KR102285267B1 - Composition curable with active energy ray and coating film - Google Patents

Abstract

[Problem] To provide a hard coating agent for a cyclic olefin resin-type film as a substitute for a TAC film used in a polarizing plate, such as a liquid crystal display device, in particular because of its high adhesion to cyclic olefin and excellent scratch resistance.
[Solution Means] When the total solid content is diluted to 80% by weight in toluene, the E-type viscosity at 25°C is 300 to 10000 mPa·s, and the active energy ray-curable oligomer (A) with respect to the total organic solid content 15 to 80% by weight, and the component (A) has (1) a (meth)acryloyl group, (2) a polypentaerythritol skeleton and (3) an isocyanurate group and/or a biuret group, An active energy ray-curable composition having a weight average molecular weight (Mw) of 3000 to 100000, a urethane bond equivalent of 350 to 2000 g/eq, and a (meth)acryloyl equivalent of 120 to 250 g/eq is used.

Description

Active energy ray-curable composition and coating film {COMPOSITION CURABLE WITH ACTIVE ENERGY RAY AND COATING FILM}

The present invention relates to an active energy ray-curable composition and a coating film.

Conventionally, a polarizing plate used in a liquid crystal display device adsorbs iodine or the like to a polyvinyl alcohol film and aligns a triacetyl cellulose film (TAC film) as a protective film on both sides of the polarizer, which is oriented according to elongation, etc., and the surface is a transparent light A fire-type resin composition is applied and cured, and a high-hardness film (hard coat layer) is formed and protected from damage or the like. As a material for forming such a cured film, an active energy ray-curable resin composition using polyfunctional (meth)acrylate or the like is known (Patent Document 1).

Recently, it is required to withstand more stringent use environments (eg, high temperature, high humidity conditions, etc.) due to the enlargement of the size or quality of liquid crystal devices and the expansion of mobile applications, and the TAC film has limitations in terms of characteristics. Among these, various examinations were made about the material of a protective film, and it exists in the situation where the replacement with the cyclic olefin resin film from TAC film is becoming promising. A cyclic olefin resin type film is excellent in transparency, low birefringence, dimensional stability, etc., and has the performance required as an optical film. In addition, it is also a great feature to have low moisture permeability, and in this respect, it is a big factor replacing the TAC film. However, a cyclic olefin resin type film has a problem that it is difficult to form the hard-coat layer which has high adhesiveness on the film surface.

Conventionally, with respect to a cyclic olefin resin type film, adhesion|attachment of a base material and a hard-coat layer was improved by application|coating of a primer layer, or electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment) (patent document 2).

Publication No. 2009-286924 Publication No. 2014-189566

However, in the above-mentioned method, when producing a coated film, the processing process for improving adhesiveness with a base material is required, and there exists a problem that it leads to high cost. In addition, since the electrical treatment changes with the lapse of time on the treated surface, there is a restriction that the hard coat layer must be applied quickly after the treatment.

An object of the present invention is to provide an active energy ray-curable composition and a coating film using the same, which have good coatability, and particularly have high adhesion and scratch resistance to a cyclic olefin substrate.

MEANS TO SOLVE THE PROBLEM As a result of earnest examination so that the above-mentioned subject could be solved, this inventor found that the above-mentioned subject could be solved by using the reactant which introduce|transduced the specific structure, and completed this invention.

That is, by the present invention, the following items are provided.

(Item 1)

When the total solid content is diluted to 80% solid content by weight in toluene, the E-type viscosity is 300 to 10000 mPa s at 25°C,

The active energy ray-curable oligomer (A) is contained in an amount of 15 to 80% by weight based on the total organic solid content, and the component (A) includes: (1) (meth)acryloyl group, (2) polypentaerythritol skeleton and (3) ) having an isocyanurate group and/or a biuret group, a weight average molecular weight (Mw) of 3000-100000, a urethane bond equivalent of 350-2000 g/eq, and a (meth)acryloyl equivalent of 120-250 g/eq An active energy ray-curable composition.

(Item 2)

The active energy ray-curable composition is for a cyclic olefin resin film, The active energy ray-curable composition according to item 1 above.

(Item 3)

The active energy ray composition contains the photoinitiator (B), The active energy ray curable composition in any one of the said items characterized by the above-mentioned.

(Item 4)

A coating film in which a cured film of the active energy ray-curable composition according to any one of the above items is formed on at least one surface of a substrate.

(Item 5)

The said base material is a cyclic olefin resin, The coating film of the said item 4 characterized by the above-mentioned.

(Item 6)

The coating film according to any one of the above items, characterized in that the substrate is not subjected to an easy-adhesive treatment.

ADVANTAGE OF THE INVENTION According to this invention, since adhesiveness to cyclic olefin is high and it is excellent also in abrasion resistance, it is suitable as a hard-coat agent with respect to a cyclic olefin resin type film as a substitute for the TAC film used especially for polarizing plates, such as a liquid crystal display device.

In one aspect, the active energy ray-curable composition of the present invention has an E-type viscosity of 300 to 10000 mPa·s at 25° C. when the total solid content is diluted to 80% by weight in toluene, and the total organic solid content with respect to the active energy ray-curable oligomer (A) (hereinafter referred to as "component (A)") in an amount of 15 to 80% by weight,

The said (A) component has (1) (meth)acryloyl group, (2) polypentaerythritol skeleton, and (3) an isocyanurate group and/or a biuret group, and has a weight average molecular weight (Mw) of 3000-100000 , urethane bond equivalent is 350 to 2000 g / eq, (meth) acryloyl equivalent is 120 to 250 g / eq. The said composition can be used for cyclic olefin resin films. In addition, examples of active energy rays include ultraviolet rays, electron beams, and radiation. Furthermore, in the present disclosure, "(meth)acryloyl" means to comprehensively include both acryloyl and methacryloyl, and in the same way, "(meth)acrylate" refers to acrylates and methacrylates. It means to include both inclusively.

(A) A cured product obtained from an active energy ray-curable composition containing the component (A) by having a polypentaerythritol skeleton and (3) an isocyanurate group and/or a biuret group as a component contained in the component (A) (coating film) ) has sufficient adhesion and scratch resistance.

As the component (A), for example, a reaction product of an isocyanate compound having a biuret structure and polypentaerythritol poly(meth)acrylate, an isocyanate compound having an isocyanurate structure, and dipentaerythritol poly(meth) ) and a reaction product with acrylate. Specifically, for example, a reaction product of a buret-modified product of hexamethylene diisocyanate and dipentaerythritol hexaacrylate, and a reaction product of a modified isocyanurate product of hexamethylene diisocyanate and dipentaerythritol hexaacrylate. can

As the isocyanate compound having the above-mentioned biuret structure, for example, a biuret modified product of an aliphatic isocyanate such as 1,6-hexamethylene diisocyanate, a biuret modified product of an alicyclic isocyanate such as hydrogenated xylene diisocyanate and isophorone diisocyanate, Biuret-modified products of aromatic isocyanates, such as xylene diisocyanate, etc. are mentioned.

As an isocyanate compound which has the said isocyanurate structure, For example, isocyanurate modified body of aliphatic isocyanate, such as 1, 6- hexamethylene diisocyanate, alicyclic, such as hydrogenated xylene diisocyanate, isophorone diisocyanate The isocyanurate modified body of aromatic isocyanate, such as a nurate modified body of isocyanate, and xylene diisocyanate, etc. are mentioned.

As the compound having the polypentaerythritol skeleton, for example, dipentaerythritol pentaacrylate, ethylene oxide modified product of dipentaerythritol pentaacrylate, caprolactone modified product of dipentaerythritol pentaacrylate, polypentaerythritol poly acrylates, ethylene oxide-modified products of polypentaerythritol polyacrylate, caprolactone-modified products of polypentaerythritol polyacrylates, and mixtures of two or more thereof.

As a method for preparing the reactant, for example, the isocyanate compound and the compound having a dipentaerythritol skeleton are mixed with triethylenediamine, 1,8-diazabicyclo[5,4,0]-undecene-7, octylic acid and a method of reacting in the presence of a urethanization catalyst such as tin or lead dioctylate at a temperature of 40 to 90°C.

Examples of the upper limit of the E-type viscosity at 25° C. when the total solid content of the active energy ray-curable composition containing the component (A) is diluted to 80% by weight in toluene is 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000, 2000, 1000, 900, 800, 700, 600, 500, 400 mPa·s and the like, and examples of the lower limit include 9000, 8000, 7000, 6000, 5000, 4000, 3000 , 2000, 1000, 900, 800, 700, 600, 500, 400, 300 mPa·s. The range of the said E-type viscosity can be set suitably (for example, by selecting from the said upper limit and a lower limit value). In one embodiment, from a viewpoint of coatability, the range of the said E-type viscosity is 300-10000 mPa*s, Preferably it is 450-2000 mPa*s. The E-type viscosity ( mPa·s) is a solution obtained by diluting the active energy ray-curable composition containing the component (A) in toluene to 80% by weight in toluene at 25° C. with an E-type viscometer (TV-22 3 manufactured by Tohoku Industries Co., Ltd.) °Cone), using about 0.4mL as a sample for measurement, it can be measured under the conditions of rotation speed of 0.5-100 rpm and rotation for 5 minutes. The active energy ray-curable composition of the present invention also contains other components such as monomers remaining in the process of producing component (A) and a polymerization initiator described later.

As an example of the upper limit of the weight average molecular weight (Mw) (polystyrene conversion value of the gel permeation chromatography) of the said (A) component, 100000, 90000, 80000, 70000, 60000, 50000, 46000, 40000, 30000, 20000, 15600 , 13500, 11000, 10500, 10000, 8500, 8000, 5000, etc., examples of the lower limit are 90000, 80000, 70000, 60000, 50000, 46000, 40000, 30000, 20000, 15600, 13500, 11000, 10500, 10000, 8500, 8000, 5000, 3000, and the like. The range of the weight average molecular weight (Mw) can be set suitably (for example, by selecting from the above upper limit and lower limit value). In one embodiment, the range of the weight average molecular weight (Mw) is 3000 to 100000 from the viewpoint of adhesion of the substrate, paint stability, and printability. Preferably it is 5000 to 80000, more preferably 8000 to 50000.

As an example of the upper limit of the urethane bond equivalent of the said (A) component, 1500, 1400, 1300, 1200, 1100, 1000, 976, 900, 800, 750, 748, 735, 725, 700, 612, 600, 500, 400 g /eq and the like, and examples of the lower limit include 1400, 1300, 1200, 1100, 1000, 976, 900, 800, 750, 748, 735, 725, 700, 612, 600, 500, 400 g/eq. can be heard The range of the urethane bond equivalent can be appropriately set (for example, by selecting from the above upper and lower limits). In one embodiment, the range of the urethane bond equivalent is 350 to 2000 g/eq, preferably 350 to 1500 g/eq, more preferably 600 to 1000 g/eq from the viewpoint of scratch resistance and adhesion. The urethane bond equivalent is a value calculated from the mixing amount of the reaction raw materials, specifically, the total weight of the total raw materials divided by the number of moles of isocyanate groups capable of reacting with the hydroxyl groups contained in the total raw materials of the component (A).

Examples of the upper limit of the (meth)acryloyl equivalent of the component (A) include 250, 240, 230, 220, 210, 200, 196, 190, 180, 170, 160, 156, 150, 147, 145, 140, 130 g/eq, and the like, and examples of the lower limit include 240, 230, 220, 210, 200, 196, 190, 180, 170, 160, 156, 150, 147, 145, 140, 130 g/eq, etc. can be heard The range of the (meth)acryloyl equivalent can be appropriately set (for example, by selecting from the upper and lower limits above). In one embodiment, the range of the (meth)acryloyl equivalent is preferably 120 to 250 g/eq, more preferably 120 to 200 g/eq, from the viewpoint of industrial synthesis and scratch resistance. The (meth)acryloyl equivalent is a value calculated from the amount of reaction raw materials mixed, specifically, the total weight of the total raw materials divided by the number of moles of (meth)acryloyl groups contained in the total raw materials of component (A). .

It is preferable that the ratio of the component (A) is 50% by weight or more with respect to 100% by weight of the active energy ray-curable oligomer having a functional group derived from an isocyanate group. Thereby, favorable adhesiveness can be expressed. More preferably, it is 75-100 weight%. In addition, when both an isocyanurate group and a biuret group are included, each ratio of the functional group may be arbitrary.

Examples of the upper limit of the content of component (A) with respect to the total organic solid content contained in the active energy ray-curable composition of the present invention include 80, 70, 60, 58, 50, 49, 43, 40, 39, 34, 30, 20, 17 wt%, and the like, and examples of the lower limit include 70, 60, 58, 50, 49, 43, 40, 39, 34, 30, 20, 17, 15 wt%. The range of the content rate of (A) component with respect to all organic substance solid content can be set suitably (for example, it selects from said upper limit and a lower limit). In one embodiment, the range of the content of the component (A) with respect to the total organic solid content is 15 to 80% by weight, preferably 15 to 50% by weight of the component (A) from the viewpoint of coatability and adhesion to the substrate. contains Here, "solid content" means a component from which a solvent is removed, and "total organic solid content" means solid content excluding solid content of inorganic substances such as silica filler from total solid content.

A coating film in which a cured film of the active energy ray-curable composition of the present invention is formed on at least one surface of a substrate is also one of the present inventions. With respect to a cyclic olefin resin-type film having high transparency and low moisture permeability, by using the active energy ray-curable composition for a cyclic olefin resin film of the present invention, a coating excellent in abrasion resistance can be applied to a substrate while ensuring high adhesion to the polarizing plate. It can be used suitably for a protective film.

Examples of the substrate include cyclic olefin-based resins, triacetyl cellulose, polycarbonate, polymethyl methacrylate, polystyrene, polyester melamine resins, epoxy resins, ABS resins, norbornene-based resins, and polyimide resins. Among these, when using cyclic olefin resin as a base material, in order to have high adhesiveness, it is preferable. More preferably, it is a base material which is not subjected to an anti-adhesive treatment. By using this, it is possible to reduce the production cost and exclude restrictions on the manufacturing process.

Examples of the reverse adhesion treatment include surface asperity treatment (sand blast method, solvent treatment method), electrical treatment (corona discharge treatment, atmospheric pressure plasma treatment), flame treatment, electron beam irradiation treatment, and the like.

The active energy ray-curable composition of the present invention includes, in the component (A), a (meth)acrylate component other than component (A), photosensitizer, antioxidant, light stabilizer, leveling agent, pigment in the range that does not impair the effects of the present invention. You may make it contain various well-known additives, such as a photoinitiator (B) (henceforth "(B) component"), etc. Here, the additive means an agent other than the (A) component, the (meth)acrylate component other than the (A) component, and the (B) component, and an example of the content in the composition is 10 parts by weight based on 100 parts by weight of the composition. less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, and the like, but is not limited thereto.

Although it does not specifically limit as a (meth)acrylate component other than the said (A) component, For example, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethyloylpropanetetra(meth) ) acrylate, trimethyloylpropane tri(meth)acrylate, ethylene oxide modified trimethyloylpropane tri(meth)acrylate, propylene oxide modified trimethyloylpropane tri(meth)acrylate, dipentaerythritol penta(meth) Acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol poly(meth)acrylate, pentaerythritol poly(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate , 1,6-hexanediol di (meth) acrylate, 1,4-nonanediol di (meth) acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, tridecyl (meth) acrylate, lauryl ( meth)acrylate, and the like. (A) When mix|blending (meth)acrylate components other than component, weight ratio with (meth)acrylate components other than (A) component mix|blended with (A) component ((A) component other than (A) component / (A) component (meth) ) acrylate component), 0.7 to 9, and the like, but is not limited to this value.

It does not specifically limit as said (B) component, A well-known thing can be used. Specifically, for example, 1-hydroxy-cyclohexyl-phenyl ketone, 2,2-dimethoxy-1,2-diphenyl ethan-1-one, 1-cyclohexyl phenyl ketone, 2-hydroxy- 2-Methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxide)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2 -Methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethyl amino-1-(4-morpholinophenyl)-butanone-1, Bis(2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, 2,4,6-trimethylbenzoyl- diphenyl- phosphine graphite, 4-methylbenzophenone, etc. are mentioned. These may be used individually by 1 type, and may mix and use 2 or more types. (B) Component is used in the case of ultraviolet curing, but is not necessarily required in the case of electron beam curing. (B) As an example of the usage-amount in the case of using (B) component, although about 1-10 weight part etc. are mentioned with respect to 100 weight part of total amounts of (A) component normally, It is not limited to this value.

In the method for forming a cured film using the active energy ray-curable composition of the present invention, it is usually coated on a plastic film or plastic sheet used as a base material, dried, and then irradiated with active energy rays to cause a curing reaction on the film surface to form a cured film. should be formed

Examples of the coating method include bar coater coating, wire bar coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, aniline printing, and screen printing.

Although the said coating amount is not specifically limited, Usually, the weight after drying ^{is preferably about 0.1-30 g/m<2>} , and 1-20 g/m<^2> is more preferable.

As an active energy ray used for hardening reaction, an ultraviolet-ray and an electron beam are mentioned, for example. As a light source of an ultraviolet-ray, the ultraviolet irradiation apparatus which has a xenon lamp, a high-pressure mercury-vapor lamp, and a metal halide lamp can be used. In addition, the amount of light, the arrangement of the light source, the transport speed, etc. can be adjusted as needed. For example, when a high-pressure mercury lamp is used, the transport speed is 5-50 m for the first lamp with a light quantity of about 80-160 W/cm normally. It is preferable to cure on the order of /min. On the other hand, in the case of an electron beam, it is preferable to harden it at a conveyance speed of about 5-50 m/min in an electron beam accelerator with an acceleration voltage of about 10-300 kV normally.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition, in the Examples, unless otherwise specified, parts or % are based on weight.

In addition, in this Example, the weight average molecular weight is gel permeation chromatography (manufactured by Tosoo Co., Ltd., trade name "HLC-8220", GARAM: manufactured by Tosoo Co., Ltd., trade name "TSKgel superHZ2000", "TSKgel superHZM-M") Measured values by ' are shown.

(Manufacture of active energy ray-curable resin)

Example 1

210 parts of an isocyanurate modified product of hexamethylene diisocyanate (Coronate HXR Tosoo Co., Ltd.) (hereinafter referred to as HDI isocyanurate) in a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube , 0.6 parts of tin octylate, 1500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio of 35:65) was added, and then the temperature in the system was raised to about 80° C. for 1 hour. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A-1) and a residual monomer (solid content: 100% by weight). (A-1) The (meth)acryloyl group equivalent of the component is 147 g/eq, the urethane bond equivalent is 735 g/eq, the weight average molecular weight is 15600, and the content of the oligomer component in 100% by weight of the solid content is 43% by weight (calculated value) ) was. 5 parts of 1-hydroxy-cyclohexyl-phenylketone (manufactured by BASF Japan Co., Ltd., trade name "Irugacure 184", hereinafter referred to as HCPK) with respect to 100 parts of this mixture is blended at a solid content ratio, and diluted with toluene and an active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) of 41% with respect to the total organic solid content.

Examples 2-6

As described in Table 1, an active energy ray-curable composition having a solid content of 40% by weight was prepared in the same manner as in Example 1, except that (A-1) to (A-3) were blended. Details are described below.

Example 2

With respect to 90 parts of the component (A-1), 10 parts of dipentaerythritol hexaacrylate, 5 parts of HCPK, and 5 parts of HCPK were mixed and diluted with toluene, solid content 40 wt%, total organic solid content (A) An active energy ray-curable composition having a component content of 37% was prepared.

Example 3

With respect to 90 parts of the component (A-1), 10 parts of pentaerythritol triacrylate, 5 parts of HCPK, and 5 parts of HCPK were blended and diluted with toluene, solids 40% by weight, total organic solids (A) component An active energy ray-curable composition having a content of 37% was prepared.

Example 4

With respect to 80 parts of the component (A-1), 20 parts of dipentaerythritol hexaacrylate, 5 parts of HCPK, and 5 parts of HCPK were blended and diluted with toluene, solid content 40 wt%, total organic solid content (A) An active energy ray-curable composition having a component content of 33% was prepared.

Example 5

In a reaction vessel equipped with the stirring device, cooling tube, dropping funnel and nitrogen introduction tube, 200 parts of a burette-modified product of hexamethylene diisocyanate (Death Module N3200A, manufactured by Sumitomo Bayer Urethane) (hereinafter referred to as HDI burette), octylic acid After adding 1500 parts of tin 0.6 parts and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (the mixing ratio is 35:65), the temperature in the system was raised to about 80° C. for about 1 hour. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture (solid content: 100% by weight) of an active energy ray-curable oligomer (A-2) and a residual monomer. (A-2) The (meth)acryloyl group equivalent of the component was 145 g/eq, the urethane bond equivalent was 725 g/eq, and the weight average molecular weight was 11000, and the content of the oligomer component in 100 wt% of the solid content was 43 wt%. With respect to 100 parts of this mixture, 5 parts of HCPK was blended at a solid content ratio, diluted with toluene, and an active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) relative to the total organic solid content of 41% was prepared.

Example 6

Isophorone diisocyanate modified isocyanurate (VESTANAT T1890/100 Evonik Co., Ltd.) (hereinafter referred to as IPDI isocyanurate) 670 in a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube After adding 4500 parts of part, 0.6 parts of tin octylate, and 4500 parts of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (the mixing ratio is 35:65), the temperature in the system was raised to about 80° C. for about 1 hour. did. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A-3) and a residual monomer (solid content: 100% by weight). (A-3) The (meth)acryloyl group equivalent of the component was 150 g/eq, the urethane bond equivalent was 748 g/eq, and the weight average molecular weight was 8500, and the content of the oligomer component in 100 wt% of the solid content was 43 wt%. With respect to 100 parts of this mixture, 5 parts of HCPK was blended at a solid content ratio, diluted with toluene, and an active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) relative to the total organic solid content of 41% was prepared.

Example 7

(A-1) With respect to 40 parts of component, as other components, 60 parts of dipentaerythritol hexaacrylate and 5 parts of HCPK were mixed in a solids ratio and diluted with toluene, solid content 40% by weight, total organic solid content (A ), an active energy ray-curable composition having a content of 16% was prepared.

Example 8

200 parts of HDI burette, 0.6 parts of tin octylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio of 35:65 ) 750 parts, 240 parts of a mixture of pentaerythritol acrylate and pentaerythritol tetraacrylate (mixing ratio: 62:38), the temperature in the system was raised to about 80° C. for about 1 hour. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A-4) and a residual monomer (solid content: 100% by weight). (A-4) The (meth)acryloyl group equivalent of the component was 156 g/eq, the urethane bond equivalent 612 g/eq, and the weight average molecular weight was 10500, and the content rate of the oligomer component in 100 weight% of solid content was 58 weight%. With respect to 100 parts of this mixture, HCPK was blended at a solid content ratio of 5 parts, diluted with toluene, and an active energy ray-curable composition having a solid content of 40 wt% and a content of component (A) of 55% with respect to the total organic solid content was prepared.

Example 9

In a reaction vessel equipped with a stirring device, a cooling tube, a dropping funnel and a nitrogen introduction tube, 205 parts of a multimer of a modified product of HDI nurate (Coronate HK Tosoh Corporation), 0.6 parts of tin octylate, dipentaerythritol pentaacrylate and After immersing 1500 parts of a mixture of dipentaerythritol hexaacrylate (the mixing ratio is 35:65), the temperature in the system was raised to about 80° C. for about 1 hour. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A-5) and a residual monomer (solid content: 100% by weight). (A-5) The (meth)acryloyl group equivalent of the component was 150 g/eq, the urethane bond equivalent was 750 g/eq, and the weight average molecular weight was 46000, and the content of the oligomer component in 100 wt% of the solid content was 43 wt%. With respect to 100 parts of this mixture, 5 parts of HCPK was blended at a solid content ratio, diluted with toluene, and an active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) relative to the total organic solid content of 41% was prepared.

Example 10

670 parts of HDI view, 0.6 parts of tin octylate, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (mixing ratio of 35:65 ) of dipentaerythritol pentaacrylate, after adding 1728 parts of a component containing 2 mol of caprolactone to the dipentaerythritol pentaacrylate, the temperature in the system was raised to about 80° C. for about 1 hour. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A-6) and a residual monomer (solid content: 100% by weight). (A-6) The (meth)acryloyl group equivalent of the component was 196 g/eq, the urethane bond equivalent of 976 g/eq, the weight average molecular weight was 13500, and the content rate of the oligomer component in 100 weight% of solid content was 49 weight%. With respect to 100 parts of this mixture, 5 parts of HCPK was blended at a solid content ratio, diluted with toluene, and an active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) with respect to the total organic solid content of 47% was prepared.

Comparative Example 1

With respect to 20 parts of component (A-1), as other components, 80 parts of dipentaerythritol hexaacrylate, 5 parts of HCPK, and 5 parts of HCPK were mixed and diluted with toluene, solid content 40% by weight, total organic solid content (A) An active energy ray-curable composition having a content of 8% was prepared.

Comparative Examples 2-7

As described in Table 1, an active energy ray-curable composition having a solid content of 40% by weight was prepared in the same manner as in Comparative Example 1 except that (A-2) and (A'-7) to (A'-11) were blended. Details are described below.

Comparative Example 2

In a reaction vessel equipped with a stirring device, cooling tube, dropping funnel and nitrogen inlet tube, 200 parts of HDI burette, 0.6 parts of tin octylate, and a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (mixing ratio 62:38) After adding 480 parts, the temperature in the system was raised to about 80° C. for about 1 hour. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A'-7) and a residual monomer (solid content: 100% by weight). (A'-7) The (meth)acryloyl group equivalent of the component was 166 g/eq, the urethane bond equivalent 498 g/eq, the weight average molecular weight was 8000, and the content rate of the oligomer component in 100 weight% of solid content was 73 weight%. . With respect to 100 parts of this mixture, 5 parts of HCPK was blended at a solid content ratio, diluted with toluene, and an active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) with respect to the total organic solid content of 0% was prepared. .

Comparative Example 3

In a reaction vessel equipped with a stirring device, cooling tube, dropping funnel and nitrogen introduction tube, 200 parts of HDI isocyanurate, 0.6 parts of tin octylate, and 150 parts of 2-hydroxyethyl acrylate were placed, and the mixture was stirred for about 1 hour. The temperature inside was heated up to about 80 degreeC. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A'-8) and a residual monomer (solid content: 100% by weight). (A'-8) The (meth)acryloyl group equivalent of the component was 344 g/eq, the urethane bond equivalent 344 g/eq, the weight average molecular weight was 2300, and the content rate of the oligomer component in 100 weight% of solid content was 98 weight% . With respect to 100 parts of this mixture, 5 parts of HCPK were blended at a solid content ratio, diluted with toluene, and an active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) with respect to the total organic solid content of 0% was prepared. .

Comparative Example 4

Into a reaction vessel equipped with a stirring device, cooling tube, dropping funnel and nitrogen introduction tube, 210 parts of HDI isocyanurate, 0.6 parts of tin octylate, 110 parts of 2-hydroxyethyl acrylate and 110 parts of 2-hydroxyethyl acrylate After adding 180 parts of caprolactone 5 mol addition, the temperature in the system was raised to about 80° C. for about 1 hour. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A'-9) and a residual monomer (solid content: 100% by weight). (A'-9) The equivalent of the (meth)acryloyl group of the component was 490 g/eq, the urethane bond equivalent of 490 g/eq, the weight average molecular weight was 4300, and the content rate of the oligomer component in 100 weight% of solid content was 98%. . 5 parts of 1-hydroxy-cyclohexyl-phenyl ketone (manufactured by BASF Japan Co., Ltd., trade name "Irugacure 184" or less, referred to as HCPK) with respect to 100 parts of this mixture at a solid content ratio, diluted with toluene and 40 wt% of solid content, an active energy ray-curable composition having a content of component (A) of 0% with respect to the total organic solid content was prepared.

Comparative Example 5

In a reaction vessel equipped with a stirring device, a cooling pipe, a dropping funnel and a nitrogen introduction tube, 260 parts of an allophanate body of hexamethylene diisocyanate (Takenate D-178NL manufactured by Mitsui Chemicals Co., Ltd.) (hereinafter referred to as HDI allophanate), jade After adding 1500 parts of tin thilate 0.6 parts and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (the mixing ratio is 35:65), the temperature in the system was raised to about 80° C. for about 1 hour. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A'-10) and a residual monomer (solid content: 100% by weight). (A'-10) The equivalent of the (meth)acryloyl group of the component is 157 g/eq, the urethane bond equivalent of 785 g/eq, the weight average molecular weight is 4000, and the content rate of the oligomer component in 100 weight% of solid content is 45 weight% it was With respect to 100 parts of this mixture, 5 parts of HCPK was blended at a solid content ratio, diluted with toluene, and an active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) with respect to the total organic solid content of 0% was prepared.

Comparative Example 6

In a reaction vessel equipped with a stirring device, cooling tube, dropping funnel and nitrogen inlet tube, 170 parts of hexamethylene diisocyanate, 0.6 parts of tin octylate, and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (the mixing ratio is 35:65) was added, and the temperature in the system was raised to about 80° C. for about 1 hour. Next, the reaction apparatus was maintained at this temperature for 2 hours and then cooled to obtain a mixture of an active energy ray-curable oligomer (A'-11) and a residual monomer (solid content: 100% by weight). (A'-11) The (meth)acryloyl group equivalent of the component was 122 g / eq, the urethane bond equivalent 610 g / eq, the weight average molecular weight was 3200, and the content rate of the oligomer component in 100 weight% of solid content was 42 weight% . With respect to 100 parts of this mixture, 5 parts of HCPK was blended at a solid content ratio, diluted with toluene, and an active energy ray-curable composition having a solid content of 40% by weight and a content of component (A) with respect to the total organic solid content of 0% was prepared.

Comparative Example 7

(A-2) With respect to 25 parts of component (A'-10), 75 parts of (A'-10) component, 5 parts of HCPK, were mixed in a solid content ratio and diluted with toluene, solid content 40 wt%, total organic solid content (A) An active energy ray-curable composition having a component content of 10% was prepared.

<Toluene-diluted E-type viscosity of the composition>

A mixture containing only solids in each Example and Comparative Example (that is, (1) a mixture of the active energy ray-curable composition and residual monomer prepared in each Example and Comparative Example, and (2) an active energy ray-curable type such as HCPK With respect to the mixture containing other solids that can be contained in the composition), measure the viscosity of the solution diluted to 80% by weight in toluene with an E-type viscometer (TV-22 3° cone manufactured by Higashi Industrial Co., Ltd.) at 25°C. was measured in As for the measurement method, about 0.4 mL was used as a measurement sample, and the toluene-diluted E-type viscosity (mPa·s) of the composition was set under the conditions of rotation at a rotation speed of 0.5 to 100 rpm and rotation for 5 minutes.

<Production of cured film>

On a 100 μm thick cyclic olefin resin film, each active energy ray-curable composition was applied with a #10 bar coater so that the cured film had a thickness of 5 μm, and dried at 70° C. for 1 minute to prepare a film. Then, the obtained film was subjected to an ultraviolet curing device (product name: UBT-080-7A/BM Co., Ltd., manufactured by Multiprivacy, high pressure mercury lamp 600 mJ/cm ² ) to obtain a plastic film provided with a cured film. About the resin composition which concerns on Examples 2-10 and Comparative Examples 1-7, the film was similarly manufactured, and the cured film was evaluated as follows. A result is shown in Table 1 and Table 2.

<Evaluation of cured film>

(1) Coatability

The film for evaluation obtained above was visually observed to confirm whether liquid agglomeration occurred.

○: no clumping

△: Liquid agglomeration is seen in some parts

×: agglomeration is seen on the front

(2) Adhesion

About the film for evaluation obtained above, according to JISK5600-5-4, the 100 square grid peeling test evaluated the adhesiveness of the cured film.

The display of the result is (number of masocks remaining in the peel test/100)

(3) scratch resistance

Steel wool (#0000, 10 mm × 10 mm) for the evaluation film obtained above was attached to the bottom and rubbed 10 reciprocally with a weight of 300 g, and the coating appearance was visually evaluated based on the following criteria.

○: no wound

○-: No more than 5 wounds occurred

△: 6 or more and 20 or less wounds occurred

×: A large number of wounds occur

[Table 1]

[Table 2]

In Tables 1 and 2, the compositional numerical value represents the number of parts by weight.

HDI isocyanurate: isocyanurate modified form of hexamethylene diisocyanate

HDI burette: burette-modified form of hexamethylene diisocyanate

HDI arophanate: arophanate modified form of hexamethylene diisocyanate

IPDI isocyanurate: isocyanurate modified form of isophorone diisocyanate

Claims (6)

When the total solid content is diluted to 80% solid content by weight in toluene, the E-type viscosity at 25 ° C is 300 to 10000 mPa s,
15 to 80% by weight of the active energy ray-curable oligomer (A) with respect to the total organic solid content,
Said (A) component,
(1) (meth) acryloyl group, (2) polypentaerythritol skeleton and (3) isocyanurate group and / or biuret group, the weight average molecular weight (Mw) is 3000 ~ 100000, urethane bond equivalent is 350 ~ 2000 g / eq, (meth) acryloyl equivalent is 120 ~ 250 g / eq,
isocyanates other than diisocyanates having an isocyanurate group and/or a biuret group; and a compound having a polypentaerythritol skeleton and a (meth)acryloyl group;
The active energy ray-curable composition for cyclic olefin resin films which is not subjected to an easy-adhesive treatment.
According to claim 1,
The active energy ray composition is an active energy ray curable composition for a cyclic olefin resin film that is not subjected to reverse adhesion treatment, characterized in that the photopolymerization initiator (B) is contained.
A coating film in which a cured film of the active energy ray-curable composition according to claim 1 or 2 is formed on at least one surface of the cyclic olefin resin film not subjected to the reverse adhesion treatment.

delete delete delete