KR20130028704A - Active energy ray-curable resin composition and cured product and film thereof - Google Patents

Abstract

The cured coating film combines the fingerprint resistance and surface hardness at a high level, and the active energy ray-curable resin composition which hardens and expresses these performances even if the environment at the time of hardening expresses in an air atmosphere, and is formed by hardening the said composition. The film which has hardened | cured material and the hardened layer of the said composition is provided. Polyalkylene glycol (a1) having a weight average molecular weight (Mw) in the range of 500 to 5,000, diol (a2) having an alkylene thioether structure in the molecular structure, diisocyanate (a3) having a molecular weight of 500 or less, and a molecule Urethane (meth) acrylate (A) which has a weight average molecular weight (Mw) obtained by making (meth) acrylate (a4) which has one hydroxyl group in a structure as an essential raw material component 10,000-10,000, and polyfunctional It is characterized by containing (meth) acrylate (B).

Description

ACTIVE ENERGY RAY-CURABLE RESIN COMPOSITION AND CURED PRODUCT AND FILM THEREOF}

The present invention particularly relates to an active energy ray-curable resin composition which can be preferably used to form a hard coat layer that protects the touch panel surface.

In recent years, devices equipped with a touch panel display have been increasing in mobile phones, game consoles, car navigation systems, and the like. In the touch panel display which operates by touching a screen directly with a finger, in addition to the chromaticity and surface hardness of a screen with respect to the hard-coat layer which protects a surface, a fingerprint trace is hard to adhere, and the fingerprint trace attached The so-called fingerprint resistance such as this hardly noticeable and easy to wipe off attached fingerprint trace is required. However, the conventional hard coating layer which emphasizes the screen's clarity and surface hardness has a problem that a fingerprint is easy to adhere because the surface is flat, and the attached fingerprint is easy to see and hard to wipe.

Thus, as a composition for obtaining a hard coating layer which is hard to be noticed and which is easy to wipe off the attached fingerprint traces, for example, polypropylene glycol having a weight average molecular weight (Mw) of 2,000 and isophorone diisocyanate; The photocurable resin composition in which the single terminal contains urethane acrylate of the acryloyl group obtained by making 1 mol of each pentaerythritol triacrylate react is known (for example, refer patent document 1). However, although the coating film which consists of a photocurable composition by which patent document 1 is disclosed can obtain the surface hardness equivalent to a normal hard coating, it is hard to see a fingerprint and it is easy to wipe off the attached fingerprint trace. Not enough performance was achieved. Regarding easiness of wiping of fingerprints in particular, when the photocurable resin composition is cured under an air atmosphere, the photocurable resin composition is cured under a nitrogen atmosphere under the influence of inhibition of the hardening of the coating film surface by peroxy radicals generated from oxygen present in the air. There existed a problem that the ease of wiping of a trace of a fingerprint falls significantly compared with the case where it was made.

JP 2008-255301 (Part 2)

The problem to be solved by the present invention is an active energy ray-curable resin composition in which a cured coating film has a high level of fingerprint resistance and surface hardness, and can express their performance even if the environment at the time of curing is in an air atmosphere, It provides the hardened | cured material formed by hardening | curing the said composition, and the film which has a hardened layer of the said composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the urethane obtained by making polyalkylene glycol which has a weight average molecular weight (Mw) in the range of 500-5,000, and diol which has an alkylene thioether structure in molecular structure as an essential raw material component ( By using a resin composition containing meth) acrylate, even when cured in an air atmosphere, the fingerprint traces are hardly noticeable, and furthermore, a hard coating layer which can easily wipe off the attached fingerprint can be obtained. The hardened layer formed finds a point which shows high hardness, etc., and has completed the present invention.

That is, the present invention provides a polyalkylene glycol (a1) having a weight average molecular weight (Mw) in the range of 500 to 5,000, a diol (a2) having an alkylene thioether structure in its molecular structure, and a diisocyanate having a molecular weight of 500 or less ( Urethane (meth) acrylate (A) whose weight average molecular weight (Mw) obtained by making a3) and (meth) acrylate (a4) which has one hydroxyl group in molecular structure as an essential raw material component ranges from 10,000-100,000. ) And a polyfunctional (meth) acrylate (B). An active energy ray-curable resin composition is provided.

Moreover, this invention provides the hardened | cured material formed by hardening | curing the said active energy ray hardening-type resin composition.

Moreover, this invention has a cured layer formed by hardening | curing the said active energy ray hardening-type resin composition on a film-form base material, It is providing the film characterized by the above-mentioned.

By using the active-energy-ray-curable resin composition of this invention, a hard-coating layer which is high in surface hardness, hardly noticeable with the attached fingerprint trace, and easy to wipe off the attached fingerprint can be formed. Therefore, the active-energy-ray-curable resin composition of this invention is suitable as a composition for forming the hard-coat layer of the article which fingerprint traces, such as a touch panel display, are easy to adhere.

This invention is demonstrated in detail below.

The urethane (meth) acrylate (A) used by this invention is a polyalkylene glycol (a1) whose weight average molecular weight (Mw) is in the range of 500-5,000, and the diol which has an alkylene thioether structure in molecular structure ( It is obtained by making a2), diisocyanate (a3) whose molecular weight is 100-500, and (meth) acrylate (a4) which has one hydroxyl group in molecular structure react as an essential raw material component.

Here, the said polyalkylene glycol (a1) which is a raw material component of the said urethane (meth) acrylate (A) is the range whose weight average molecular weights (Mw) are 500-5,000. When the weight average molecular weight (Mw) is less than 500, sufficient performance is not exhibited in terms of difficulty of the attached fingerprint, and when it exceeds 5,000, the ease of wiping of the attached fingerprint is not sufficiently expressed. . Also in the said polyalkylene glycol (a1), it is excellent in affinity with a fingerprint component, compatibility with polyfunctional (meth) acrylate (B) is favorable, and a high hardness coating film can be obtained. In that point, it is preferable that the weight average molecular weight (MW) is in the range of 700 to 4,500, and it is more preferable that the weight average molecular weight (Mw) is in the range of 1,000 to 4,000.

In addition, in this invention, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are the values measured by the gel permeation chromatography (GPC) of the following conditions.

Measuring device; HLC-8220GPC manufactured by TOSOH CORPORATION

column; TSK-GARDCOLUMN SuperHZ-L + made in Tosoh Kabuki Kaisha TSK-GEL SuperHZM-M * 4

Detectors; RI (differential refractometer)

Data processing; Multistation GPC-8020modelⅡ made by Toso Corporation

Measuring conditions; Column temperature 40 ° C

Solvent tetrahydrofuran

Flow rate 0.35ml / min

Standard; Monodisperse polystyrene

sample; A 0.2 wt% tetrahydrofuran solution in terms of resin solids was filtered through a micro filter (100 µl).

The number of polyalkyleneoxy structural units derived from polyalkylene glycol (a1) contained in urethane (meth) acrylate (A) varies depending on the weight average molecular weight (Mw) of the polyalkylene glycol used, Since the resin composition which is excellent in any of affinity of a component, compatibility with polyfunctional (meth) acrylate (B), and the surface hardness of a coating film can be obtained, 1-20 range is preferable, and 2-10 range is more preferable desirable. In particular, when the weight average molecular weight (Mw) of polyalkylene glycol (a1) is in the range of 1,000-4,000, it is preferable that it is 2-6.

Examples of the polyalkylene glycol (a1) include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutylene glycol, poly3-chloropropylene glycol, and the like. These may be used alone or in combination of two or more. Among these, polypropylene glycol and polybutylene glycol are preferable, and polypropylene glycol is more preferable, since the hard-coat layer in which fingerprint traces are hard to be outstanding is obtained.

In the present invention, as described above, by using diol (a2) having an alkylene thioether structure in the molecular structure as a raw material component of the urethane (meth) acrylate (A), either under nitrogen atmosphere or under air atmosphere Even if it is hardening conditions, the cured coating film excellent in the easy wiping of a fingerprint can be obtained.

Diol (a2) which has the alkylene thioether structure used by this invention in molecular structure is 2,2'- thiodiethanol, 3-thia-1, 6- hexanediol, 1- (2-hydride, for example). Hydroxyethylthio) -2-propanol, 4-methyl-2-thiapentane-1,5-diol, 1-chloro-3- (2-hydroxyethylthio) -2-propanol, 3,3'-thiobis (1-propanol), 2,2'-thiobis (1-propanol), 1,1'-thiobis (2-propanol), 5-methyl-3-thiahexane-1,6-diol, 3-oxa Compounds having one sulfur atom in a molecular structure such as -6-thiaoctane-1,8-diol;

2,2 '-(methylenebisthio) diethanol, 1,2-bis (2-hydroxyethylthio) ethane, 3,3'-dithiobis (1-propanol), 1,1'-dithiobis (2 -Propanol), bis (2-hydroxy-1-methylethyl) persulfide, 2,2 '-[oxybis (methylenethio)] bisethanol, 3,9-dithia-6-oxanonane-1,9 -Diol, 2,2 '-(trimethylenebisthio) diethanol, 2,2'-(tetramethylenebisthio) diethanol, 4,4'-dithiobis (1-butanol), 1,1 '-( Ethylenebisthio) bis (2-propanol), 3- [2- (3-hydroxypropylsulfanyl) ethylsulfanyl] propan-1-ol, 2,2 '-[oxybis (ethylenethio)] diethanol , 2,2 '-[(2-methyl-1,4-butanediyl) bis (thio)] bisethanol, 2,2'-(pentamethylenebisthio) diethanol, 2,2 '-(hexamethylenebisti O) diethanol, 1,1 '-(ethylenebisthio) bis (2-butanol), 3,3'-dithiobis (3-methyl-2-butanol), bis (5-hydroxypentyl) persulfide, 4,9-Dithiadodecane-1,12-diol, 1- (2- [2- (2-hydroxypropylsulfanyl) ethoxy ] Ethylsulfanyl) propan-2-ol, 2,2 '-[ethylenebis (oxyethylenethio)] diethanol, 2,2'-(oxyethylenethioethyleneoxyethylenethio) diethanol, 2,2'- (Octamethylenebisthio) diethanol, 6,6'-dithiobis (1-hexanol), 4,11-dithiatetradecane-1,14-diol, bis [1- (hydroxymethyl) -1- Sulfur in molecular structures such as ethylpropyl] persulfide, 2- [9- (2-hydroxyethylthio) nonylthio] ethanol, thiadenol, 2,2 '-(1,10-decanediylbisthio) diethanol Compounds having two atoms;

2,2 '-[thiobis (ethylenethio)] diethanol, 2,2'-[thioethyleneoxyethylene (dithio)] diethanol, 1- (2- [2- (2-hydroxypropylsulfanyl ) Ethylsulfanyl] ethylsulfanyl) propan-2-ol, 2- [2- [2- (2-hydroxyethylthio) propylthio] -1-methylethylthio] ethanol, 6-oxa-3,9 , 12-trithia-1,14-tetradecanediol, 1- (2- [2- (2-hydroxypropylsulfanyl) propylsulfanyl] 1-methyl-ethylsulfanyl) propan-2-ol, 2 Three sulfur atoms in a molecular structure such as 2 '-[thiobis (ethyleneoxyethylenethio)] diethanol and 3,12-dioxa-6,9,15-trithia-1,17-heptadecanediol Compound having;

2,2 '-[1,2-ethanediylbis (dithio)] bisethanol, 2- [2- [2- (2-hydroxyethylthio) ethyldithio] ethylthio] ethanol, 3,6, The compound which has four sulfur atoms in molecular structures, such as 9,12- tetra- tetra tetradecane- 1, 14- diol, is mentioned.

Among these, the compound represented by following General formula (1) or (2) is preferable at the point which is excellent in the balance of sclerosis | hardenability and anti-fingerprint property in the air atmosphere of a coating film.

(Wherein R ₁ and R ₂ are each an alkyl or halogenated alkyl group having 1 to 4 carbon atoms)

(Wherein l, m and n are each 0 or 1, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each an alkyl or halogenated alkyl group having 1 to 4 carbon atoms. Is a sulfur atom or an oxygen atom, and at least half of the X contained in the compound is a sulfur atom)

As a specific example of the compound represented by the said General formula (1), 2,2'- thiodiethanol, 3- thia- 1, 6- hexanediol, 1- (2-hydroxyethylthio) -2-, for example. Propanol, 4-methyl-2-thiapentane-1,5-diol, 1-chloro-3- (2-hydroxyethylthio) -2-propanol, 3,3'-thiobis (1-propanol), 2 , 2'-thiobis (1-propanol), 1,1'-thiobis (2-propanol), 5-methyl-3-thiahexane-1,6-diol, 3-oxa-6-thiaoctane-1 Compounds having one sulfur atom in a molecular structure such as 8-diol; 2,2 '-(methylenebisthio) diethanol, 1,2-bis (2-hydroxyethylthio) ethane, 2,2'-[oxybis (methylenethio)] bisethanol, 2,2 '-( Trimethylenebisthio) diethanol, 2,2 '-(tetramethylenebisthio) diethanol, 1,1'-(ethylenebisthio) bis (2-propanol), 3- [2- (3-hydroxypropyl Sulfanyl) ethylsulfanyl] propan-1-ol, 2,2 '-[oxybis (ethylenethio)] diethanol, 1,1'-(ethylenebisthio) bis (2-butanol)), 4,9 -Dithiadodecane-1,12-diol, 1- (2- [2- (2-hydroxypropylsulfanyl) ethoxy] ethylsulfanyl) propan-2-ol, 2,2 '-[ethylenebis ( Compounds having two sulfur atoms in molecular structures such as oxyethylenethio)] diethanol and 2,2 '-(oxyethylenethioethyleneoxyethylenethio) diethanol; 2,2 '-[thiobis (ethylenethio)] diethanol, 1- (2- [2- (2-hydroxypropylsulfanyl) ethylsulfanyl] ethylsulfanyl) propan-2-ol, 2- [ 2- [2- (2-hydroxyethylthio) propylthio] -1-methylethylthio] ethanol, 6-oxa-3,9,12-trithia-1,14-tetradecanediol, 1- (2 -[2- (2-hydroxypropylsulfanyl) propylsulfanyl] 1-methyl-ethylsulfanyl) propan-2-ol, 2,2 '-[thiobis (ethyleneoxyethylenethio)] diethanol, 3 Compounds having three sulfur atoms in a molecular structure such as, 12-dioxa-6,9,15-trithia-1,17-heptadecanediol; The compound etc. which have four sulfur atoms etc. are mentioned in molecular structures, such as 3,6,9,12- tetrathia tetradecane- 1,14- diol.

Moreover, in the said compound, 2,2'- thiobis (1-propanol) and 1,2-bis (2-hydroxyethylthio) ethane are more excellent in the balance of sclerosis | hardenability and anti-fingerprint in the air atmosphere of a coating film. , 2- [2- [2- (2-hydroxyethylthio) propylthio] -1-methylethylthio] ethanol, 1- (2- [2- (2-hydroxypropylsulfanyl) propylsulfanyl] 1-methyl-ethylsulfanyl) propan-2-ol is particularly preferred.

The diisocyanate (a3) used by this invention has a molecular weight of 500 or less. When molecular weight exceeds 500, the fingerprint property of a coating film is not fully expressed. Among these, it is more preferable that the molecular weight is the range of 150-450 from the point which is excellent in the fingerprint-proof property of a coating film. As such diisocyanate, aromatic diisocyanate, aliphatic diisocyanate, etc. are mentioned, for example.

The aromatic diisocyanate is, for example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), p-phenylene diisocyanate, naphthalene diisocyanate, xylylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate ( TMXDI) etc. can be mentioned.

Examples of the aliphatic diisocyanate include chain diisocyanates such as hexamethylene diisocyanate (HMDI), 2,2,4-trimethylhexane diisocyanate and lysine diisocyanate; 1,4-cyclohexanediisocyanate (CDI), isophorone diisocyanate (IPDI), 4,4'-dicyclohexyl methane diisocyanate (hydrogenated MDI), methylcyclohexanediisocyanate, isopropylidenedicyclohexyl-4 Alicyclic diisocyanates such as 4'-diisocyanate, 1,3-diisocyanate methylcyclohexane (hydrogenated XDI), 4-methyl-1,3-cyclohexylene diisocyanate (hydrogenated TDI), norbornane diisocyanate, etc. Can be mentioned.

The said diisocyanate (a3) may be used independently, respectively and may use two or more types together. Especially, since the urethane (meth) acrylate (A) obtained becomes a compound excellent in compatibility with polyfunctional (meth) acrylate (B), aromatic diisocyanate or alicyclic diisocyanate is preferable, tolylene diisocyanate, 4,4'- dicyclohexyl methane diisocyanate and isophorone diisocyanate are more preferable.

The (meth) acrylate (a4) which has one hydroxy group in the molecular structure used by this invention is hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth), for example. Hydroxy (meth) acrylate which has one (meth) acryloyl group, such as an acrylate and 2-hydroxy-3- phenoxy propyl (meth) acrylate; Such as glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, Hydroxy (meth) acrylate etc. which have two or more metha) acryloyl group are mentioned. These may be used alone or in combination of two or more.

Among these, hydroxy (meth) acrylate having one (meth) acryloyl group is preferable, because a hard coating layer is hardly noticeable and a hard coating layer which is easy to wipe off the attached fingerprint can be obtained. Hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate are more preferable.

The method of manufacturing the urethane (meth) acrylate (A) used by this invention is a polyalkylene glycol (a1) whose said weight average molecular weight is the range of 500-5,000, and the said alkylene thioether structure, for example. Step (step 1) of preparing the isocyanate group-containing urethane prepolymer obtained by reacting diol (a2) in the molecular structure with the diisocyanate (a3), followed by one hydroxyl group in the urethane prepolymer and the molecular structure. The method by the process (step 2) which makes the (meth) acrylate (a4) which have which react is mentioned.

As mentioned above with respect to the said process 1, the manufacturing method of the said isocyanate group containing urethane prepolymer is, for example, polyalkylene glycol (a1), diol (a2) which has an alkylene thioether structure in molecular structure, and diisocyanate ( The method of making a3) react with 500 ppm of tin octanoate (II) which is a urethanation catalyst, and 300 ppm of polymerization inhibitor metoquinones is carried out under the temperature conditions of 70-120 degreeC.

In the said process 1, when the molar ratio [(a1) / (a2)] of content of the polyalkylene glycol (a1) and the diol (a2) which has an alkylene thioether structure in a molecular structure is hardened under air atmosphere, Since the hard coat layer which is easy to wipe off the fingerprint attached also can be obtained, it is preferable that it is the range of [1.0 / 0.2]-[1.0 / 5.0], and it is more preferable that it is the range of [1.0 / 0.5]-[1.0 / 2.0]. desirable.

In the above Step 1, a polyalkylene glycol, a diol (a2) the number of moles of hydroxy group F _2, diisocyanate (a3) in which the number of moles of hydroxy group to F _1, alkylene thioether structure in the molecular structure of (a1) The number of moles of the isocyanate group is F ₃ , and the ratio [(F ₁ + F ₂ ) / F ₃ ] of the number of moles of the hydroxy group and the number of moles of the isocyanate group contained in the system is [1 / 1.05] to [1 / It is preferable that it is the range of 3, and it is more preferable that it is the range of [1 / 1.1]-[1/2].

The above step 2 will be described in detail. For example, the isocyanate group-containing urethane prepolymer and (meth) acrylate (a4) having one hydroxy group in the molecular structure are tin octanoate (II) which is a urethanization catalyst. It adds in the range of -800 ppm, and also adds the metoquinone which is a polymerization inhibitor in the range of 100-500 ppm, and makes it react on 80 degreeC temperature conditions.

In the above step 2, the isocyanate group-containing mol number of isocyanate group of the urethane prepolymer F _NCO, and a (meth) of the mole number F _OH in the acrylate hydroxyl group ratio [F _NCO / F _OH] having a hydroxyl group in the molecular structure of [1 / It is preferable that it is the range of 1]-[1 / 1.2], and it is more preferable that it is the range of [1 / 1.01]-[1 / 1.05].

Since the said urethane (meth) acrylate (A) obtained in this way can obtain the resin composition excellent in all of the affinity of a fingerprint component, the hardness of a coating film, and compatibility with polyfunctional (meth) acrylate (B). The weight average molecular weight (Mw) is in the range of 10,000 to 100,000. Among these, it is more preferable that it is the range of 20,000-80,000 from the point which can obtain the coating film excellent in the balance of both the outstanding difficulty of the attached fingerprint and the easily wiping performance.

The polyfunctional (meth) acrylate (B) used by this invention is a monomer type polyfunctional (meth) acrylate (b1) whose molecular weight is less than 600, and oligomer type polyfunctional (meth) acryl whose molecular weight is the range of 600-3,000. Rate b2 can be mentioned. As a monomer type polyfunctional (meth) acrylate (b1) whose molecular weight is less than 600, for example, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di (meth) acrylate, and pro Foxiated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Di (meth) acrylates such as ethoxylated neopentyl glycol di (meth) acrylate and hydroxy pivalate neopentyl glycol di (meth) acrylate;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloyl morpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) ) Acrylate, benzyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene Oxide modified phosphoric acid (meth) acrylate, phenoxy group ( Ta) acrylate, ethylene oxide modified phenoxy group (meth) acrylate, propylene oxide modified phenoxy group (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified nonylphenol (meth) acrylate, propylene oxide modified nonyl Phenol (meth) acrylate, methoxy ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy propylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2- Hydroxypropyl phthalate, 2-hydroxy-3-phenoxylpropyl (meth) acrylate, 2- (meth) acryloyloxyethylhydrogenphthalate, 2- (meth) acryloyloxypropylhydrogenphthalate, 2 -(Meth) acryloyloxypropylhexahydrohydrogenphthalate, 2- (meth) acryloyloxypropyltetrahydrohydrogenphthalate, dimethylami Ethyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, octafluoro Mono (meth) acrylates such as propyl (meth) acrylate and adamantyl mono (meth) acrylate;

Acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, tris 2-hydroxyethylisocyanurate tri Tri (meth) acrylate such as glycerin tri (meth) acrylate;

Pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylol propane penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ditrimethylol (Meth) acrylates more than tetrafunctional, such as propane hexa (meth) acrylate;

And (meth) acrylates in which some of the various polyfunctional (meth) acrylates described above are substituted with an alkyl group or? -Caprolactone.

Since the coating film of higher hardness can be obtained among the said monomer type polyfunctional (meth) acrylate (b1), tetrafunctional or more (meth) acrylate is preferable, and dipentaerythritol pentaacrylate and dipentaerythritol hexa Acrylate is more preferable. Further, from the viewpoint of excellent surface hardness and curl resistance of the coating film, a mixture (b56) of dipentaerythritol pentaacrylate (b5) and dipentaerythritol hexaacrylate (b6) is particularly preferable, and at this time, dipenta The mass ratio [(b5) / (b6)] between erythritol pentaacrylate (b5) and dipentaerythritol hexaacrylate (b6) is preferably in the range of 3/7 to 7/3, and is preferably 4/6 to 5 It is more preferable that it is the range of / 5.

The said oligomer type polyfunctional (meth) acrylate (b2) can obtain the coating film excellent in the surface hardness of a coating film, and curl resistance by the weight average molecular weight (Mw) of the range of 600-3,000. As said oligomer type polyfunctional (meth) acrylate (b2), a polyester (meth) acrylate, a urethane (meth) acrylate, an epoxy (meth) acrylate, an acryl (meth) acrylate, etc. are mentioned, for example. have. These polyfunctional (meth) acrylates (B) may be used independently, respectively and may use two or more types together. Among these, polyfunctional urethane (meth) acrylate (b4) is preferable at the point which can obtain a higher hardness coating film.

The polyfunctional urethane (meth) acrylate (b4) used as said oligomer type polyfunctional (meth) acrylate (b2) is a polyisocyanate and the polyfunctional (meth) acrylate which has a hydroxyl group in molecular structure, for example. , polyisocyanate (meth) acrylate of the number of moles of the hydroxyl group of the hydroxyl group with a number of moles and F _NCO, molecular structure of the isocyanate group [F F _OH ratio _NCO / _OH] a [1/1] F ~ a [1 / 1.2] It can be obtained by making it react in the range of.

Examples of the polyisocyanate include various diisocyanates listed as the diisocyanate (a3). In addition, the polyfunctional (meth) acrylate which has a hydroxyl group in the said molecular structure can mention various (meth) acrylates opened as (meth) acrylate (a4) which has one hydroxyl group in the said molecular structure, for example. have. Among these, since a higher hardness coating film can be obtained, the urethane (meth) acrylate obtained by making hexamethylene diisocyanate and pentaerythritol tri (meth) acrylate react is preferable.

Among the polyfunctional (meth) acrylates (B) used in the present invention, a hard coating layer having high curability, high hardness, and excellent transparency can be obtained, so that the monomer-type polyfunctional (meth) acrylate (b1) having the above molecular weight is less than 600. ) And an oligomeric polyfunctional (meth) acrylate having the above molecular weight in the range of 600 to 3,000 are preferably used in combination. Further, in terms of excellent hardness, transparency, and curl resistance of the coating film, as the monomeric polyfunctional (meth) acrylate (b1), dipentaerythritol pentaacrylate (b5) and dipentaerythritol hexaacrylate ( It is preferable to use urethane (meth) acrylate (b4) as said oligomer type polyfunctional (meth) acrylate using the mixture (b56) of b6), and these mass ratios ((b56) / (b4)] are It is preferable that it is the range of [1/2]-[2-1].

In the present invention, the urethane (meth) acrylate (A) and the polyfunctional (meth) acrylate (B) have a mass ratio [(A) / (B)] of [0.1 / 99.9] to [15/85]. It is characterized by containing so that it may become a range. By using the urethane (meth) acrylate (A) in the above range, it is difficult to notice the attached fingerprint traces without lowering the hardness of the hard coating layer, and also to obtain a hard coating layer that can easily wipe off the attached fingerprint. have. It is preferable to contain a urethane (meth) acrylate (A) and a polyfunctional (meth) acrylate (B) in 0.1 / 99.9-10 / 90 by mass ratio [(A) / (B)], (A) / (B)] is more preferably contained in the range of 0.1 / 99 to 5/95.

You may mix the organic solvent with the active-energy-ray-curable resin composition of this invention in the range which does not impair the effect of this invention. As an organic solvent, a thing with a boiling point of 50-200 degreeC normally can obtain the resin composition for active-energy-ray-curable coatings, and the active energy-ray-curable coating material which is excellent in the workability at the time of coating, and the drying property before and after hardening. Preferable examples thereof include alcohol solvents such as methanol, isopropyl alcohol, n-butanol and isobutanol; Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, and ethylene glycol monobutyl ether acetate; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Aromatic solvents, such as toluene and xylene, or these mixtures, etc. are mentioned.

When the organic energy is contained in the active energy ray-curable resin composition obtained by the present invention, for example, the resin composition for active energy ray-curable paint is applied to a support to form a layer of the active energy ray-curable resin composition on the support. It is preferable to remove the organic solvent before irradiating an active energy ray to the layer. As a means for removing an organic solvent, a hot air dryer etc. can be used, for example. In addition, the usage-amount of an organic solvent is although it does not specifically limit, Usually, it is the range which solid content concentration of a coating becomes 10 to 70 weight%.

A photoinitiator can be added to the active energy ray hardening type resin composition of this invention according to the objective. Various things can be used as a photoinitiator. As a photoinitiator, the compound of the type which generate | occur | produces a radical by hydrogen extraction, such as benzophenone, benzyl, Michler's ketone, thioxanthone, anthraquinone, etc. are mentioned, for example. It is common to use these compounds together with 3rd amine, such as methylamine, diethanolamine, N-methyl diethanolamine, and tributylamine.

Moreover, as a photoinitiator, the compound of the type which generate | occur | produces a radical by intramolecular cleavage is also mentioned, for example. Specifically, benzoin, dialkoxy acetophenone, acyl oxime ester, benzyl ketal, hydroxyalkyl phenone, halogeno ketone, etc. are mentioned, for example.

If necessary, in combination with a photopolymerization initiator, polymerization inhibitors such as hydroquinone, benzoquinone, toluhydroquinone and paratert-butylcatechol may be added.

Moreover, in order to improve the smoothness of a coating film surface, various leveling agents, such as a fluorine type, a silicone type, and a hydrocarbon type, can be added (0.005-1 mass%) by the addition amount of the range which does not impair a fingerprint. Moreover, in order to improve coating film hardness, inorganic fine particles (particle size 5-100 nm), such as a celica gel, can be added (0.1-50 mass%) by the addition amount of the range which does not impair transparency.

The hardened | cured material of this invention hardens the said energy-beam curable resin composition. As an active energy ray, an electron beam, an ultraviolet-ray, a gamma ray, etc. are mentioned, for example. The irradiation conditions are determined according to the composition of the active energy ray-curable coating material used to obtain the protective layer, but in the case of ultraviolet irradiation, it is usually preferable to irradiate the accumulated light amount to be 10 to 5,000 mj / cm 2, and the accumulated light amount is 50 to It is more preferable to irradiate so that it may become 1,000 mj / cm <2>. Moreover, when irradiating an electron beam, it is preferable that it is an irradiation amount of 1-5 Mrad. Among these, ultraviolet curing is preferable at the point which is easy to handle.

The film of this invention has a cured layer formed by hardening | curing the said active energy ray hardening-type resin composition on a film-form base material.

As said film-form base material, the film made from polyethylene, polypropylene, triacetyl cellulose, polyethylene terephthalate, vinyl chloride, polycarbonate etc. are mentioned as a plastic film, for example further, for example.

As a coating means for forming the layer of an active energy ray hardening type resin composition on a film base material, For example, coating methods, such as the gravure coating method, the roll coating method, the spray coating method, the lip coating method, the comma coating method, Printing methods, such as the gravure printing method and the screen printing method, are mentioned. When coating, it is preferable to coat so that the thickness of the hardened protective layer may be 0.1-400 micrometers, and it is more preferable to coat so that it may be 1-50 micrometers especially.

When using the active energy ray hardening-type resin composition containing the organic solvent, after forming a layer of an active energy ray hardening-type resin composition on a base film, an organic solvent is normally removed. As a method of removing the organic solvent, it may be left to leave it as it is and volatilized, or it may be dried using a dryer etc., The temperature at the time of removing an organic solvent is 70-130 degreeC normally, and a drying time is 10 second-10 It is preferable that it is the range of minutes.

After forming a layer of an active energy ray hardening-type coating material by the said method etc., an active energy ray is irradiated to the layer of this coating material, and the film of this invention is obtained.

(Example)

An Example and a comparative example are shown to the following, and this invention is demonstrated to it further in detail. In the following, parts and% are based on mass unless otherwise specified.

In addition, in the Example of this invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using the gel permeation chromatography (GPC) of the following conditions.

Measuring device; HLC-8220GPC manufactured by TOSOH CORPORATION

column; TSK-GARDCOLUMN SuperHZ-L + made in Tosoh Kabuki Kaisha TSK-GEL SuperHZM-M * 4

Detectors; RI (differential refractometer)

Data processing; Multistation GPC-8020modelⅡ made by Toso Corporation

Measuring conditions; Column temperature 40 ° C

Solvent tetrahydrofuran

Flow rate 0.35ml / min

Standard; Monodisperse polystyrene

sample; A 0.2 wt% tetrahydrofuran solution in terms of resin solids was filtered through a micro filter (100 µl).

Synthesis Example 1 [Synthesis of urethane acrylate (A)]

4,000 g (2 mol) of polypropylene glycol having a weight average molecular weight (Mw) 2,000 and 91 g (1 mol) of 1,2-bis (2 hydroxyethylthio) ethane were added to the flask, and tin octanoate was used as a catalyst. 200 ppm of Ⅱ) and zinc octanoate (II), 3,000 ppm of dibutylhydroxytoluene, 300 ppm of metoquinone as a polymerization inhibitor, and normal butyl acetate as a solvent were added, and the mixture was mixed well, The temperature in the system was adjusted to 50 ° C. Then, 261 g (3 mol) of toluene diisocyanate was divided | segmented and added, paying attention to exotherm, and it was made to react at 80 degreeC for 1 hour. Furthermore, 260 g (2 mol) of hydroxypropyl acrylates were added, it was made to react at 80 degreeC, until the isocyanate group completely disappeared, blowing in air, and the urethane acrylate (A1) which is a weight average molecular weight (Mw) 24,000 was obtained.

Synthesis Examples 2 to 7 (Side Statue)

Urethane acrylates (A2) to (A7) were obtained in the same manner as in Synthesis example 1 except that the synthesis was carried out with the raw materials and the compounding amounts shown in Table 1. The value of each weight average molecular weight (Mw) is shown in Table 1.

[Table 1]

Footnotes of Table 1

Polyalkylene glycol 1: Polypropylene glycol having a weight average molecular weight of 2,000

Polyalkylene glycol 2: Polypropylene glycol having a weight average molecular weight of 1,000

Polyalkylene glycol 3: Polypropylene glycol having a weight average molecular weight of 4,000

Polyalkylene glycol 4: Polypropylene glycol having a weight average molecular weight of 700

Synthesis Examples 8-10 [Synthesis of Comparative Comparative Urethane (Meta) acrylate (a)]

The comparative control urethane acrylates (a1) to (a3) were obtained in the same manner as in Synthesis example 1 except that the synthesis was carried out with the raw materials and the compounding amounts shown in Table 2. The value of each weight average molecular weight (Mw) and number average molecular weight (Mn) is shown in Table 2.

[Table 2]

Footnotes in Table 2

Polyalkylene glycol 5: Polypropylene glycol having a weight average molecular weight of 400

Polyalkylene glycol 6: Polypropylene glycol having a weight average molecular weight of 8,000

Polyalkylene glycol 7: Polypropylene glycol having a weight average molecular weight of 2,000

Synthesis Example 11 [Synthesis of Polyfunctional (meth) acrylate (B)]

535.5 g of a mixture (weight ratio 60/40) of pentaerythritol triacrylate and pentaerythritol tetraacrylate was charged into a flask. 200 ppm of tin octanoate and zinc octanoate as catalysts, 3,000 ppm of dibutylhydroxytoluene as antioxidants, and 300 ppm of metoquinone as polymerization inhibitors were added to the flask. It mixed so that it might be 80% and adjusted the temperature in system to 50 degreeC.

84 g of hexamethylene diisocyanate was divided | segmented and added, blowing air into the system. The temperature in the system was raised to 80 ° C. and reacted at 80 ° C. until the isocyanate group disappeared completely to obtain urethane acrylate (B1). According to GPC analysis, the weight average molecular weight of urethane acrylate (B1) was 1,400. In addition, the acryloyl equivalent was 109 g / mol.

Example 1

3 g of urethane acrylates (A1), 48.5 g of urethane acrylates (B1), 48.5 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (weight ratio 40/60), 1-hydroxycyclohexylphenyl 4 g of ketones and 104 g of butyl acetate were mixed to obtain an active energy ray-curable composition (1) having a solid content of 50% by mass. Using the composition (1), a hard coat layer was formed on the film under the following conditions, and the noticeable difficulty of the attached fingerprint trace and the ease of wiping the attached fingerprint trace were evaluated according to the following criteria. The inconspicuous difficulty of attached fingerprint traces and the ease of wiping off the attached fingerprint traces were evaluated for each of the initial stages of forming the hard coating layer and the stages after 20 times of attachment and removal of the fingerprint traces. Removal of the attached fingerprint trace was performed by the evaluation method of the easy wiping of the fingerprint trace mentioned later. In addition, the acryloyl equivalent of the mixture of 48.5 g of urethane acrylates (B1) and the mixture (weight ratio 40/60) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate was 104 g / mol.

<Formation method of the hard coating layer>

Composition (1) It coated with PET film (125 micrometers) using the bar coater so that dry film thickness might be set to 5 micrometers. After drying the solvent at 70 ° C. for 5 minutes, ultraviolet rays were irradiated with a high pressure mercury lamp (80 μs / cm) so that the irradiation amount was 500 mJ / cm 2, thereby obtaining a hard coating layer. In addition, irradiation of the ultraviolet-ray was performed in air atmosphere or nitrogen atmosphere.

<Evaluation of Fingerprint Trail Hardness (Quantitative Evaluation)>

Inconspicuous difficulty of fingerprint traces was quantitatively evaluated by the viewing angle. The viewing angle means the angle at which the visual angle with respect to the fingerprint trace attached to the hard coating layer is gradually lowered from 90 ° C. and the fingerprint trace starts to be confirmed. The smaller the viewing angle is, the better the visibility of the fingerprint traces is.

<Evaluation (quantity evaluation) of wiping off of fingerprint trace>

Ease of wiping of a fingerprint trace was evaluated by the number of wiping when removing a fingerprint trace from a hard coating layer. Specifically, the tissue paper was reciprocated at 1 kg (per 5.7 square centimeters) on the fingerprint traces attached to the hard coat layer, and quantitatively evaluated by the number of round trips until the attached fingerprint traces were completely invisible. The smaller the number of round trips, the better the ease of wiping off the fingerprint traces.

<Evaluation of Coating Hardness>

Pencil hardness measurement was performed in accordance with JIS K5600-5-4. It measured five times about one hardness, and made the hardness which a cured coating film has not to be scratched four times or more.

Examples 2-9 and Comparative Examples 1-3

Except having performed by the compounding shown in Table 3 and Table 4, it carried out similarly to Example 1, and prepared active energy ray hardening-type resin compositions 2-9 and comparative control active energy ray hardening-type resin compositions 1'-3 '. Evaluation similar to Example 1 is performed and the result is shown to Tables 5-7.

[Table 3]

[Table 4]

Footnotes from Table 3 and Table 4

Polyfunctional acrylate (B2): mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (weight ratio 40/60)

The acryloyl group equivalent of the mixture of polyfunctional acrylate (B1) and polyfunctional acrylate (B2) is 104 g / mol

Photoinitiator: 1-hydroxycyclohexylphenyl ketone

Diluent Solvent: Normal Butyl Acetate

[Table 5]

TABLE 6

[Table 7]

Claims (12)

Polyalkylene glycol (a1) having a weight average molecular weight (Mw) in the range of 500 to 5,000, diol (a2) having an alkylene thioether structure in the molecular structure, diisocyanate (a3) having a molecular weight of 500 or less, and a molecule Urethane (meth) acrylate (A) which has a weight average molecular weight (Mw) obtained by making (meth) acrylate (a4) which has one hydroxyl group in a structure as an essential raw material component 10,000-10,000, and polyfunctional (Meth) acrylate (B) is contained, The active-energy-ray-curable resin composition characterized by the above-mentioned. The method of claim 1,
The active energy ray-curable resin composition wherein the polyalkylene glycol (a1) is polypropylene glycol. The method of claim 1,
The active-energy-ray-curable resin composition whose diol (a2) which has the said alkylene thioether structure in a molecular structure is a compound represented by following General formula (1) or General formula (2).

(Wherein R ₁ and R ₂ are each an alkyl or halogenated alkyl group having 1 to 4 carbon atoms)

(Wherein l, m and n are each 0 or 1, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ are each an alkyl or halogenated alkyl group having 1 to 4 carbon atoms. Is a sulfur atom or an oxygen atom, and at least half of the X contained in the compound is a sulfur atom) The method of claim 1,
The diol (a2) having the alkylene thioether structure in the molecular structure is 2,2'-thiobis (1-propanol), 1,2-bis (2-hydroxyethylthio) ethane, 2- [2- [ 2- (2-hydroxyethylthio) propylthio] -1-methylethylthio] ethanol, 1- (2- [2- (2-hydroxypropylsulfanyl) propylsulfanyl] 1-methyl-ethylsulfanyl Active energy ray-curable resin composition which is at least 1 type of compound chosen from the group which consists of a propan-2-ol. The method of claim 1,
The molar ratio [(a1) / (a2)] of the content of the diol (a2) having the polyalkylene glycol (a1) and the alkylene thioether structure in the molecular structure in the raw material of the urethane (meth) acrylate (A) is 1 Active-energy-ray-curable resin composition which is a range used as /0.2-1/5. The method of claim 1,
The active energy ray curable resin composition which is (meth) acrylate (a4) which has one hydroxyl group in the said molecular structure is monohydroxy mono (meth) acrylate which has one methacryloyl group in a molecular structure. The method of claim 1,
The active energy ray curable resin composition whose mass ratio [(A) / (B)] of the said urethane (meth) acrylate (A) and a polyfunctional (meth) acrylate (B) is 0.1 / 99.9-15 / 85. The method of claim 1,
As said polyfunctional (meth) acrylate (B), the monomer type polyfunctional (meth) acrylate (b1) whose molecular weight is less than 600, and the oligomeric polyfunctional (meth) acrylate (b2) whose molecular weight is 600-3,000 range. Using together an active energy ray hardening-type resin composition. 9. The method of claim 8,
The active-energy-ray-curable resin composition whose oligomer type polyfunctional (meth) acrylate (b2) whose said molecular weight is the range of 600-3,000 is polyfunctional urethane (meth) acrylate. 9. The method of claim 8,
The mass ratio [(b1) / (b2)] of the monomer type polyfunctional (meth) acrylate (b1) whose said molecular weight is less than 600, and the oligomer type polyfunctional (meth) acrylate (b2) whose molecular weight is 600-3,000 Active-energy-ray-curable resin composition which is a range of 1 / 2-2 / 2. Hardened | cured material formed by hardening | curing the active-energy-ray-curable resin composition of any one of Claims 1-10. The cured layer formed by hardening | curing the active-energy-ray-curable resin composition of any one of Claims 1-10 on a film-form base material, The film characterized by the above-mentioned.