the same carbon atoms of the carbon skeleton, and two R ₃ the art are all hydroxyl groups, these hydroxyl groups are condensed.

The polymer represented by the formula (I) is preferably a polymer in which R ₂ is a single bond (directly bonded) and m is 0.

The polymer comprising the structure represented by formula (I) is obtained by copolymerizing (meth) acrylate having an adamantyl group bonded thereto and (meth) acrylate having an epoxy group bonded thereto and then adding (meth) acrylic acid to the epoxy group of the obtained copolymer React; Alternatively, it can be produced by copolymerizing a (meth) acrylate having an adamantyl group bonded thereto and (meth) acrylic acid, and then reacting a carboxyl group of the obtained copolymer with (meth) acrylate having an epoxy group bonded thereto.

(Meth) acrylate having an adamantyl group bonded thereto is, for example, a compound having the following structure.

[Chemical Formula 4]

(Wherein R ₁ , R ₂ , R ₃ and m are the same as in the formula (I)).

(Meth) acrylate to which an epoxy group is bonded is, for example, a compound having the following structure. In the following formula, a group in which R _{5 '} and a ring-opened epoxy group are combined corresponds to R ₅ .

[Chemical Formula 5]

(Wherein R ₄ is the same as in formula (I).

R _{5 '} is a divalent aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group or a single bond each containing at least one selected from a hydroxyl group, a halogen atom and a hetero atom.

(Meth) acrylic acid is, for example, a compound having the following structure.

[Chemical Formula 6]

(Wherein R ₆ is the same as in formula (I)).

The copolymerization can be carried out, for example, by a known radical polymerization method, and polymerization may be carried out using a radical polymerization initiator or the like in a solvent or without solvent.

Examples of the radical polymerization initiator include azo-based initiators such as 2,2'-azobisisobutyronitrile and 2,2'-azobis-methylbutyronitrile; Peroxide initiators such as benzoyl peroxide, methyl ethyl ketone peroxide, and methyl isobutyl ketone peroxide.

If necessary, a chain transfer agent such as dodecyl mercaptan, lauryl mercaptan, thioglycolic acid ester, or mercaptoethanol may be used.

The amount of the radical polymerization initiator to be used is preferably such that the total amount of the (meth) acrylate and the (meth) acrylic acid to which the adamanthyl group is copolymerized and the (meth) acrylate to which the epoxy group is bonded, Is usually from 0.01 to 50 parts by mass, and preferably from 0.01 to 30 parts by mass, per 100 parts by mass. When the amount of the radical polymerization initiator used is within the above range, the reaction time and yield can be improved, and the aimed weight average molecular weight can be obtained.

Examples of the solvent used in the copolymerization include alkyl alcohols such as methanol, ethanol, n-propanol and isopropanol; Glycol ethers such as methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; Ethers such as tetrahydrofuran, dioxane and diisopropyl ether; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; And esters such as methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate, and propylene glycol monoethyl ether acetate. These solvents may be used alone or in combination of two or more.

The solvent to be used for the copolymerization is preferably a copolymerizable component (a (meth) acrylate having an adamantyl group bonded thereto and a (meth) acrylate having an epoxy group bonded thereto, or a (meth) acrylate and a (meth) For example, 0.5 mass% or more, and preferably 5 mass% or more. At this time, the copolymerization component may be in a suspended state, but it is preferably dissolved.

The reaction temperature for the copolymerization reaction is usually from 0 to 200 ° C, preferably from 20 to 150 ° C. If the temperature is lower than 0 ° C, the reaction rate may be lowered. On the other hand, when the temperature is higher than 200 ° C, there is a possibility that coloration of the obtained polymer tends to be increased.

The reaction pressure of the copolymerization reaction is usually from 0.01 to 10 MPa, and preferably from normal pressure to 1 MPa at an absolute pressure. If the pressure exceeds 10 MPa, there is a safety problem and a special device is required, which is undesirable.

The reaction time is usually 1 minute to 24 hours, preferably 1 to 10 hours, though it depends on the type and amount of the polymerization initiator, reaction temperature, and the like.

During the copolymerization reaction, other (meth) acrylic monomers may be added as a copolymerization component within the range not to impair the effect of the present invention.

Examples of other (meth) acrylic monomers include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and gamma -butyrolactone (meth) acrylate.

(Meth) acrylic acid is added to the addition reaction after the copolymerization reaction, that is, a copolymer of a (meth) acrylate having an adamantyl group bonded (meth) acrylate and an epoxy group bonded thereto; Or a (meth) acrylate having an epoxy group bonded to a copolymer of (meth) acrylate and (meth) acrylic acid having an adamantyl group bonded thereto may be reacted in a solvent.

Examples of the solvent that can be used in the addition reaction include cyclohexane, methylcyclohexane, ethylcyclohexane, toluene, xylene, MEK (methyl ethyl ketone), MIBK (methyl isobutyl ketone), DMF (dimethylformamide) (N, N-dimethylacetamide), DMSO (dimethylsulfoxide), and propylene glycol monomethyl ether acetate.

In the addition reaction, a catalyst may be used. Examples of the catalyst include tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, triphenylphosphine and pyridine.

The proportion of the constituent units (molar ratio) of the adamantyl unit and the (meth) acrylic unit of the polymer having the structure represented by the formula (I) is 1% to 99%, the proportion of the adamantyl unit is 1% And preferably 10% to 90%. If the adamantyl unit is less than 10%, there is a possibility that the obtained hard coat film has a large curl, and if it exceeds 90%, there is no great difference in the physical properties of the obtained hard coat film.

The polymerization type of the polymer represented by the formula (I) is not particularly limited, but is, for example, a random copolymer.

(7)

The polymer comprising the structure represented by formula (I) can be obtained by polymerizing a polymer comprising only adamantyl unit of formula (I) and a (meth) acrylic unit (that is, a polymer represented by formula (I) But it is a polymer substantially consisting of a til unit and a (meth) acrylic unit.

Means that the total amount of the adamantyl unit and the (meth) acrylic unit of the formula (I) in the polymer is, for example, 90 mol% or more, 95 mol% or more, 98 mol% % Or more, and further includes an unreacted epoxy terminal, an unreacted (meth) acrylate terminal and the like within a range not to impair the effect of the present invention.

The weight average molecular weight of the polymer represented by the formula (I) is not particularly limited, but is preferably 1,000 to 100,000. If the molecular weight is less than 1,000, the hard coat film obtained may have a large curl. On the other hand, if the molecular weight exceeds 100,000, the solution viscosity of the resin becomes high, and handling may become difficult.

The composition of the present invention contains the above-mentioned polymer of the present invention and a photopolymerization initiator.

[Photopolymerization initiator]

As the photopolymerization initiator, known photopolymerization initiators can be used, and for example, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1 -hydroxy-cyclohexyl- Phenyl-2-methyl-1-propan-1-one, 2 - [ - benzyl] phenyl} -2-methyl-propan-1-one, 2,4,6-trimethylbenzoyl- Diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

These may be used alone or in combination of two or more.

To the above photopolymerization initiator, tertiary amines such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, triethylamine and triethanolamine A photoinitiator may be added. Further, a titanocene compound such as CGI-784 (manufactured by Chiba Specialty Chemicals Co., Ltd.) having absorption in the visible light region may be added in order to promote the photoreaction.

The photopolymerization initiator can be used not only as a photopolymerization initiator and a photostabilization auxiliary, as long as it is a compound that absorbs light in ultraviolet light or visible light region and radically polymerizes a photosensitive unsaturated double bond.

The content of the photopolymerization initiator in the composition is, for example, from 0.1 to 20% by mass, and preferably from 1 to 10% by mass. When the content of the photopolymerization initiator is less than 0.1% by mass, the photocurability may be lowered. On the other hand, when the content is more than 20% by mass, precipitation of crystals of the photopolymerization initiator and poor photocuring of the lower part of the coating film may occur.

The composition of the present invention may contain a polymer represented by the formula (I) and a photopolymerization initiator, and may be composed substantially of these components, or may be composed of only these components.

Means that the content of these components in the composition is, for example, 90 mass% or more, 95 mass% or more, 97 mass% or more, 98 mass% or more, or 99 mass% or more .

[solvent]

The composition of the present invention may be dissolved in a solvent as required.

Examples of the solvent include alkyl alcohols such as methanol, ethanol, n-propanol and isopropanol; Glycol ethers such as methyl cellosolve, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane; Ethers such as tetrahydrofuran, dioxane and diisopropyl ether; Ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; And esters such as methyl acetate, ethyl acetate, n-propyl acetate, ethyl propionate, and propylene glycol monoethyl ether acetate. These may be used alone or in combination of two or more.

The content of the solvent is, for example, 5% by mass to 90% by mass, and preferably 10% by mass to 50% by mass from the standpoint of drying.

[Other components]

The composition of the present invention may further contain other (meth) acrylic compounds, inorganic fine particles, leveling agents and the like within a range that does not impair the effect of the present invention and does not impair the balance of performance.

Examples of other (meth) acrylic compounds include methyl (meth) acrylate, ethyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, gamma -butyrolactone (meth) acrylate, ethylene glycol di Butanediol di (meth) acrylate, butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tricyclodecanedimethanol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, adamantanetriol tri (meth) acrylate, adamantanetrimethanol tri Pentaerythritol penta (meth) acrylate Sites, and the like can be mentioned dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate.

As the inorganic fine particles, those having a particle diameter of several nm to 10 mu m may be used depending on the application, and examples thereof include known inorganic fine particles such as glass powder, silica powder, titania, zinc oxide, zirconia and alumina.

Examples of the leveling agent include silicon-based and fluorine-based leveling agents.

The composition of the present invention can be preferably used as a hard coat resin composition (hard coat agent) for forming a hard coat layer. The adamantane skeleton of the polymer of the present invention enables the hard coat layer to have a high hardness, the hard coat layer to curl, and the (meth) acrylate to be a crosslinking unit.

Since the hard coat layer formed by curing the resin composition of the present invention has excellent adhesion with the polyester film, the hard coat layer can be formed directly on the surface of the polyester film without any surface treatment such as corona treatment. Is coated and cured to obtain a hard coat film.

In general, a polyester film is a film obtained by laminating a hard coat layer obtained by curing the composition of the present invention on both sides of a polyester film, although the oligomer is precipitated by heating and the film becomes cloudy to increase haze. Or a hard coat film capable of reducing white turbidity can be obtained.

The hard coat agent is a material mainly used for improving the chemical resistance and preventing scratches such as polycarbonate resin, acrylic resin, and polyethylene terephthalate resin. For example, a hard coat resin composition is applied and cured by a coating method such as spin coating, spraying, flow, dipping or the like to form a hard coat layer having a film thickness of 2 to 10 mu m on a substrate, Can be given.

The curing method of the composition of the present invention is not particularly limited, and usually a heat curing method or a curing method by ultraviolet irradiation can be used.

In the heat curing method, the curing temperature is usually about 50 to 200 占 폚, preferably 100 to 180 占 폚. When the temperature is not lower than 50 캜, the hardening does not occur. When the temperature is lower than 200 캜, the hardening does not occur.

The curing time varies depending on the components contained in the composition, but is usually preferably 0.5 to 6 hours.

In the curing method by ultraviolet irradiation, ultraviolet rays are irradiated so that the light amount is usually about 50 to 5000 mJ / cm 2, preferably 100 to 4000 mJ / cm 2. Post-heating may be carried out after irradiation with ultraviolet rays, and it is preferably carried out at 70 to 200 ° C for 0.5 to 12 hours.

Example

Example 1

In a 1000 ml round-bottomed flask equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube, 88.1 g of 1-adamantyl methacrylate, 56.9 g of glycidyl methacrylate and 300 g of methyl isobutyl ketone And nitrogen bubbling was performed for 30 minutes. Then, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 DEG C and reacted for 3 hours. Thereafter, the reaction solution was cooled to room temperature, and the nitrogen introduction tube was replaced with an air introduction tube, and 29.4 g of acrylic acid, 2.3 g of triphenylphosphine and 35 mg of mesoquinone were added, and while bubbling air, The reaction was allowed to proceed for 12 hours until the acid value became 5 mg-KOH / g or less.

The obtained polymer solution was lowered to room temperature, and MIBK was added so that the solid content concentration became 35 wt% to obtain a reactive polymer A solution.

Example 2

Except that 112.2 g of 1-adamantyl methacrylate, 33.5 g of glycidyl methacrylate, 7.5 g of azobisisobutyronitrile, 17.3 g of acrylic acid and 1.4 g of triphenylphosphine were used, 1, a reactive polymer B solution was obtained.

Example 3

Except that 52.9 g of 1-adamantyl methacrylate, 79.6 g of glycidyl methacrylate, 8.8 g of azobisisobutyronitrile, 41.2 g of acrylic acid and 3.3 g of triphenylphosphine were used, 1, a reactive polymer C solution was obtained.

Example 4

88.1 g of 1-adamantyl methacrylate, 34.4 g of methacrylic acid and 300 g of methyl isobutyl ketone were added to a 1000 ml round-bottomed flask equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube, Nitrogen bubbling was performed for 30 minutes. Then, 8.2 g of azobisisobutyronitrile was further added, and the mixture was heated to 80 DEG C and reacted for 3 hours. Thereafter, the reaction solution was cooled to room temperature, and the nitrogen introduction tube was replaced with an air introduction tube, and 56.9 g of glycidyl methacrylate, 2.7 g of triphenylphosphine and 35 mg of mesoquinone were added. Air was bubbled, and the temperature was raised to 110 ° C., and the reaction was carried out for 12 hours until the acid value became 5 mg-KOH / g or less.

The obtained polymer solution was lowered to room temperature, and MIBK was added thereto so as to have a solid concentration of 35 wt% to obtain a reactive polymer D solution.

Example 5

A reactive polymer E solution was obtained in the same manner as in Example 1 except that 94.5 g of 3-hydroxy-1-adamantyl methacrylate was used instead of 1-adamantyl methacrylate.

Example 6

Instead of 1-adamantyl methacrylate, 117.6 g of perfluoro-1-adamantyl methacrylate, 79.6 g of glycidyl methacrylate, 8.8 g of azobisisobutylonitrile, 8.8 g of methyl isobutyl ketone A reactive polymer F solution was obtained in the same manner as in Example 1 except that the amount of the reactive polymer F was changed to 400 g, acrylic acid 41.2 g, and triphenylphosphine 3.3 g.

Example 7

55.1 g of methyl methacrylate was used instead of 1-adamantyl methacrylate, and 78.2 g of glycidyl methacrylate, 12.3 g of azobisisobutyronitrile, 40.4 g of acrylic acid and 0.02 g of triphenylphosphine A reactive polymer G solution was obtained in the same manner as in Example 1 except that the amount of the reactive polymer G was changed to 3.2 g.

[Preparation of composition and evaluation of hard coat layer]

Example 8

2.1 g of 1-hydroxy-cyclohexyl-phenyl-ketone (product name: Irgacure 184) as a polymerization initiator was added to 200 g of the reactive polymer A solution prepared in Example 1 to prepare a hard coat resin solution.

The prepared hard coat resin solution was applied to a PET film (Lamier T60 manufactured by Toray Co., Ltd.) having a thickness of 100 탆 by a bar coater and dried at 90 캜 for 2 minutes. Thereafter, irradiation was performed at 500 mJ / min using a high-pressure mercury lamp, and the coating layer was cured to form a hard coat layer having a thickness of 5 탆.

The following items were evaluated for the obtained PET film and the hard coat film as a lamination layer of the hard coat layer. The results are shown in Table 2.

[Pencil hardness]

The pencil hardness of the hard coat film was measured using a pencil hardness tester with a load of 750 g according to JIS K5600.

[Scratch resistance]

A load of 200 gf was applied to a steel wool # 0000, and the hard coat layer of the hard coat film was subjected to a round-trip of 10 times. The surface scratch condition was visually observed and evaluated according to the following criteria.

○: No scratches

△: Less than 10 scratches

×: More than 10 scratches

[curl]

The hard coat film was cut into 10 cm x 10 cm, and the bent height of the corners of the film 4 was measured.

[Adhesion]

According to JIS K5600, a checkerboard sheath (1 mm x 1 mm, 100 cells) was placed in a hard coat layer and subjected to a peel test with a cellophane tape, and the remaining number of the hard coat layer after the peel test was evaluated as adhesion . For example, when there is no peeling, the remaining number is 100, and when all peeling is done, the remaining number is zero.

[Total light transmittance]

The total light transmittance of the hard coat film was measured in accordance with JIS K7105 using HGM-2DP (manufactured by Suga Test Instruments Co., Ltd.) (unit:%).

Examples 9-14 and Comparative Examples 1-2

A hard coat resin solution was prepared in the same manner as in Example 8, and the hard coat resin solution was used in the same manner as in Example 8 to prepare hard coat films. The results are shown in Table 2.

Example 15

The hard coat solution prepared in Example 12 was applied to a PET film (Lamier T60 manufactured by Toray Co., Ltd.) having a thickness of 100 mu m using a bar coater and dried at 90 DEG C for 2 minutes. Thereafter, irradiation was performed at 500 mJ / min using a high-pressure mercury lamp, and the coating layer was cured to form a hard coat layer having a thickness of 3 占 퐉. This operation was also performed on the opposite side of the film to obtain a PET film having a hard coat layer formed on both sides thereof.

The obtained hard-coated film was heated at 150 占 폚 for 1 hour, and the total light transmittance and haze before and after heating were measured. The haze was measured with a haze meter according to JIS K7136. The results are shown in Table 3.

Comparative Example 3

A hard coat film having a hard coat layer formed on both sides of a PET film was prepared and evaluated in the same manner as in Example 15 except that the hard coat solution prepared in Comparative Example 2 was used. The results are shown in Table 3.

Comparative Example 4

PET film (Lumirror T60 manufactured by Toorel Co., Ltd.) was evaluated in the same manner as in Example 15. The results are shown in Table 3.

Industrial availability

The hard coat film having the hard coat layer obtained from the composition containing the polymer of the present invention has high hardness and can suppress curling, and is useful as a film for display, particularly a film for a touch panel.

Although the embodiments and / or examples of the present invention have been described in some detail above, those skilled in the art will readily recognize that many changes, modifications, and alterations to these illustrative embodiments and / or examples may be made without departing substantially from the novel teachings and advantages of the present invention It is easy to add. Accordingly, many modifications thereof are within the scope of the present invention.

The contents of this specification and the contents of the Japanese patent application which is the basis of the Paris priority of this application are all incorporated herein by reference.

Claims (5)

A polymer comprising a structure represented by the following formula (I)
The sum of the adamantyl unit and the (meth) acrylic unit of the formula (I) in the polymer is at least 90 mol%
The molar ratio of the adamantyl unit to the (meth) acrylic unit is 50 mol% or more.

(Wherein R ₁ , R ₄ and R ₆ are each a hydrogen atom or a methyl group.
R ₂ and R ₅ are each a divalent aliphatic hydrocarbon group, a divalent aliphatic hydrocarbon group or a single bond containing at least one selected from a hydroxyl group, a halogen atom and a hetero atom.
R ₃ is a hydrocarbon group, a halogen-substituted hydrocarbon group, a cyclic hydrocarbon group, a halogen-substituted cyclic hydrocarbon group, a halogen atom, a hydroxyl group, a carboxyl group, or an oxo group.
and m represents an integer of 0 to 15.) The method according to claim 1,
Wherein R < ₂ > of the polymer represented by the formula (I) is a single bond and m is 0. (Meth) acrylic acid with an epoxy group of a copolymer obtained by copolymerizing a (meth) acrylate having an adamantyl group and a (meth) acrylate having an epoxy group bonded thereto, (Meth) acrylate having an epoxy group bonded to a carboxyl group of a copolymer obtained by copolymerizing (meth) acrylic acid with (meth) acrylic acid is reacted with a (meth) acrylate having an epoxy group bonded to the carboxyl group of the copolymer. A resin composition comprising the polymer according to any one of claims 1 to 3 and a photopolymerization initiator. A hard coat film having a cured layer obtained from the resin composition according to claim 4.