KR101537150B1 - Urethane (meth)acrylate and curable resin composition comprising the same - Google Patents

Abstract

(Meth) acrylate obtained by reacting (A) a polyol having two or more hydroxyl groups in one molecule, (B) a polyisocyanate, and (C) a (meth) acrylate component containing a hydroxyl group in the molecule, (Meth) acrylate having a functional group number of polyurethane obtained by reacting (A) and (B) of not less than 3.0 and not more than 6.0 can obtain a cured product having appropriate hardness, scratch resistance and resilience And a curable resin composition containing the same can be provided.

Description

TECHNICAL FIELD The present invention relates to a urethane (meth) acrylate and a curable resin composition containing the same. BACKGROUND ART [0002] Urethane (meth)

The present invention relates to a urethane (meth) acrylate and a curable resin composition containing the same.

Hard coating agents such as an ultraviolet ray hardening type hard coating agent, an electron ray hardening type hard coating agent and a silica type hard coating agent are hardened and cured with scratch resistance when they are cured, and therefore they are used as paints or coating agents in areas requiring scratch resistance. Since the ultraviolet ray curable composition containing an ultraviolet ray curable urethane (meth) acrylate oligomer and a photoinitiator has scratch resistance based on a self-recovery function of the cured product, scratch resistance is required (See Patent Document 1).

Japanese Patent Application Laid-Open No. 2004-035600

However, there is a demand for suitable hardness as a coating agent, but conventional coatings have not achieved suitable hardness, scratch resistance and resilience. Disclosure of the Invention In order to solve such conventional problems, it is an object of the present invention to provide a urethane (meth) acrylate and a curable resin composition containing the same which can obtain a cured product having suitable hardness, scratch resistance and resilience do.

(B) a polyisocyanate; and (C) a (meth) acrylate component containing a hydroxyl group in the molecule, wherein the component (A) is a polyol having two or more hydroxyl groups in one molecule, (Meth) acrylate obtained by reacting (A) with (B), wherein the number of functional groups of the polyurethane obtained by reacting (A) and (B) is not less than 3.0 and not more than 6.0.

The present invention also provides a curable resin composition containing urethane (meth) acrylate of the first aspect, which has a glass transition temperature measured by dynamic viscoelasticity measurement of 0 ° C or more and 30 ° C or less, The second point.

That is, the inventors of the present invention have conducted intensive studies to obtain a urethane (meth) acrylate capable of obtaining a cured product having appropriate hardness, scratch resistance, and resilience. In the course of the research, a urethane (meth) acrylate obtained by reacting (A) a polyol having two or more hydroxyl groups in one molecule, (B) a polyisocyanate, and (C) (Meth) acrylate, and the number of functional groups of the polyurethane obtained by reacting (A) and (B) is from 3.0 to 6.0. The present inventors have found that a urethane (meth) did.

Hereinafter, embodiments of the present invention will be described in detail.

The urethane (meth) acrylate of the present invention is obtained by copolymerizing (A) a polyol having two or more hydroxyl groups in one molecule, (B) a polyisocyanate, and (C) a (meth) acrylate component containing a hydroxyl group in the molecule (Meth) acrylate obtained by reacting (A) with (B), wherein the number of functional groups of the polyurethane obtained by reacting (A) and (B) is from 3.0 to 6.0.

The polyol having two or more hydroxyl groups in the molecule (A) is not particularly limited, but specific examples thereof include a polyester polyol, a polycarbonate polyol, a polyether polyol, an aliphatic hydrocarbon-based polyol and an alicyclic hydrocarbon- have.

The number average molecular weight of the polyol is not particularly limited, but is preferably 200 or more and 3,000 or less. If it is less than 200, the cured product becomes too hard to impart stability, while if it exceeds 3,000, the hardness of the cured product becomes low and hardness is hardly given. The number of hydroxyl groups in the polyol is not particularly limited, but is preferably 2 or more and 4 or less. If it is less than 2, the crosslinking property of the cured product may be too low, and if it is more than 4, the crosslinking property of the cured product may be too high, and the resilience may not be imparted.

The polyisocyanate (B) is not particularly limited, but specific examples thereof include an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and an aromatic aliphatic polyisocyanate.

Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, dodecamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2 Methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, and the like.

Examples of the alicyclic polyisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, methylcyclohexylene diisocyanate, 1,3-bis (Isocyanatomethyl) cyclohexane, and the like.

Examples of the aromatic polyisocyanate include tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI) Dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

Examples of the aromatic aliphatic polyisocyanate include dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, and alpha, alpha, alpha, alpha-tetramethylxylene diisocyanate. Further, these modified polyisocyanates include dimers, trimers, and bifunctional isocyanates of these organic polyisocyanates. These may be used alone or in combination of two or more.

The (meth) acrylate having a hydroxyl group in the molecule (C) is not particularly limited, but specifically includes 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, Hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, caprolactone modified 2-hydroxyethyl acrylate, polyethylene glycol mono (meth) acrylic acid ester, polypropylene glycol monoacrylate, polybutylene glycol mono (Meth) acrylic acid esters, such as 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, phenylglycidyl ether (meth) acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, caprolactone And modified dipentaerythritol penta (meth) acrylate. These may be used alone or in combination of plural kinds Can. Among these, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and pentaerythritol triacrylate can be preferably used.

The urethane (meth) acrylate of the present invention can be synthesized by a known method. For example, a predetermined amount of the component (B) is added to an excessive excess of the component (A), and the mixture is reacted until a predetermined amount of free isocyanate is obtained at 90 캜. The reaction mixture is heated to 130 캜 x 0.04 kPa (C) in a batch at 70 to 80 ° C and in the presence of a polymerization inhibitor such as hydroquinone monomethyl ether at a temperature of 70 to 80 ° C to obtain a polyisocyanate It can be synthesized by heating and stirring until disappearing. At this time, in order to promote the reaction, a tin catalyst such as dibutyltin dilaurate may be added.

The urethane (meth) acrylate of the present invention has a number of functional groups of polyurethane obtained by reacting (A) and (B) of 3.0 or more and 6.0 or less. When the number of the functional groups is less than 3.0, it is difficult to impart the scratch resistance of the cured product. When the number exceeds 6.0, the cured product becomes too hard and it becomes difficult to obtain the stability. The ratio of (C) to (b) - (a) is 1.0 to 2.0, preferably 1.0 to 1.5.

The curable resin composition containing the urethane (meth) acrylate of the present invention preferably has a glass transition temperature measured by dynamic viscoelasticity measurement of 0 ° C or more and 30 ° C or less. If the glass transition temperature is lower than 0 占 폚, stickiness may occur. If the glass transition temperature is higher than 30 占 폚, it is difficult to impart resilience at room temperature. The glass transition temperature is more preferably 0 deg. C or more and 28 deg. C or less, and particularly preferably 0 deg. C or more and 25 deg. C or less.

The curable resin composition containing urethane (meth) acrylate of the present invention may contain an organic solvent such as ethyl acetate, methyl ethyl ketone or monomers. It is preferable that the content of the urethane (meth) acrylate of the present invention in the curable resin composition is 50 wt% or more.

(Meth) acrylate, styrene, methyl methacrylate, acryloylmorpholine, tetrahydrofurfuryl (meth) acrylate, and the like may be used as the monomer to be blended. (Meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, benzyl (meth) acrylate, polyethoxyphenyl (Meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, octylphenol (meth) acrylate, (Meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polytetramethylene (meth) acrylate, (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, EO (Meth) acrylate, ethylene oxide (hereinafter the same) modified bisphenol di (meth) acrylate, PO (propylene oxide, hereinafter the same) modified bisphenol di (meth) acrylate, dimethylol dicyclopentanedi Acrylate, neopentyl glycol di (meth) acrylate, trimethylol propane tri (meth) acrylate, EO modified trimethylol propane tri (meth) acrylate, PO modified trimethylol propane tri Acrylate, pentaerythritol tetra (meth) acrylate, EO-modified pentaerythritol tetra (meth) acrylate, PO (meta) acryloyloxyethyl isocyanurate, Acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, EO modified ditrimethylol propane tetra (meth) acrylate, PO modified ditrimethylol propane tetra (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO modified dipentaerythritol hexa (meth) acrylate, PO-modified dipentaerythritol hexa (metha) acrylate, caprolactone modified dipentaerythritol hexa Acrylate, and the like. These may be used alone or in combination.

To the curable resin composition of the present invention, a polymerization initiator by an active energy ray is added as needed. Herein, the polymerization initiator by the active energy ray includes both a photopolymerization initiator and a polymerization initiator by an active energy ray such as ultraviolet rays.

As the photopolymerization initiator, for example, aromatic ketones such as benzophenone, aromatic compounds such as anthracene and? -Chloromethylnaphthalene, and sulfur compounds such as diphenyl sulfide and thiocarbamate can be used.

Examples of the polymerization initiator by an active energy ray such as ultraviolet rays other than visible light include acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenylethane 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-dimethoxybenzophenone, Benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2- 2-methyl-1-phenylpropan-1-one, dioxanthone, diethyl dioxanthone, 2-isopropyl dioxanone, 2- chlorodioxanthone, 2- 2-morpholino-propan-1-one, 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) ) Phenyl- (2-hydroxy-2-propyl) ketone, 2,4,6-trimethylbenzoyldiphe Phosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy- Phenyl) propanone).

Examples of commercial products of the polymerization initiator by the active energy ray are IRGACURE 184, 369, 651, 500, 819, 907, 784, 2959, 1000, 1300, 1700, 1800, 1850, DAROCUR 1116, 1173, LUCIRIN TPO manufactured by BASF Corporation, EBECRYL P36 manufactured by UCB, trade names: ESACURE KIP150, KIP100F, KT37, KT55, KTO46, TZT, KIP75LT and Nippon Kayaku manufactured by FRATELLI LAMBERTI Trade name: KAYACURE DETX, manufactured by Nippon Shokubai Co., Ltd., and the like.

If necessary, a radical polymerization initiator may be used in combination with the active energy ray initiator. Examples of the radical polymerization initiator include benzoyl peroxide, methylcyclohexanone peroxide, cumene hydroperoxide, diisopropylbenzene peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, Organic peroxides such as oxycarbonate and t-butylperoxyisopropyl monocarbonate, and azo compounds such as 2,2'-azobisisobutyronitrile (AIBN) can be used.

The content of these polymerization initiators varies depending on the kind thereof, but is generally 1 to 8 parts by weight based on 100 parts by weight of urethane acrylate. If the content is too small, the active energy ray sensitivity becomes insufficient. If the content is too large, the active energy ray can not reach the deep portion of the film sufficiently, and the curability at the deep portion of the film tends to be lowered. The energy source for curing the curable resin composition of the present invention is not particularly limited, and examples thereof include metal halide lamps such as high-pressure mercury lamp, electron beam,? -Ray, carbon arc, and xenon.

In the curable resin composition of the present invention, various additives usually included in the above organic solvents, monomers, various initiators, paints, coating agents and the like can be added as needed. Examples of the additive include light stabilizers, ultraviolet absorbers, catalysts, leveling agents, antifoaming agents, polymerization accelerators, antioxidants, flame retardants, infrared absorbers, antistatic agents and slip agents.

The curable resin composition of the present invention is used as a coating material, a coating material, and the like. Electric or electronic devices such as mobile phones, wrist watches, compact discs, audio devices, and OA devices; Electronic parts such as touch panels, anti-reflection plates of cathode ray tubes; Household appliances such as refrigerators, vacuum cleaners, and microwave ovens; Automobile interior products such as meter panels and dashboards; PCM (Pre-coated Metal) steel; Automobile parts such as body, bumper, spoiler, door handle, handle, head lamp, gasoline tank of motorcycle, plated / vaporized or sputtered aluminum wheel, door mirror; Carport roof, mining roof; A protective layer for various optical lenses such as a protective layer for optical disk recording media, a sunglass or an orthodontic spectacles lens, plastic molded articles such as polyethylene vinyl chloride, acrylic resin, polyethylene terephthalate, polycarbonate and ABS resin; Woodworking products such as stairs, floors, desks, chairs, dressers, and other furniture; Cloth, paper, and the like.

The coating can be carried out by a conventional method, and examples thereof include an air spray method, an electrostatic coating method, a roll coating method, a flow coating method and a spin coating method. The thickness of the coating obtained by coating or coating is preferably about 1 to 100 mu m. If the thickness of the film is less than 1 mu m, the function as a film is difficult to achieve. If the thickness exceeds 100 mu m, the thickness of the film becomes too thick and the physical properties of the object to be coated become difficult to exhibit.

By the urethane (meth) acrylate of the present invention, a cured product having appropriate hardness, scratch resistance and resilience can be obtained.

[Example]

Next, examples will be described together with comparative examples. However, the present invention is not limited to these embodiments.

<Synthesis of urethane acrylate>

[Synthesis Example 1]

1,400 g (1 mole) of hexamethylene diisocyanate allophanate adduct of 1,6-hexane diol polycarbonate diol (NCO content 13.5%, average 4.5-function), 1.4 g of hydroquinone monomethyl ether, 1265 g (5.5 mol) of caprolactone 1 mole adduct of ethyl acrylate (molecular weight 230) was added thereto, and the reaction was continued at 70 to 80 ° C until the amount of free isocyanate was 0.1% or less to obtain urethane acrylate A.

[Synthesis Example 2]

The flask was charged with 1,300 g (1 mole) of hexamethylene diisocyanate allophanate adduct of polytetramethylene glycol (NCO content 16.5%, average 5.1), 1.3 g of hydroquinone monomethyl ether, 2-hydroxyethyl acrylate (2.0 mol) of 2-hydroxyethyl acrylate and 1,100 g (3.2 mol) of caprolactone adduct of 2 mol of caprolactone (molecular weight: 344) were charged and when the amount of free isocyanate reached 70% To obtain urethane acrylate B.

[Synthesis Example 3]

The flask was charged with 1,340 g (1 mole) of hexamethylene diisocyanate adduct of trimethylolpropane ethylene oxide adduct (NCO content: 9.4%, average trifunctional), 0.8 g of hydroquinone monomethyl ether, 2-hydroxyethyl acrylate 116) was added thereto, and the reaction was continued at 70 to 80 캜 until the amount of the free isocyanate reached 0.1% or less to obtain urethane acrylate C.

[Synthesis Example 4]

To the flask was added 504 g (1 mole) of hexamethylene diisocyanate isocyanurate (NCO content 25%, average trifunctional), 0.8 g of hydroquinone monomethyl ether, 2 mol adduct of caprolactone of 2-hydroxyethyl acrylate Molecular weight 344), and the reaction was continued at 70 to 80 ° C until the amount of free isocyanate reached 0.1% or less to obtain urethane acrylate D.

[Synthesis Example 5]

262 g (1 mole) of dicyclohexylmethane diisocyanate (NCO content 32%, average bifunctional), 0.5 g of hydroquinone monomethyl ether, 2 mol adduct of caprolactone of 2-hydroxyethyl acrylate (molecular weight 344) 722.4 g (2.1 mol) of diisocyanate were added thereto, and the reaction was continued at 70 to 80 캜 until the amount of free isocyanate reached 0.1% or less to obtain urethane acrylate E.

[Synthesis Example 6]

To the flask was added 2,524 g (1 mole) of propylene glycol and dicyclohexylmethane diisocyanate adduct of 1,4-butanediol polycarbonate diol (NCO content: 3.33%, average bifunctional), 1.4 g of hydroquinone monomethyl ether, 243.6 g (2.1 mol) of hydroxyethyl acrylate (molecular weight 116) was added thereto, and the reaction was continued at 70 to 80 캜 until the amount of free isocyanate became 0.1% or less to obtain urethane acrylate F.

&Lt; Preparation and Evaluation of Curable Resin Composition >

Three parts of a photopolymerization initiator (IRGACURE 184 manufactured by Ciba Specialty Chemicals) were compounded and dissolved in 100 parts of each of the urethane acrylates A to F obtained in the above Synthesis Example. The film was coated on a polyethylene terephthalate substrate (PET manufactured by TORAY INDUSTRIES, INC., Model number: # 100 T60) to a film thickness of about 20 μm. Using a high-pressure mercury lamp of 80 W / cm, Cm &lt; 2 &gt; in a nitrogen atmosphere. For each of the obtained cured products, the glass transition temperature, pencil hardness, and stability were examined by the following methods. The results are shown in Table 1 below.

Urethane acrylate Stability Pencil hardness Glass transition temperature / ° C Example 1 A ○ F 18.5 Example 2 B ○ F 15.6 Example 3 C ○ F 10.3 Comparative Example 1 D × B 5.1 Comparative Example 2 E △ F 24.0 Comparative Example 3 F △ HB -3.8

[Glass transition temperature]

The maximum glass transition temperature was measured using a dynamic viscoelasticity measuring device (manufactured by UBM, model number: Rheogel-E4000) at a frequency of 1 Hz and a temperature rise of 3 ° C / min under the conditions of tensile sinusoidal wave, Transition temperature.

[Pencil hardness]

According to JIS K5400, a load of 750 g was worn by a pencil scratching tester, and the hardest pencil hardness without scratches was obtained.

[Stability]

The cured film obtained above was rubbed five times with a brass wire brush (No. 9 produced by Fujiwara Sangyo Co., Ltd.) under a load of 2 kg, and the state of flaws on the cured film was visually observed. The evaluation was conducted as follows: the evaluation was made at room temperature 23 占 폚, the restoration of flaws within 10 seconds was evaluated as?, The evaluation of 10 seconds to 10 minutes was evaluated as?, And the restoration was evaluated as? As can be seen from Table 1, the curable resin composition containing the urethane (meth) acrylate of the present invention was able to form a cured product capable of exhibiting restitution. As can be seen from Comparative Example 1, the cured product containing urethane methacrylate containing no polyol and the urethane (meth) acrylate containing polyurethane having less than 3 functional groups as shown in Comparative Examples 2 and 3 It was confirmed that the hardness of the cured product was poor.

Also in the case of urethane (meth) acrylates using polyols other than the polyols described in Examples 1 to 3, isocyanates and (meth) acrylates containing hydroxyl groups in the molecule, the number of functional groups of the polyurethane is preferably 3.0 or more and 6.0 or less , It was confirmed that the same pencil hardness and resilience as in the Examples can be obtained.

The curable resin composition containing the urethane (meth) acrylate of the present invention is suitable as a coating material or a coating material in a field requiring scratch resistance because it can obtain a cured product having suitable hardness and scratch resistance and restitution property . Specifically, electric and electronic devices such as a cellular phone, a wrist watch, a compact disk, an audio device, and an OA device; Electronic parts such as touch panels; Household appliances such as refrigerators, vacuum cleaners, microwave ovens, and flat panel TVs; Interior parts of automobiles such as meter panels and dashboards; It can be applied to automobile parts and the like.

While the invention has been described in detail and with reference to specific embodiments thereof, it is evident to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention.

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2012-048712) filed on March 6, 2012, the contents of which are incorporated herein by reference.

Claims (2)

(A) a polyol having a number average molecular weight of 200 or more and 3000 or less, and containing at least two hydroxyl groups in a molecule, (B) a polyisocyanate containing at least one dimer, trimer or biuret isocyanate of a polyisocyanate, and (C) a urethane (meth) acrylate obtained by reacting a (meth) acrylate component containing a hydroxyl group in a molecule,
(Meth) acrylate characterized in that the number of functional groups of the polyurethane obtained by reacting (A) and (B) is from 3.0 to 6.0. A curable resin composition containing the urethane (meth) acrylate according to claim 1,
Wherein a cured product having a glass transition temperature measured by dynamic viscoelasticity measurement is 0 占 폚 or more and 30 占 폚 or less.