KR20190019944A - Urethane (meth) acrylate resin and laminated film - Google Patents

Abstract

(Meth) acrylate resin excellent in scratch resistance, abrasion resistance, flexibility and impact resistance in a cured coating film, a curable composition containing the same, a cured product thereof, and a laminated film. (Meth) acrylate resin having an essential reaction material as a raw material, a curing composition containing the polyisocyanate compound (A) having an aromatic ring or alicyclic structure in the molecule and dipentaerythritol (meth) acrylate Its cured product, and laminated film.

Description

Urethane (meth) acrylate resin and laminated film

The present invention relates to a urethane (meth) acrylate resin excellent in various properties such as abrasion resistance, lubrication resistance, flexibility and impact resistance in a cured coating film, a curable composition containing the same and a cured product thereof, Lt; / RTI >

The plastic film produced by using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin or the like can be used as a polarizing plate protective film or a surface protective film of a touch panel introduced into a flat panel display, It is widely used in applications. Since these plastic films are insufficient in performance such as those which are easily scratched on their surfaces and that are easily broken or cracked due to low workability, these plastic films are usually provided with a coat layer made of an active energy ray- , And these functions are supplemented.

As a coating agent for plastic film reinforcement, for example, a resin composition containing urethane acrylate obtained by reacting dipentaerythritol polyacrylate having a hydroxyl value of 80 to 120 mgKOH / g with hexamethylene diisocyanate is known (See Patent Document 1). The resin composition described in Patent Document 1 has a high surface hardness and an excellent scratch resistance in a cured product, but is prone to curling and has insufficient toughness and flexibility of the coating film. Therefore, It was easy to cause cracking.

International Publication No. 2010/146801

Accordingly, an object to be solved by the present invention is to provide a urethane (meth) acrylate resin excellent in various properties such as scratch resistance, lubrication resistance, flexibility and impact resistance in a cured coating film, a curable composition containing the same, And to provide a laminated film.

The inventor of the present invention has made intensive studies to solve the above problems. As a result, the present inventors have found that a urethane (meth) acrylate obtained by reacting a polyisocyanate compound having an aromatic ring or alicyclic structure in a molecule with dipentaerythritol (meth) Acrylate resin solves the above problems, and has accomplished the present invention.

That is, the present invention relates to a urethane (meth) acrylate resin having a polyisocyanate compound (A) having an aromatic ring or alicyclic structure in a molecule and dipentaerythritol (meth) acrylate will be.

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

The present invention also relates to a cured product obtained by curing the above-mentioned curable composition.

The present invention also relates to a laminated film having a layer composed of the cured product and other plastic film layers.

According to the present invention, there is provided a urethane (meth) acrylate resin excellent in scratch resistance, lubrication resistance, flexibility and impact resistance, a curable composition containing the same, a cured product thereof, and a laminated film . The curable composition containing the urethane (meth) acrylate resin of the present invention can be suitably used as a coating agent for reinforcing various plastic films, and the laminated film obtained by using the curable composition of the present invention is excellent in scratch resistance and longevity It is excellent in flexibility and is resistant to cracking when bent or wound, and has an impact resistance that is hard to break even when there is a fallen object on the film.

The urethane (meth) acrylate resin of the present invention essentially contains a polyisocyanate compound (A) having an aromatic ring or alicyclic structure in its molecule and dipentaerythritol (meth) acrylate (B) as essential reaction materials.

The polyisocyanate compound (A) is not particularly limited as long as it has an aromatic ring or alicyclic structure in the molecule, and a wide variety of polyisocyanate compounds can be used. Among them, as the polyisocyanate compound (A) which can be preferably used in the present invention, the following three polyisocyanate compounds (A) can be exemplified.

1. A compound represented by the following structural formulas (A1-1) to (A1-3)

(Wherein R ¹ is each independently an alkyl group of 1 to 4 carbon atoms and j is 0 or an integer of 1 to 4. R ² independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms One)

A diisocyanate compound (A1) represented by any one of the following formulas

2. A compound represented by the following structural formula (A2-1) or (A2-2)

(Wherein l is an integer of 0 or 1 or more and m is 1 or 2. R ³ each independently represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, Methylene group, k is 0, 1 or 2, and n is 0 or an integer of 1 to 8,

A polyisocyanate compound (A2) represented by any one of

3. Isophorone diisocyanate or its modified product (A3)

When the polyisocyanate compound (A) is any one of the diisocyanate compound (A1) or its modified product, the polyisocyanate compound (A2) or its modified product, isophorone diisocyanate or its modified product (A3) , And preferable forms of the urethane (meth) acrylate resin of the present invention will be described in detail below.

The case where the polyisocyanate compound (A) is the diisocyanate compound (A1) or its modification is explained. The urethane (meth) acrylate resin of the present invention in this case is referred to as urethane (meth) acrylate resin (1). The urethane (meth) acrylate resin (1) has an excellent adhesion to various plastic substrates in addition to scratch resistance, lubrication resistance, flexibility and impact resistance in a cured coating film.

R ¹ in each of the structural formulas (A1-1) to (A1-3) is independently an alkyl group having 1 to 4 carbon atoms and n is 0 or an integer of 1 to 4 with respect to the diisocyanate compound (A1) . Of these, urethane (meth) acrylate resin (1) is excellent in the balance of surface hardness, flexibility and impact resistance in the cured coating film, so that n is preferably 0.

Each of R ² in the structural formulas (A1-1) to (A1-3) is independently any one of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Among them, a urethane (meth) acrylate resin (1) having excellent balance of surface hardness, flexibility and impact resistance in a cured coating film is preferable, and therefore, it is preferably a hydrogen atom or a methyl group.

The modified product of the diisocyanate compound (A1) is a modified polyisocyanate compound having the diisocyanate compound (A1) as a raw material. For example, the modified product of the diisocyanate compound (A1) (A), an amine modified product obtained by reacting the diisocyanate compound (A1) with a polyol compound, a biuret modified product of the diisocyanate compound (A1), an allophanate modified product of the diisocyanate compound . In the present invention, one diisocyanate compound (A1) or a modified product thereof may be used alone or two or more thereof may be used in combination.

The dipentaerythritol (meth) acrylate (B) is a product obtained by (meth) acrylating a part of the hydroxyl groups of dipentaerythritol and having a hydroxyl group capable of reacting with the diisocyanate compound (A) The compound may be a single compound or a mixture of a plurality of compounds. That is, in the case of the former, as the dipentaerythritol (meth) acrylate (B), dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate are used singly. In the latter case, it is preferable to use at least one monomer selected from the group consisting of dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate and pentaerythritol penta (meth) acrylate, and may further contain dipentaerythritol hexa (meth) acrylate as required.

In particular, since the urethane (meth) acrylate resin (1) is excellent in the balance of surface hardness, flexibility and impact resistance in the cured coating film, the dipentaerythritol (meth) acrylate (Meth) acrylate (b1) as essential components, and those containing dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (metha) acrylate (B1), dipentaerythritol penta (metha) acrylate (b2) and dipentaerythritol hexa (metha) acrylate (b3) are more preferable, and particularly preferred are those containing dipentaerythritol tetra desirable.

When the dipentaerythritol (meth) acrylate (B) contains dipentaerythritol tetra (meth) acrylate (b1) as an essential component, the content thereof is preferably in the range of 1 to 30% , More preferably from 1 to 25%, and particularly preferably from 3 to 20%.

In the present invention, the ratio of the content of each component in the dipentaerythritol (meth) acrylate (B) and the content of each component is a value calculated from the area ratio of the liquid chromatography chart measured under the following conditions .

[Measuring conditions]

Device: Kabushiki Kaisha Shimazu Seisaku Joze "LCMS-2010EV"

Data processing: " LCMS Solution ", Shimazu Seisaku Joze Co.,

Column: "ODS-100V" (2.0 mm ID × 150 mm, 3 μm) manufactured by Tosoh Corporation 40 ° C.

Eluent: water / acetonitrile, 0.4 mL / min

Detector: PDA, MS

Sample preparation: 1. Dissolve 50 mg of the data in 10 ml of acetonitrile (LC)

     2. Stir with vortex for 30 seconds

     3. Politics for 30 minutes

     4. Passed through a 0.2 mu m filtration filter to obtain a measurement sample

Calculation of area ratio: Calculated at UV wavelength of 210 nm

When the dipentaerythritol (meth) acrylate (B) contains dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (metha) acrylate (b2) The ratio [(b1) / (b2)] is preferably in the range of 1/99 to 50/50, more preferably in the range of 5/95 to 30/70.

When the dipentaerythritol (meth) acrylate (B) contains dipentaerythritol hexa (metha) acrylate (b3), the content thereof is preferably from 1 to 60%, more preferably from 5 to 50% Is more preferable.

Further, the hydroxyl value of the dipentaerythritol (meth) acrylate (B) becomes urethane (meth) acrylate resin (1) having excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, More preferably in the range of 65 to 130 mgKOH / g, and particularly preferably in the range of 75 to 115 mgKOH / g. In the present invention, the hydroxyl value of dipentaerythritol (meth) acrylate (B) is calculated from the measured composition based on JIS K 0070 or the composition ratio of each component calculated from the area ratio of the liquid chromatography chart It is a calculated value.

The method for producing the dipentaerythritol (meth) acrylate (B) is not particularly limited, and for example, a method of producing dipentaerythritol by the esterification reaction of dipentaerythritol and acrylic acid can be mentioned. (B ') such as an addition reaction product of dipentaerythritol (meth) acrylate (B) as a by-product other than dipentaerythritol (meth) acrylate (B) ) May be generated. The high molecular weight component (b ') may be purified to remove the crude product of the urethane (meth) acrylate resin (1), which is a crude product of dipentaerythritol (meth) . At this time, the content of the high molecular weight component (b ') in the dipentaerythritol (meth) acrylate (B) crude product is preferably in the range of 1 to 20 mass%.

Further, the hydroxyl value of the crude product of dipentaerythritol (meth) acrylate (B) becomes urethane (meth) acrylate resin (1) having excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, It is preferably in the range of 60 to 150 mgKOH / g, particularly preferably in the range of 85 to 135 mgKOH / g. In the present invention, the hydroxyl value of dipentaerythritol (meth) acrylate (B) is an actual value measured in accordance with JIS K 0070.

The urethane (meth) acrylate resin (1) contains the diisocyanate compound (A1) or its modified product and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials, . Specifically, other polyisocyanate compounds (C) and other monohydroxy (meth) acrylates can be used together with the diisocyanate compound (A1) or its modified product and dipentaerythritol (meth) acrylate (B) Acrylate compounds (D), other polyol compounds (E), and the like.

Examples of other polyisocyanate compounds (C) include aliphatic polyisocyanates such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate. Diisocyanate compounds; Alicyclic diisocyanate compounds such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate; Aromatic diisocyanate compounds such as diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate; A polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); And isocyanurate-modified products, buret-modified products and allophanate-modified products thereof. These may be used alone or in combination of two or more.

Wherein each R ³ independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁴ are each independently any one of an alkyl group having 1 to 4 carbon atoms or a bonding point connecting a structural moiety represented by the structural formula (1) and a methylene group given with an * mark. m is 0 or an integer of 1 to 3, and 1 is an integer of 1 or more]

When the other polyisocyanate compound (C) is used, the effect of the present invention is sufficiently exhibited. Therefore, the total mass of the diisocyanate compound (A1) or its modified product and the other polyisocyanate compound The proportion of the diisocyanate compound (A1) or the modified product thereof is preferably 30% by mass or more, more preferably 40 to 90% by mass, and particularly preferably 50 to 70% by mass.

Examples of other monohydroxy (meth) acrylate compounds (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate compounds such as trimethylolpropane di (meth) acrylate, glycerine di (meth) acrylate, trimethylolpropane di (meth) acrylate and pentaerythritol tri (meth) acrylate; Hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy- Aromatic ring-containing (meth) acrylate compounds such as 3-phenoxypropyl acrylate; The above-mentioned (meth) acrylate compound may be copolymerized with at least one member selected from the group consisting of ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether and allyl glycidyl ether A polyether-modified (meth) acrylate compound obtained by ring-opening polymerization with various cyclic ether compounds; Lactone-modified (meth) acrylate compounds obtained by polycondensation of the (meth) acrylate compound with a lactone compound such as epsilon -caprolactone. These may be used alone or in combination of two or more. Among them, an aliphatic (meth) acrylate compound, a polyether-modified product thereof, and a lactone-modified product are preferable because they are urethane (meth) acrylate resins (1) excellent in flexibility and impact resistance in a cured product. When the other monohydroxy (meth) acrylate compound (D) is used, the effects of the present invention are sufficiently exhibited. Therefore, the dipentaerythritol (meth) acrylate (B) and the monohydroxy Acrylate (B) relative to the total mass of the acrylic copolymer (A) and the acrylate compound (D) is preferably 70 mass% or more, more preferably 90 mass% or more.

The other polyol compound (E) may be, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono (meth) acrylate, trimethylolethane, trimethylolmethane mono (meth) acrylate, trimethylolpropane, trimethyl Polyol monomers such as olpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and pentaerythritol di (meth) acrylate; Wherein the polyol monomer is selected from the group consisting of succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, , 4-cyclohexanedicarboxylic acid and the like; a polyester polyol obtained by co-condensation with a dicarboxylic acid such as 4-cyclohexanedicarboxylic acid; A lactone-type polyester polyol obtained by polycondensation reaction of the polyol monomer with various lactones such as? -Caprolactone,? -Valerolactone and 3-methyl-delta-valerolactone; And polyether polyols obtained by ring-opening polymerization of the polyol monomer with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These other polyol compounds (E) may be used alone or in combination of two or more. When these other polyol compounds (E) are used, the effect of the present invention is sufficiently exhibited. Therefore, it is preferable that the total amount of the dipentaerythritol (meth) acrylate (B) and the other polyol compound The proportion of the dipentaerythritol (meth) acrylate (B) is preferably 70% by mass or more, and more preferably 90% by mass or more.

The method for producing the urethane (meth) acrylate resin (1) of the present invention can be carried out, for example, by reacting the diisocyanate compound (A1) or its modified product with dipentaerythritol (meth) (NCO) / (OH)] of the isocyanate group of the isocyanate compound (A1) or a modified product thereof to the hydroxyl group of the dipentaerythritol (meth) acrylate (B) is from 1 / 0.95 to 1 / 1.05 , And a method in which the urethanization catalyst is used in a temperature range of 20 to 120 캜, if necessary, according to need, and the like.

In addition to the diisocyanate compound (A1) or its modified product and the dipentaerythritol (meth) acrylate (B), the other polyisocyanate compound (C) and the other monohydroxy (meth) In the case of reacting the acrylate compound (D) and the other polyol compound (E), the three components may be reacted at once. The polyisocyanate component and the polyol component are reacted first to obtain an intermediate, Or a method of reacting the polyisocyanate component with a monoalcohol component to obtain an intermediate, and then reacting the polyol component. The reaction ratio of each component is preferably such that the molar ratio [(NCO) / (OH)] of the sum of the isocyanate group of the polyisocyanate component and the hydroxyl group of the alcohol component is in the range of 1 / 0.95 to 1 / 1.05 Do.

The (meth) acryloyl group equivalent of the urethane (meth) acrylate resin (1) is urethane (meth) acrylate resin (1) having excellent curability and high surface hardness in the cured coating film. / eq, more preferably in the range of 100 to 200 g / eq. In the present invention, the (meth) acryloyl group equivalent of the urethane (meth) acrylate resin (1) is a value calculated from the starting materials as a theoretical value.

The weight average molecular weight (Mw) of the urethane (meth) acrylate resin (1) is urethane (meth) acrylate resin (1) excellent in balance of performance in the cured product, , And more preferably in the range of 2,000 to 15,000.

In the present invention, the molecular weight of the resin is a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8220GPC manufactured by TOSOH CORPORATION

column; TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation

      + TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation

Detector; RI (differential refractometer)

Data processing; Multi station GPC-8020modelII manufactured by Tosoh Corporation

Measuring conditions; Column temperature 40 ° C

           Solvent tetrahydrofuran

           Flow rate 0.35 ml / min

Standard; Monodisperse polystyrene

sample; A tetrahydrofuran solution of 0.2 mass% in terms of the solid content of the resin was filtered with a microfilter (100 μl)

The case where the polyisocyanate compound (A) is the polyisocyanate compound (A2) or a modification thereof will be described. The urethane (meth) acrylate resin of the present invention in this case is referred to as urethane (meth) acrylate resin (2).

1 in the structural formula (A2-1) or (A2-2) is an integer of 0 or 1 or more. Among them, urethane (meth) acrylate resin (2) is excellent in balance of surface hardness, flexibility and impact resistance in the cured coating film, and thus 1 is preferably 0 or 1. When 1 is 0, m in the formula is preferably 2, and when 1 is 1, m is preferably 1 in the formula. That is, the polyisocyanate compound (A1) is preferably a diisocyanate compound having two isocyanate groups in one molecule. Specifically, the polyisocyanate compound (A1-3)

(Wherein R ⁴ is independently an alkyl group having 1 to 4 carbon atoms, k is 0, 1 or 2, and n is 0 or an integer of 1 to 8)

Is more preferably a diisocyanate compound represented by any one of the following.

The modified product of the polyisocyanate compound (A2) is a modified polyisocyanate compound containing the polyisocyanate compound (A2) as a raw material. For example, the modified product of the polyisocyanate compound (A2) (A2), an allophanate-modified product of the polyisocyanate compound (A2), and the like are used as the amine-modified product obtained by reacting the polyisocyanate compound (A2) with the polyisocyanate compound . In the present invention, as the polyisocyanate compound (A2) or a modified product thereof, one type may be used alone, or two or more types may be used in combination.

The dipentaerythritol (meth) acrylate (B) is a product obtained by (meth) acrylating a part of the hydroxyl groups of dipentaerythritol and having a hydroxyl group capable of reacting with the polyisocyanate compound (A) The compound may be a single compound or a mixture of a plurality of compounds. That is, in the case of the former, as the dipentaerythritol (meth) acrylate (B), dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate are used singly. In the latter case, it is preferable to use at least one monomer selected from the group consisting of dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate and pentaerythritol penta (meth) acrylate, and may further contain dipentaerythritol hexa (meth) acrylate as required.

Among them, urethane (meth) acrylate resin (2) is excellent in balance of surface hardness, flexibility and impact resistance in the cured coating film. Therefore, the dipentaerythritol (meth) acrylate (Meth) acrylate (b1) as essential components, and those containing dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (metha) acrylate (B1), dipentaerythritol penta (metha) acrylate (b2) and dipentaerythritol hexa (metha) acrylate (b3) are more preferable, and particularly preferred are those containing dipentaerythritol tetra desirable.

When the dipentaerythritol (meth) acrylate (B) contains dipentaerythritol tetra (meth) acrylate (b1) as an essential component, the content thereof is preferably in the range of 1 to 30% , More preferably from 1 to 25%, and particularly preferably from 3 to 20%.

In the present invention, the ratio of the content of each component in the dipentaerythritol (meth) acrylate (B) and the content of each component is a value calculated from the area ratio of the liquid chromatography chart measured under the following conditions .

[Measuring conditions]

Device: Kabushiki Kaisha Shimazu Seisaku Joze "LCMS-2010EV"

Data processing: " LCMS Solution ", Shimazu Seisaku Joze Co.,

Column: "ODS-100V" (2.0 mm ID × 150 mm, 3 μm) manufactured by Tosoh Corporation 40 ° C.

Eluent: water / acetonitrile, 0.4 mL / min

Detector: PDA, MS

Sample preparation: 1. Dissolve 50 mg of the data in 10 ml of acetonitrile (LC)

     2. Stir with vortex for 30 seconds

     3. Politics for 30 minutes

     4. The sample was passed through a 0.2 mu m filter to obtain a measurement sample

Calculation of area ratio: Calculated at UV wavelength of 210 nm

When the dipentaerythritol (meth) acrylate (B) contains dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta (metha) acrylate (b2) The ratio [(b1) / (b2)] is preferably in the range of 1/99 to 50/50, more preferably in the range of 5/95 to 30/70.

When the dipentaerythritol (meth) acrylate (B) contains dipentaerythritol hexa (metha) acrylate (b3), the content thereof is preferably from 1 to 60%, more preferably from 5 to 50% Is more preferable.

The hydroxyl value of the dipentaerythritol (meth) acrylate (B) is urethane (meth) acrylate resin (2) having excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, More preferably in the range of 65 to 130 mgKOH / g, and particularly preferably in the range of 75 to 115 mgKOH / g. In the present invention, the hydroxyl value of dipentaerythritol (meth) acrylate (B) is calculated from the measured composition based on JIS K 0070 or the composition ratio of each component calculated from the area ratio of the liquid chromatography chart It is a calculated value.

The method for producing the dipentaerythritol (meth) acrylate (B) is not particularly limited, and for example, a method of producing dipentaerythritol by the esterification reaction of dipentaerythritol and acrylic acid can be mentioned. (B ') such as an addition reaction product of dipentaerythritol (meth) acrylate (B) as a by-product other than dipentaerythritol (meth) acrylate (B) ) May be generated. The high-molecular-weight component (b ') may be purified or may be used as a raw material for the urethane (meth) acrylate resin (2) as a crude product of dipentaerythritol (meth) acrylate (B) containing the same. At this time, the content of the high molecular weight component (b ') in the dipentaerythritol (meth) acrylate (B) crude product is preferably in the range of 1 to 20 mass%.

Further, the hydroxyl value of the crude product of the dipentaerythritol (meth) acrylate (B) becomes urethane (meth) acrylate resin (2) having excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, It is preferably in the range of 60 to 150 mgKOH / g, particularly preferably in the range of 85 to 135 mgKOH / g. In the present invention, the hydroxyl value of dipentaerythritol (meth) acrylate (B) is an actual value measured in accordance with JIS K 0070.

The urethane (meth) acrylate resin (2) contains the polyisocyanate compound (A2) or its modified product and dipentaerythritol (meth) acrylate (B) as essential reaction raw materials, . Concretely, other polyisocyanate compounds (C) and other monohydroxy (meth) acrylates can be used together with the polyisocyanate compound (A2) or its modified product and dipentaerythritol (meth) Acrylate compounds (D), other polyol compounds (E), and the like.

Examples of other polyisocyanate compounds (C) include aliphatic polyisocyanates such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate. Diisocyanate compounds; Alicyclic diisocyanate compounds such as isophorone diisocyanate; And isocyanurate-modified products, buret-modified products and allophanate-modified products thereof. These may be used alone or in combination of two or more.

When the other polyisocyanate compound (C) is used, the effect of the present invention is sufficiently exhibited. Therefore, the total mass of the polyisocyanate compound (A2) or its modified product and the other polyisocyanate compound , The proportion of the polyisocyanate compound (A2) or modified product thereof is preferably 30 mass% or more, more preferably 50 mass% or more, and particularly preferably 90 mass% or more.

Examples of other monohydroxy (meth) acrylate compounds (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate compounds such as trimethylolpropane di (meth) acrylate, glycerine di (meth) acrylate, trimethylolpropane di (meth) acrylate and pentaerythritol tri (meth) acrylate; Hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy- Aromatic ring-containing (meth) acrylate compounds such as 3-phenoxypropyl acrylate; The above-mentioned (meth) acrylate compound may be copolymerized with at least one member selected from the group consisting of ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether and allyl glycidyl ether A polyether-modified (meth) acrylate compound obtained by ring-opening polymerization with various cyclic ether compounds; Lactone-modified (meth) acrylate compounds obtained by polycondensation of the (meth) acrylate compound with a lactone compound such as epsilon -caprolactone. These may be used alone or in combination of two or more. Among them, an aliphatic (meth) acrylate compound, a polyether-modified product thereof, and a lactone-modified product are preferable because they are a urethane (meth) acrylate resin (2) excellent in flexibility and impact resistance in a cured product. When the other monohydroxy (meth) acrylate compound (D) is used, the effects of the present invention are sufficiently exhibited. Therefore, the dipentaerythritol (meth) acrylate (B) and the monohydroxy Acrylate (B) relative to the total mass of the acrylic copolymer (A) and the acrylate compound (D) is preferably 70 mass% or more, more preferably 90 mass% or more.

The other polyol compound (E) may be, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono (meth) acrylate, trimethylolethane, trimethylolmethane mono (meth) acrylate, trimethylolpropane, trimethyl Polyol monomers such as olpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and pentaerythritol di (meth) acrylate; Wherein the polyol monomer is selected from the group consisting of succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, , 4-cyclohexanedicarboxylic acid and the like; a polyester polyol obtained by co-condensation with a dicarboxylic acid such as 4-cyclohexanedicarboxylic acid; A lactone-type polyester polyol obtained by polycondensation reaction of the polyol monomer with various lactones such as? -Caprolactone,? -Valerolactone and 3-methyl-delta-valerolactone; And polyether polyols obtained by ring-opening polymerization of the polyol monomer with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These other polyol compounds (E) may be used alone or in combination of two or more. When these other polyol compounds (E) are used, the effect of the present invention is sufficiently exhibited. Therefore, it is preferable that the total amount of the dipentaerythritol (meth) acrylate (B) and the other polyol compound The proportion of the dipentaerythritol (meth) acrylate (B) is preferably 70% by mass or more, and more preferably 90% by mass or more.

The method for producing the urethane (meth) acrylate resin (2) of the present invention can be carried out, for example, by reacting the polyisocyanate compound (A2) or its modified product with dipentaerythritol (meth) (NCO) / (OH)] of the isocyanate group of the isocyanate compound (A2) or a modified product thereof to the hydroxyl group of the dipentaerythritol (meth) acrylate (B) is from 1 / 0.95 to 1 / 1.05 , And a method in which the urethanization catalyst is used in a temperature range of 20 to 120 캜, if necessary, according to need, and the like.

The above polyisocyanate compound (C) and other monohydroxy (meth) acrylate compounds as well as the polyisocyanate compound (A2) or a modified product thereof and the dipentaerythritol (meth) acrylate (B) In the case of reacting the acrylate compound (D) and the other polyol compound (E), the three components may be reacted at once. The polyisocyanate component and the polyol component are reacted first to obtain an intermediate, Or a method of reacting the polyisocyanate component with a monoalcohol component to obtain an intermediate, and then reacting the polyol component. The reaction ratio of each component is preferably such that the molar ratio [(NCO) / (OH)] of the sum of the isocyanate group of the polyisocyanate component and the hydroxyl group of the alcohol component is in the range of 1 / 0.95 to 1 / 1.05 Do.

The (meth) acryloyl group equivalent of the urethane (meth) acrylate resin (2) is urethane (meth) acrylate resin (2) having excellent hardenability and high surface hardness in the cured coating film. Therefore, 100 to 500 g / eq. < / RTI > In the present invention, the (meth) acryloyl group equivalent of the urethane (meth) acrylate resin (2) is a value calculated from the starting materials as a theoretical value.

Since the urethane (meth) acrylate resin (2) has a weight average molecular weight (Mw) of urethane (meth) acrylate resin (2) excellent in balance of performance in the cured product, , And more preferably in the range of 2,000 to 15,000.

The case where the polyisocyanate compound (A) is isophorone diisocyanate or its modified product (A3) is explained. The urethane (meth) acrylate resin of the present invention in this case is referred to as urethane (meth) acrylate resin (3).

With respect to the isophorone diisocyanate or the modified product thereof (A3), the modified product of isophorone diisocyanate is a modified polyisocyanate compound having isophorone diisocyanate as a raw material, and examples thereof include isophorone diisocyanate and isomer An isocyanurate denatured product obtained by reacting an isophorone diisocyanate with an isophorone diisocyanate and an isocyanurate denatured product obtained by reacting isophorone diisocyanate with a polyol compound, a biuret modified product of isophorone diisocyanate, an allophanate denatured product of isophorone diisocyanate, have. In the present invention, as the isophorone diisocyanate or the modified product thereof (A3), one type may be used alone, or two or more types may be used in combination.

The dipentaerythritol (meth) acrylate (B) is a product obtained by (meth) acrylating a part of the hydroxyl groups of dipentaerythritol and having a hydroxyl group capable of reacting with the polyisocyanate compound (A) The compound may be a single compound or a mixture of a plurality of compounds. That is, in the case of the former, as the dipentaerythritol (meth) acrylate (B), dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (Meth) acrylate, dipentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate are used singly. In the latter case, it is preferable to use at least one monomer selected from the group consisting of dipentaerythritol mono (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (Meth) acrylate and pentaerythritol penta (meth) acrylate, and may further contain dipentaerythritol hexa (meth) acrylate as required.

In particular, the urethane (meth) acrylate resin (3) is excellent in the balance of surface hardness, flexibility and impact resistance in the cured coating film. Therefore, the dipentaerythritol (meth) (B1) / (b2) of the content of both (meth) acrylate (b1) and dipentaerythritol penta (metha) acrylate (b2) in the range of 5/95 to 30/70 .

In the present invention, the ratio of the content of each component in the dipentaerythritol (meth) acrylate (B) and the content of each component is a value calculated from the area ratio of the liquid chromatography chart measured under the following conditions .

[Measuring conditions]

Device: Kabushiki Kaisha Shimazu Seisaku Joze "LCMS-2010EV"

Data processing: " LCMS Solution ", Shimazu Seisaku Joze Co.,

Column: "ODS-100V" (2.0 mm ID × 150 mm, 3 μm) manufactured by Tosoh Corporation 40 ° C.

Eluent: water / acetonitrile, 0.4 mL / min

Detector: PDA, MS

Sample preparation: 1. Dissolve 50 mg of the data in 10 ml of acetonitrile (LC)

     2. Stir with vortex for 30 seconds

     3. Politics for 30 minutes

     4. The sample was passed through a 0.2 mu m filter to obtain a measurement sample

Calculation of area ratio: Calculated at UV wavelength of 210 nm

(Meth) acrylate resin (3) having excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, it is possible to use dipentaerythritol tetra (meth) acrylate (b1) and dipentaerythritol penta It is more preferable to contain dipentaerythritol hexa (meth) acrylate (b3) in addition to the (meth) acrylate (b2).

The content of dipentaerythritol tetra (meth) acrylate (b1) in the dipentaerythritol (meth) acrylate (B) is preferably in the range of 1 to 30%, more preferably in the range of 1 to 25% , And particularly preferably in the range of 3 to 20%.

The content of dipentaerythritol hexa (meth) acrylate (b3) in the dipentaerythritol (meth) acrylate (B) is preferably in the range of 1 to 60%, more preferably in the range of 5 to 50% desirable.

The hydroxyl value of the dipentaerythritol (meth) acrylate (B) is urethane (meth) acrylate resin (3) having excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, More preferably in the range of 65 to 130 mgKOH / g, and particularly preferably in the range of 75 to 115 mgKOH / g. In the present invention, the hydroxyl value of dipentaerythritol (meth) acrylate (B) is calculated from the measured composition based on JIS K 0070 or the composition ratio of each component calculated from the area ratio of the liquid chromatography chart It is a calculated value.

The method for producing the dipentaerythritol (meth) acrylate (B) is not particularly limited, and for example, a method of producing dipentaerythritol by the esterification reaction of dipentaerythritol and acrylic acid can be mentioned. (B ') such as an addition reaction product of dipentaerythritol (meth) acrylate (B) as a by-product other than dipentaerythritol (meth) acrylate (B) ) May be generated. The high-molecular-weight component (b ') may be purified or may be used as a raw material for a urethane (meth) acrylate resin (3) while being a crude dipentaerythritol (meth) acrylate (B) product. At this time, the content of the high molecular weight component (b ') in the dipentaerythritol (meth) acrylate (B) crude product is preferably in the range of 1 to 20 mass%.

Further, the hydroxyl value of the crude product of the dipentaerythritol (meth) acrylate (B) becomes urethane (meth) acrylate resin (3) having excellent balance of surface hardness, flexibility and impact resistance in the cured coating film, It is preferably in the range of 60 to 150 mgKOH / g, particularly preferably in the range of 85 to 135 mgKOH / g. In the present invention, the hydroxyl value of dipentaerythritol (meth) acrylate (B) is an actual value measured in accordance with JIS K 0070.

The urethane (meth) acrylate resin (3) is an essential reaction raw material for the above isophorone diisocyanate or its modified product (A3) and dipentaerythritol (meth) acrylate (B) It may be used as a raw material. Concretely, other polyisocyanate compounds (C) and other monohydroxy (meth) acrylates can be used together with the isophorone diisocyanate or its modified product (A3) and dipentaerythritol (meth) Acrylate compounds (D), other polyol compounds (E), and the like.

Examples of other polyisocyanate compounds (C) include aliphatic polyisocyanates such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate. Diisocyanate compounds; Alicyclic diisocyanate compounds such as norbornane isocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; Aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate; A polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1); And isocyanurate-modified products, buret-modified products and allophanate-modified products thereof. These may be used alone or in combination of two or more.

Wherein each R ³ independently represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ⁴ are each independently any one of an alkyl group having 1 to 4 carbon atoms or a bonding point connecting a structural moiety represented by the structural formula (1) and a methylene group given with an * mark. m is 0 or an integer of 1 to 3, and 1 is an integer of 1 or more]

When the other polyisocyanate compound (C) is used, the effect of the present invention is sufficiently exhibited. Therefore, the total mass of the isophorone diisocyanate or its modified product (A3) and the other polyisocyanate compound Is preferably at least 30% by mass, more preferably at least 50% by mass, and particularly preferably at least 90% by mass, based on the total amount of the isophorone diisocyanate or its modified product (A3)

Examples of other monohydroxy (meth) acrylate compounds (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate compounds such as trimethylolpropane di (meth) acrylate, glycerine di (meth) acrylate, trimethylolpropane di (meth) acrylate and pentaerythritol tri (meth) acrylate; Hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxyethyl acrylate, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy- Aromatic ring-containing (meth) acrylate compounds such as 3-phenoxypropyl acrylate; The above-mentioned (meth) acrylate compound may be copolymerized with at least one member selected from the group consisting of ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether and allyl glycidyl ether A polyether-modified (meth) acrylate compound obtained by ring-opening polymerization with various cyclic ether compounds; Lactone-modified (meth) acrylate compounds obtained by polycondensation of the (meth) acrylate compound with a lactone compound such as epsilon -caprolactone. These may be used alone or in combination of two or more. Among them, an aliphatic (meth) acrylate compound, a polyether-modified product thereof, and a lactone-modified product are preferable since they are urethane (meth) acrylate resin (3) excellent in flexibility and impact resistance in a cured product. When the other monohydroxy (meth) acrylate compound (D) is used, the effects of the present invention are sufficiently exhibited. Therefore, the dipentaerythritol (meth) acrylate (B) and the monohydroxy Acrylate (B) relative to the total mass of the acrylic copolymer (A) and the acrylate compound (D) is preferably 70 mass% or more, more preferably 90 mass% or more.

The other polyol compound (E) may be, for example, ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, Butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono (meth) acrylate, trimethylolethane, trimethylolmethane mono (meth) acrylate, trimethylolpropane, trimethyl Polyol monomers such as olpropane mono (meth) acrylate, pentaerythritol mono (meth) acrylate, and pentaerythritol di (meth) acrylate; Wherein the polyol monomer is selected from the group consisting of succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, orthophthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, , 4-cyclohexanedicarboxylic acid and the like; a polyester polyol obtained by co-condensation with a dicarboxylic acid such as 4-cyclohexanedicarboxylic acid; A lactone-type polyester polyol obtained by polycondensation reaction of the polyol monomer with various lactones such as? -Caprolactone,? -Valerolactone and 3-methyl-delta-valerolactone; And polyether polyols obtained by ring-opening polymerization of the polyol monomer with cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, and propyl glycidyl ether. These other polyol compounds (E) may be used alone or in combination of two or more. When these other polyol compounds (E) are used, the effect of the present invention is sufficiently exhibited. Therefore, it is preferable that the total amount of the dipentaerythritol (meth) acrylate (B) and the other polyol compound The proportion of the dipentaerythritol (meth) acrylate (B) is preferably 70% by mass or more, and more preferably 90% by mass or more.

The method for producing the urethane (meth) acrylate resin (3) of the present invention can be carried out, for example, by reacting the isophorone diisocyanate or its modified product (A3) with dipentaerythritol (meth) (NCO) / (OH)] of the isocyanate group of the isophorone diisocyanate or the modified product thereof (A3) to the hydroxyl group of the dipentaerythritol (meth) acrylate (B) 1 / 1.05, and using a urethane-forming catalyst for publicly-known catalysts in a temperature range of 20 to 120 캜, if necessary.

In addition to the isophorone diisocyanate or its modified product (A3) and the dipentaerythritol (meth) acrylate (B), the other polyisocyanate compound (C) and the other monohydroxy (meth) In the case of reacting the acrylate compound (D) and the other polyol compound (E), the three components may be reacted at once. The polyisocyanate component and the polyol component are reacted first to obtain an intermediate, Or a method of reacting the polyisocyanate component with a monoalcohol component to obtain an intermediate, and then reacting the polyol component. The reaction ratio of each component is preferably such that the molar ratio [(NCO) / (OH)] of the sum of the isocyanate group of the polyisocyanate component and the hydroxyl group of the alcohol component is in the range of 1 / 0.95 to 1 / 1.05 Do.

(Meth) acryloyl group equivalent of the urethane (meth) acrylate resin (3) of the present invention is urethane (meth) acrylate resin (3) having excellent curability and high surface hardness in the cured coating film, To 500 g / eq, more preferably from 100 to 135 g / eq. In the present invention, the (meth) acryloyl group equivalent of the urethane (meth) acrylate resin (3) is a value calculated as a theoretical value from the reaction raw material.

Since the urethane (meth) acrylate resin (3) has a weight average molecular weight (Mw) of urethane (meth) acrylate resin (3) excellent in balance of performance in the cured product, , And more preferably in the range of 2,000 to 15,000.

The curable composition of the present invention contains the urethane (meth) acrylate resin and a photopolymerization initiator. Examples of the photopolymerization initiator include benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, 4 , 4'-dichlorobenzophenone, Michler's ketone, and various benzophenones such as 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone;

Xanthone such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone and 2,4-diethylthioxanthone, thioxanthones; Various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether;

? -Diketones such as benzyl and diacetyl; Sulfhydrides such as tetramethylthiuram disulfide and p-tolyl disulfide; Various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;

2-methyl-2-methyl-2-methyl-2-methylpropane, 3,3'-carbonyl-bis (7-diethylamino) coumarin, 1-hydroxycyclohexyl phenyl ketone, 2,2'- 2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- 2-methyl-1-phenylpropane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 1- Methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy- 1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone Benzyl dimethyl ketal, benzyl-beta-methoxy ethyl acetal, methyl o-benzoyl benzoate, bis (4-dimethylaminophenyl) ketone, p- dimethylaminoacetophenone,?,? -Dichloro- Pentyl-4-dimethylaminobenzo Di (ethoxycarbonylmethyl) amino] phenyl-S (2-hydroxyphenyl) imidazolyl dimer, 2,4-bis-trichloromethyl-6- -Triazine, 2,4-bis-trichloromethyl-6- (4-ethoxy) phenyl-S-triazine, 2,4-bis- trichloromethyl-6- (3- 2-t-butyl anthraquinone, 2-amylanthraquinone, and? -Chloroanthraquinone. These may be used alone or in combination of two or more.

Among the above photopolymerization initiators, preferred are 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) Methyl-1-propane-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyl (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one can be used for a broad range of wavelengths of light And exhibits activity, and is a curable composition having high curability.

Commercially available products of the photopolymerization initiator include, for example, those available from Chiba Specialty Chemicals Co., "Irgacure-184", "Irgacure-149", "Irgacure-261", "Irgacure- Cure-500 "," Irgacure-651 "," Irgacure-754 "," Irgacure-784 "," Irgacure-819 "," Irgacure-907 " Quot; Irgacure-1816 ", " Irgacure -2959 ", " Irgacure-4043 ", "Quot;, " Multi-cure-1173 "; BASF Shuze "Lucirin TPO"; Kaya Cure-DETX "," Kaya Cure-MBP "," Kaya Cure-DMBI "," Kaya Cure-EPA "and" Kaya Cure-OA "manufactured by Nihon Kayaku Co., Bicure-10 ", " Bicure-55 " manufactured by Sturup Chemical Co., Ltd.; Arc irradiation agent "Trigonal P1"; &Quot; Sandrai 1000 " manufactured by Sandoz; "Dip" made by the ascendant; Quanta Cure-PDO ", " Quanta Cure-ITX ", and " Quanta Cure-EPD "

The amount of the photopolymerization initiator to be added is an amount capable of sufficiently exhibiting its function as a photopolymerization initiator and is preferably such a range that crystal precipitation or deterioration of physical properties of the coating film does not occur. Specifically, 100 parts by mass of the curable composition Is preferably in the range of 0.05 to 20 parts by mass, and particularly preferably in the range of 0.1 to 10 parts by mass.

The curable composition of the present invention may contain various photo sensitizers in addition to the above-mentioned photopolymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur compounds, phosphorus compounds, chlorine compounds or nitriles or other nitrogen-containing compounds.

The curable composition of the present invention may further contain other photo-curing compound (R) other than the urethane (meth) acrylate resin of the present invention, organic solvent, ultraviolet absorber, antioxidant, silicone additive, fluorine additive, silane coupling agent , Phosphoric ester compounds, organic beads, inorganic fine particles, inorganic fillers, rheology control agents, defoaming agents, anti-fogging agents, coloring agents and the like.

The other photo-curing compound (R) may be, for example, various (meth) acrylate monomers (R1) and other urethane (meth) acrylate resins other than the urethane (meth) R2), an epoxy (meth) acrylate resin (R3), a dendrimer type (meth) acrylate resin (R4) and a (meth) acryloyl group containing acrylic resin (R5).

The (meth) acrylate monomer (R1) is, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, glycidyl (meth) acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofuran (Meth) acrylate, isooctyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (Meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, 2-ethoxyethyl Carbitol (meth) acrylate, phosphoric acid (meth) acrylate, ethylene (Meth) acrylate, ethylene oxide modified phenoxy (meth) acrylate, propylene oxide modified phenoxy (meth) acrylate, nonylphenol (meth) acrylate, ethylene oxide modified Acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) 2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2- (Meth) acryloyloxypropylhydrogenphthalate, 2- (meth) acryloyloxypropylhexahydrohydrogenphthalate, 2- (meth) acryloyloxypropyltetra (Meth) acrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropropyl (meth) acrylate, ) Mono (meth) acrylates such as acrylate, octafluoropropyl (meth) acrylate and adamantyl mono (meth) acrylate;

Acrylate, propoxylated hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, hexanediol di (meth) acrylate, ethoxylated hexanediol di Acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, Di (meth) acrylates such as trimethylolpropane di (meth) acrylate, glycerine di (meth) acrylate, trimethylol propane di (meth) acrylate and pentaerythritol di (meth) acrylate;

(Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri Tri (meth) acrylate such as pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate and dipentaerythritol tri (meth) acrylate;

(Meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acrylate such as dipentaerythritol hexa (meth) acrylate, ditrimethylol propane hexa (meth) acrylate and the like;

And (meth) acrylates in which some or all of the various polyfunctional (meth) acrylates described above are modified with polyoxyalkylene chains or polyester chains.

The other urethane (meth) acrylate resin (R2) may be, for example, a urethane (meth) acrylate resin obtained by using a compound other than the polyisocyanate compound (A) having an aromatic ring or alicyclic structure in the molecule as a polyisocyanate compound And urethane (meth) acrylate resins using compounds other than dipentaerythritol (meth) acrylate (B) as the hydroxy (meth) acrylate compound.

The epoxy (meth) acrylate resin (R3) is a compound obtained by reacting various epoxy resins such as a bisphenol epoxy resin and a novolak epoxy resin with (meth) acrylic acid or a derivative thereof to give a (meth) acrylate have.

The dendrimer-type (meth) acrylate resin (R4) refers to a resin having a multi-branched structure with regularity and having a (meth) acryloyl group at the end of each branched chain. In addition to the dendrimer type, Star polymer and the like. Such compounds include, for example, those represented by the following Structural Formulas (2-1) to (2-8), but the present invention is not limited thereto. The compound may have a regular multi-branched structure, Any resin having a (meth) acryloyl group at the end of the branched chain can be used.

(Wherein R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms)

As the dendrimer type (meth) acrylate resin (R4), "Biscott # 1000" [mass average molecular weight (Mw) 1,500 to 2,000, average (meth) acryloyl SP-1106 "manufactured by MIWON (weight average molecular weight (Mw): 15,000 to 23,000)," Viscoat 1020 "having a weight average molecular weight (Mw) of 1,000 to 3,000," SIRIUS501 " (Average number of (meth) acryloyl groups per one molecule 18), CN2301 by SARTOMER, average number of (meth) acryloyl groups per one molecule 16, CN2303 (Meth) acryloyl group number 6], "CN2304" [average (meth) acryloyl group number per one molecule 18], Shin-Tenetsu Sumikin Kagaku Kabushiki Kaisha " Quot; A-HBR-5 " manufactured by Nippon Kayaku Co., Ltd., " New Frontier R-1150 " manufactured by Dai- Syaje may be used a commercially available product such as "hayipeotek UR-101".

The dendrimer-type (meth) acrylate resin (R4) preferably has a mass average molecular weight (Mw) in the range of 1,000 to 30,000. The average number of (meth) acryloyl groups per molecule is preferably in the range of 5 to 30.

The (meth) acryloyl group-containing acrylic resin (R5) can be produced, for example, by polymerizing a (meth) acrylate monomer (a) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group or a glycidyl group as an essential component (Meth) acrylate monomer (s) having a reactive functional group capable of reacting with the functional group (s) is further reacted with an acrylic resin intermediate obtained by subjecting a (meth) acryloyl group to a reaction with a (meth) acryloyl group.

The (meth) acrylate monomer (a) having a reactive functional group includes, for example, a hydroxyl group-containing (meth) acrylate monomer such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; (Meth) acrylate monomers containing a carboxyl group such as (meth) acrylic acid; Isocyanate group-containing (meth) acrylate monomers such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate; (Meth) acrylate monomers having glycidyl groups such as glycidyl (meth) acrylate and 4-hydroxybutyl acrylate glycidyl ether. These may be used alone or in combination of two or more.

The acrylic resin intermediate may be obtained by copolymerizing other polymerizable unsaturated group-containing compounds, if necessary, in addition to the (meth) acrylate monomer (?). The other polymerizable unsaturated group-containing compound may be, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) (Meth) acrylic acid alkyl esters such as acrylate; (Meth) acrylate containing a cyclic ring such as cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and dicyclopentanyl (meth) acrylate; Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate and phenoxyethyl acrylate; Silyl group-containing (meth) acrylates such as 3-methacryloxypropyltrimethoxysilane; And styrene derivatives such as styrene,? -Methylstyrene and chlorostyrene. These may be used alone or in combination of two or more. Among them, it is preferable to use the alkyl (meth) acrylate.

When the acrylic resin intermediate is obtained by copolymerizing the (meth) acrylate monomer (a) and the other polymerizable unsaturated group-containing compound, the reaction ratio of the acrylic resin intermediate and the The proportion of the (meth) acrylate monomer (a) relative to the total of both is preferably in the range of 20 to 70 mass%, more preferably in the range of 30 to 60 mass% Do.

The acrylic resin intermediate may be prepared in the same manner as a general acrylic resin. As an example of the production conditions, it is possible to produce, for example, by polymerizing various monomers in the temperature range of 60 ° C to 150 ° C in the presence of a polymerization initiator. As the polymerization method, for example, bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization and the like can be given. The polymerization mode includes, for example, random copolymers, block copolymers and graft copolymers. In the case of the solution polymerization, for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or a ketone solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether Glycol ether solvents can be preferably used.

The (meth) acrylate monomer (?) Is not particularly limited as long as it is capable of reacting with the reactive functional group possessed by the (meth) acrylate monomer (?), But from the viewpoint of reactivity, the following combination is preferable. That is, in the case of using the (meth) acrylate containing a hydroxyl group as the (meth) acrylate monomer (a), it is preferable to use an isocyanate group-containing (meth) acrylate as the (meth) acrylate monomer . When the carboxyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (a), the glycidyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer . When the isocyanate group-containing (meth) acrylate is used as the (meth) acrylate monomer (a), the hydroxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer (). When the glycidyl group-containing (meth) acrylate is used as the (meth) acrylate monomer (a), the carboxyl group-containing (meth) acrylate is preferably used as the (meth) acrylate monomer .

The reaction between the acrylic resin intermediate and the (meth) acrylate monomer (β) can be carried out, for example, in the presence of an esterification reaction such as triphenylphosphine or the like in the temperature range of 60 to 150 ° C. Or the like may be used. When the reaction is a urethanization reaction, the reaction is carried out while dropping the compound (?) To the acrylic resin intermediate in a temperature range of 50 to 120 占 폚.

The (meth) acryloyl group-containing acrylic resin (R5) preferably has a mass average molecular weight (Mw) in the range of 5,000 to 80,000. It is also preferable that the (meth) acryloyl group equivalent is in the range of 200 to 500 g / equivalent.

These other photo-curable compounds (R) may be used alone or in combination of two or more. Among them, various (meth) acrylate monomers (R1) are preferably used because the composition is excellent in curability. When these other photo-curing compounds (R) are used, in the total 100 parts by mass of the urethane (meth) acrylate resin of the present invention and other photo-curable compounds (R), the urethane (meth) It is preferably used in a proportion such that the amount of the resin becomes 5 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 80 parts by mass or more.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Cyclic ether solvents such as tetrahydrofuran and dioxolane; Esters such as methyl acetate, ethyl acetate and butyl acetate; Aromatic solvents such as toluene and xylene; Alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether; And glycol ether solvents such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether and propylene glycol monopropyl ether. These may be used alone or in combination of two or more.

These organic solvents are mainly used for the purpose of adjusting the viscosity of the curable composition, but it is usually preferable to adjust the non-volatile content to be in the range of 10 to 80 mass%.

The ultraviolet absorber may be, for example, 2- [4 - {(2-hydroxy-3-dodecyloxypropyl) oxy} -2-hydroxyphenyl] ) -1,3,5-triazine, 2- [4 - {(2-hydroxy-3-tridecyloxypropyl) oxy} -2-hydroxyphenyl] Dimethylphenyl) -1,3,5-triazine, and the like, 2- (2'-xanthone carboxy-5'-methylphenyl) benzotriazole, 2- -Methylphenyl) benzotriazole, 2-xanthone carboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like. These may be used alone or in combination of two or more.

Examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, an organic sulfur-based antioxidant, and a phosphoric acid ester-based antioxidant. These may be used alone or in combination of two or more.

Examples of the silicone additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, amino-modified dimethyl Polydimethylsiloxane having a polyether-modified acrylic group, polydimethylsiloxane having a polyester-modified acrylic group, and the like can be given. These may be used alone or in combination of two or more.

Examples of the fluorine-based additive include "Megaface" series of DIC Corporation. These may be used alone or in combination of two or more.

The silane coupling agent may be, for example, vinyl trichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3- 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3 (methoxycarbonyloxypropyltrimethoxysilane) Aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, N- Aminopropyltrimethoxysilane, hydrochloride of N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, special aminosilane, 3-ureidopropyltriethoxysilane, 3- (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis But are not limited to, silane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2- Ethoxy) silane; vinyl silane coupling agents;

(Glycidyloxypropyl) methylsilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, Epoxy silane coupling agents such as 3-glycidoxypropyltriethoxysilane;

styrene-based silane coupling agents such as p-styryltrimethoxysilane;

Methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Siloxane coupling agents of (meth) acryloxime such as ethoxysilane;

Aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) Aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl- Amino-based silane coupling agents such as silane;

Silane coupling agents of ureido, such as 3-ureidopropyltriethoxysilane;

3-chloropropyltrimethoxysilane, chloropropyl type silane coupling agents;

A mercapto-based silane coupling agent such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like;

Silane coupling agents such as bis (triethoxysilylpropyl) tetrasulfide;

And an isocyanate-based silane coupling agent such as 3-isocyanatepropyltriethoxysilane. These may be used alone or in combination of two or more.

Examples of commercially available phosphoric ester compounds include Kayama PM-2, Kayama PM-21 (trade name) manufactured by Nihon Kayaku Co., Ltd., a phosphoric acid ester compound having a (meth) acryloyl group in its molecular structure, Light Ester P-1M "," Light Ester P-2M "," Light Acrylate P-1A (N) "manufactured by Kyoeisha Chemical Co., Ltd.," SIPOMER PAM 100 " PAM 200 "," SIPOMER PAM 300 "," SIPOMER PAM 4000 ", Osaka Yuki Kagaku Kogyo Co., Ltd." Viscot # 3PA "," Viscot # 3PMA "," Daiichi Gosei Iyakusha "New Frontier S- &Quot; SIPOMER PAM 5000 " manufactured by SOLVAY, which is a phosphate ester compound having an allyl ether group in the molecular structure, and the like.

The organic beads include, for example, polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicon beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, Based resin beads, polyester-based resin beads, polyamide resin beads, polyimide-based resin beads, polyfluorinated ethylene resin beads, and polyethylene resin beads. These may be used alone or in combination of two or more. The average particle diameter of these organic beads is preferably in the range of 1 to 10 mu m.

Examples of the inorganic fine particles include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide and the like. These may be used alone or in combination of two or more. The average particle size of these inorganic fine particles is preferably in the range of 95 to 250 nm, and more preferably in the range of 100 to 180 nm. When these inorganic fine particles are contained, a dispersion auxiliary agent may be further used. The dispersion auxiliary agent may be, for example, phosphoric acid ester such as isopropyl acid phosphate, triisodecyl phosphite or ethylene oxide modified phosphoric acid dimethacrylate Compounds and the like. These may be used alone or in combination of two or more.

Commercially available products of the above dispersion aid include, for example, "Kayama PM-21", "Kayama PM-2" manufactured by Nihon Kayaku Co., Ltd., "LIGHT ESTER P- 2M " and the like.

The curable composition of the present invention can be used for a coating material. The coating material can be used as a coat layer for protecting the surface of a substrate by applying it on various substrates and curing by irradiation of active energy rays. In this case, the curable composition of the present invention may be applied directly to the surface protecting member, or may be used as a protective film coated on a plastic film. Alternatively, the curable composition of the present invention may be applied to a plastic film and the coated film may be used as an optical film such as an antireflection film, a diffusion film, and a prism sheet. Since the cured coating film of the curable composition of the present invention is characterized by high surface hardness and excellent flexibility and impact resistance, it can be applied to various kinds of plastic films in a film thickness according to the application, and can be used as a protective film or a film- .

The plastic film may be formed of a resin such as polycarbonate, polymethylmethacrylate, polystyrene, polyester, polyolefin, cycloolefin, epoxy resin, melamine resin, triacetylcellulose resin, ABS resin, AS resin, norbornene resin, A plastic film or a plastic sheet made of a polyimide resin or the like.

Among the above plastic films, triacetylcellulose film is a film particularly favorably used for a polarizing plate of a liquid crystal display, but generally has a thickness of 40 to 100 占 퐉, so that even when a hard coat layer is provided, the surface hardness is sufficiently high And also has a characteristic that it is largely curled. The coating film made of the curable composition of the present invention exhibits an effect that the surface hardness is high and the curling resistance, flexibility, transparency, and impact resistance are also excellent, even when a triacetyl cellulose film is used as a base material. When the triacetylcellulose film is used as a substrate, the application amount of the curable composition of the present invention is such that the film thickness after drying is in the range of 1 to 20 m, preferably 2 to 10 m desirable. Examples of the coating method include bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexo printing, screen printing and the like.

Among the above plastic films, the polyester film includes, for example, polyethylene terephthalate, and its thickness is generally about 20 to 300 mu m. Although it is inexpensive and easy to process, it is a film used for various applications such as a touch panel display. However, it is very flexible and it is difficult to make the surface hardness sufficiently high even when a hard coat layer is provided. When the polyethylene film is used as a substrate, the coating amount when the curable composition of the present invention is applied is adjusted such that the film thickness after drying is in the range of 1 to 100 mu m, preferably 1 to 20 mu m It is preferable to apply it. Generally, a cured coating film having a thickness of more than 20 占 퐉 tends to be curled largely as compared with the case of a thinner film. However, since the curable composition of the present invention also has excellent curling resistance, It is difficult for curling to occur even when it is applied to a film thickness, so that it can be used suitably. Examples of the coating method include bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexo printing, screen printing and the like.

Among the above plastic films, the polymethyl methacrylate film is relatively thick and durable, typically about 50 to 2,000 mu m in thickness, and is therefore suitable for applications requiring a particularly high surface hardness such as a front plate of a liquid crystal display It is a film used to make. When the polymethylmethacrylate film is used as a substrate, the coating amount upon application of the curable composition of the present invention is preferably in the range of 1 to 100 mu m after drying, preferably in the range of 1 to 20 mu m By weight based on the total weight of the composition. Examples of the coating method include bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexo printing, screen printing and the like.

Among the above plastic films, the cycloolefin polymer film is generally known to be vulnerable to lateral force such as tearing and to have poor folding resistance. On the other hand, in view of transparency and heat resistance, The use area thereof is widening. The cured coating film obtained from the curable composition of the present invention can effectively increase its flexibility and impact resistance even in such a fragile film. From the viewpoint of satisfactorily manifesting such effects, it is preferable that the thickness of the cured coating film is adjusted in the range of 1 to 10 mu m. Examples of the coating method include bar coater coating, Meyer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexo printing, screen printing and the like.

Examples of the active energy ray to be irradiated when the curable composition of the present invention is cured to form a coating film include ultraviolet rays and electron beams. In the case of curing by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED or the like is used as a light source, and the amount of light, In the case of using a high-pressure mercury lamp, it is preferable to cure the lamp 1 having a light amount in the range of 80 to 160 W / cm or so in a conveying speed of 5 to 50 m / min. On the other hand, in the case of curing by electron beams, it is preferable to cure the electron beam accelerating apparatus having an acceleration voltage in the range of 10 to 300 kV at a conveying speed of 5 to 50 m / min.

The substrate to which the curable composition of the present invention is applied can be used not only as a plastic film but also as a surface coating agent for various plastic molded articles such as cellular phones, household appliances, automobile bumpers and the like. In this case, examples of the method for forming the coating film include a coating method, a transfer method, and a sheet bonding method.

The coating method is a method in which the coating material is applied by spray coating or using a printing machine such as a curtain coater, a roll coater or a gravure coater as a topcoat, and then irradiated with active energy rays to cure the coating.

The laminated film of the present invention has a cured film or the like of the curable composition of the present invention and a plastic film layer and may have a functional film layer such as an antireflection film, a diffusion film and a polarizing film. These various layer constitutions may be formed by a method of directly applying the resin raw material and drying or curing, or may be formed by a method of joining together through an adhesive layer.

(Example)

Hereinafter, the present invention will be described in more detail with reference to specific production examples and examples, but the present invention is not limited to these examples. All parts and percentages are by mass unless otherwise stated.

In the present embodiment, the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permeation chromatograph (GPC).

Measuring device; HLC-8220 manufactured by Tosoh Corporation

column; Guard Column H _XL- H manufactured by Tosoh Corporation

      + TSKgel G5000HXL manufactured by Tosoh Corporation

      + TSKgel G4000HXL manufactured by Tosoh Corporation

      + TSKgel G3000HXL manufactured by Tosoh Corporation

      + TSKgel G2000HXL manufactured by Tosoh Corporation

Detector; RI (differential refractometer)

Data processing; SC-8010 manufactured by TOSOH CORPORATION

Measuring conditions; Column temperature 40 ° C

           Solvent tetrahydrofuran

           Flow rate 1.0 ml / min

Standard; polystyrene

sample; A tetrahydrofuran solution of 0.4 mass% in terms of the solid content of the resin was filtered with a microfilter (100 mu l)

The liquid chromatographic chart in this example was measured under the following conditions.

[Measuring conditions]

Device: Kabushiki Kaisha Shimazu Seisaku Joze "LCMS-2010EV"

Data processing: " LCMS Solution ", Shimazu Seisaku Joze Co.,

Column: "ODS-100V" (2.0 mm ID × 150 mm, 3 μm) manufactured by Tosoh Corporation 40 ° C.

Eluent: water / acetonitrile, 0.4 mL / min

Detector: PDA, MS

Sample preparation: 1. Dissolve 50 mg of the data in 10 ml of acetonitrile (LC)

     2. Stir with vortex for 30 seconds

     3. Politics for 30 minutes

     4. The sample was passed through a 0.2 mu m filter to obtain a measurement sample

Calculation of area ratio: Calculated at UV wavelength of 210 nm

Production Example 1 Preparation of dipentaerythritol polyacrylate (B1) crude product

300 g of acrylic acid, 180 g of dipentaerythritol, 15 g of sulfuric acid, 1.5 g of cupric chloride and 300 g of toluene were fed into a flask equipped with a thermometer, a stirrer and a condenser. The temperature was raised to 105 ° C while stirring, and the reaction was carried out at the same temperature for 12 hours while refluxing the system. The water produced was 68.5 g. 425 g of toluene was added to the reaction mixture, and the mixture was washed with 200 g of distilled water. Further, a 20% aqueous solution of sodium hydroxide was added to neutralize the reaction mixture, and the mixture was washed with 100 g of distilled water. After adding 500 ppm of hydroquinone monomethyl ether to the resin solid content, toluene was distilled off to obtain dipentaerythritol poly (meth) acrylate (B1). The hydroxyl value of the crude product of the dipentaerythritol polyacrylate (B1) was 88 mgKOH / g, the content of dipentaerythritol tetraacrylate (b1) calculated from the area ratio of the liquid chromatography chart was 7.2%, the dipentaerythritol penta The content of acrylate (b2) was 48.3%, the content of dipentaerythritol hexaacrylate (b3) was 30.7%, and the content of high molecular weight component (b ') was 13.8%. The hydroxyl value of the dipentaerythritol polyacrylate (B1) calculated from the content ratio of each component is 79.9 mgKOH / g.

Production Example 2 to 4 Production of crude product of dipentaerythritol polyacrylate (B2) to (B4)

A mixture of dipentaerythritol polyacrylate (B2) to (B4) was obtained in the same manner as in Production Example 1, except that the amount of acrylic acid and the reaction time were changed as shown in Table 1. The dipentaerythritol polyacrylate (B2) to (B4) dipentaerythritol polyacrylate (hereinafter referred to as "dipentaerythritol polyacrylate") calculated from the content of each component calculated from the area ratio of the liquid chromatography chart and the content ratio of each component Table 2 shows the hydroxyl value of each of B2 to B4.

Example 1 Preparation of urethane (meth) acrylate resin (1-1) composition

638 g of the crude product of dipentaerythritol polyacrylate (B1) obtained in Preparation Example 1, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added to a flask equipped with a thermometer, a stirrer and a condenser, . The flask was heated until the inner temperature of the flask became 50 캜, and 72.8 g of 1,3-bis (isocyanatomethyl) cyclohexane ("Takenate 600" manufactured by Mitsui Chemicals, Inc.) and a nylate-modified product of hexamethylene diisocyanate ("Banok DN-901S" manufactured by DIC Co., Ltd., content of isocyanate group: 23.5 mass%) was added thereto over a period of about 1 hour. After reacting at 80 占 폚 for 3 hours and confirming disappearance of isocyanate groups in the infrared absorption spectrum, the nonvolatile content was adjusted to 80 mass% using butyl acetate to obtain a urethane (meth) acrylate resin (1-1) composition . The acryloyl group equivalent of the urethane (meth) acrylate resin (1-1) calculated from the raw material charging ratio was 117 g / equivalent and the weight average molecular weight (Mw) was 4,100.

Example 2 Preparation of urethane (meth) acrylate resin (1-2) composition

To a flask equipped with a thermometer, a stirrer and a condenser, 524 g of the crude product of dipentaerythritol polyacrylate (B2) obtained in Production Example 2, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, . The flask was warmed to an internal temperature of 50 캜, and 97 g of 1,3-bis (isocyanatomethyl) cyclohexane ("Takenate 600" manufactured by Mitsui Chemicals, Inc.) was added thereto over a period of about 1 hour. After reacting at 80 DEG C for 3 hours and confirming disappearance of isocyanate groups in the infrared absorption spectrum, the nonvolatile component was adjusted to 80 mass% using butyl acetate to obtain a urethane (meth) acrylate resin (1-2) composition . The acryloyl group equivalent of the urethane (meth) acrylate resin (1-2) calculated from the raw material charging ratio was 118 g / equivalent and the weight average molecular weight (Mw) was 4,500.

Example 3 Preparation of urethane (meth) acrylate resin (1-3) composition

432 g of the crude product of dipentaerythritol polyacrylate (B3) obtained in Production Example 3, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added to a flask equipped with a thermometer, a stirrer and a condenser, . The flask was warmed to an internal temperature of 50 캜, and 97 g of 1,3-bis (isocyanatomethyl) cyclohexane ("Takenate 600" manufactured by Mitsui Chemicals, Inc.) was added thereto over a period of about 1 hour. After the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy at 80 ° C for 3 hours, the nonvolatile component was adjusted to 80 mass% using butyl acetate to obtain a urethane (meth) acrylate resin (1-3) composition . The acryloyl group equivalent of the urethane (meth) acrylate resin (1-3) calculated from the raw material addition ratio was 122 g / equivalent and the weight average molecular weight (Mw) was 8,000.

Example 4 Preparation of urethane (meth) acrylate resin (2-1) composition

638 g of the crude product of dipentaerythritol polyacrylate (B1) obtained in Preparation Example 1, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added to a flask equipped with a thermometer, a stirrer and a condenser, . The flask was heated until the internal temperature of the flask became 50 DEG C, and 131.2 g of 4,4-methylenedicyclohexyl-diisocyanate ("VESTANAT H12MDI" manufactured by Ebonic Degussa Japan Co., Ltd.) was added thereto over a period of about 1 hour. After the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy at 80 ° C for 3 hours, the nonvolatile component was adjusted to 80 mass% using butyl acetate to obtain a urethane (meth) acrylate resin (2-1) composition . The acryloyl group equivalent of the urethane (meth) acrylate resin (2-1) calculated from the raw material charging ratio was 120 g / equivalent and the weight average molecular weight (Mw) was 4,100.

Example 5 Preparation of urethane (meth) acrylate resin (2-2) composition

To a flask equipped with a thermometer, a stirrer and a condenser, 524 g of the crude product of dipentaerythritol polyacrylate (B2) obtained in Production Example 2, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, . The flask was heated until the inner temperature of the flask became 50 DEG C, and 90 g of tolylene diisocyanate was added thereto over a period of about 1 hour. After the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy at 80 ° C for 3 hours, the nonvolatile content was adjusted to 80 mass% using butyl acetate to obtain a urethane (meth) acrylate resin (2-2) composition . The acryloyl group equivalent of the urethane (meth) acrylate resin (2-2) calculated from the raw material charging ratio was 116 g / equivalent and the weight average molecular weight (Mw) was 4,700.

Example 6 Preparation of urethane (meth) acrylate resin (2-3) composition

432 g of the crude product of dipentaerythritol polyacrylate (B3) obtained in Production Example 2, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added to a flask equipped with a thermometer, a stirrer and a condenser, . The flask was heated until the internal temperature of the flask became 50 DEG C, and 131.2 g of 4,4-methylenedicyclohexyl-diisocyanate ("VESTANAT H12MDI" manufactured by Ebonic Degussa Japan Co., Ltd.) was added thereto over a period of about 1 hour. The reaction was carried out at 80 DEG C for 3 hours, and disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy. Then, nonvolatile component was adjusted to 80 mass% using butyl acetate to obtain a urethane (meth) acrylate resin (2-3) composition . The acryloyl group equivalent of the urethane (meth) acrylate resin (2-3) calculated from the raw material charging ratio was 130 g / equivalent and the weight average molecular weight (Mw) was 7,800.

Example 7 Preparation of urethane (meth) acrylate resin (3-1) composition

638 g of the crude product of dipentaerythritol polyacrylate (B1) obtained in Preparation Example 1, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added to a flask equipped with a thermometer, a stirrer and a condenser, . The flask was heated until the inner temperature of the flask became 50 DEG C, and 111 g of isophorone diisocyanate was added thereto over a period of about 1 hour. After the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy at 80 ° C for 3 hours, the nonvolatile component was adjusted to 80 mass% using butyl acetate to obtain a urethane (meth) acrylate resin (3-1) composition . The acryloyl group equivalent of the urethane (meth) acrylate resin (3-1) calculated from the raw material loading ratio was 117 g / equivalent and the weight average molecular weight (Mw) was 3,800.

Example 8 Preparation of urethane (meth) acrylate resin (3-2) composition

To a flask equipped with a thermometer, a stirrer and a condenser, 524 g of the crude product of dipentaerythritol polyacrylate (B2) obtained in Production Example 2, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added, . The flask was heated until the inner temperature of the flask became 50 DEG C, and 111 g of isophorone diisocyanate was added thereto over a period of about 1 hour. The reaction was carried out at 80 ° C for 3 hours, and disappearance of isocyanate groups was confirmed by infrared absorption spectroscopy. The content of nonvolatile components was adjusted to 80 mass% using butyl acetate to obtain a urethane (meth) acrylate resin (3-2) composition . The acryloyl group equivalent of the urethane (meth) acrylate resin (3-2) calculated from the raw material charging ratio was 116 g / equivalent and the weight average molecular weight (Mw) was 4,400.

Example 9 Preparation of urethane (meth) acrylate resin (3-3) composition

432 g of the crude product of dipentaerythritol polyacrylate (B3) obtained in Production Example 2, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added to a flask equipped with a thermometer, a stirrer and a condenser, . The flask was heated until the inner temperature of the flask became 50 DEG C, and 111 g of isophorone diisocyanate was added thereto over a period of about 1 hour. After the disappearance of the isocyanate group was confirmed by infrared absorption spectroscopy at 80 ° C for 3 hours, the urethane (meth) acrylate resin (3-3) composition was obtained by adjusting the nonvolatile content to 80 mass% using butyl acetate . The acryloyl group equivalent of the urethane (meth) acrylate resin (3-3) calculated from the raw material charging ratio was 126 g / equivalent and the weight average molecular weight (Mw) was 7,800.

Comparative Preparation Example 1 Preparation of urethane (meth) acrylate resin (1 ') composition

684 g of the crude product of dipentaerythritol polyacrylate (B4) obtained in Production Example 4, 0.2 g of dibutyltin dilaurate and 0.2 g of hydroquinone were added to a flask equipped with a thermometer, a stirrer and a condenser, . The flask was warmed to an internal temperature of 50 캜, and 84 g of hexamethylene diisocyanate (Dyuranate 50M-HDI, available from Asahi Chemical Co., Ltd.) was added thereto over a period of about 1 hour. The reaction was carried out at 80 占 폚 for 3 hours. The disappearance of the isocyanate group was confirmed in the infrared absorption spectrum, and then the nonvolatile content was adjusted to 80 mass% by using butyl acetate to obtain a urethane (meth) acrylate resin (1 ') composition. The acryloyl group equivalent and the weight average molecular weight (Mw) of the urethane (meth) acrylate resin (1 ') calculated from the raw material loading ratio were 112 g / equivalent and 3,700, respectively.

Examples 10 to 18 and Comparative Example 1

, 125 parts by mass of the urethane (meth) acrylate resin composition obtained in Examples 1 to 9 and Comparative Production Example, 4 parts by mass of a photoinitiator ("Irgacure # 184" manufactured by Chiba Specialty Chemicals Co., Ltd.) and 75 parts by mass of methyl ethyl ketone were mixed To obtain a curable composition. Various evaluation tests were carried out on the curable composition by the following methods. The results are shown in Tables 2 to 4.

Production of laminated film 1

The curable composition was coated on a 100 탆 thick PET film with a bar coater and dried at 80 캜 for 2 minutes. Subsequently, ultraviolet rays were irradiated at 300 mJ / cm 2 using a 80 W high-pressure mercury lamp in a nitrogen atmosphere to obtain a laminated film 1 having a cured coating film having a thickness of 5 탆 on a PET film.

Pencil hardness test

With respect to the laminated film 1, the pencil hardness of the cured coating film surface of the curable composition was measured under a load of 500 g in accordance with JIS K5600-5-4. Five measurements were made at one hardness and the hardness at which no scratches were measured four times or more was determined as the hardness of the hardened coating film.

Scratch resistance test

An indenter on a disk having a diameter of 2.4 cm was wrapped with 0.5 g of steel wool ("BONSTA # 0000" manufactured by Nihon Steel Wool Co., Ltd.), and a load of 500 g was applied to the indenter to make the surface of the cured coating film of the laminated film 1 200 reciprocating A wear test was conducted. The haze value of the coating film before and after the abrasion test was measured using an automatic haze computer ("HZ-2" manufactured by Suga Shikenki K.K.), and scratch resistance was evaluated by the value (dH) of the difference. The smaller the value of the difference, the higher the resistance to scratches.

Flexibility test

The laminated film 1 was wound around a test rod using a mandrel testing machine (TP Kikenshae flexure tester) to check whether or not a crack occurred, and the minimum diameter of the test rod which did not crack was evaluated . Test rods having diameters ranging from 2 mm to 6 mm were used in units of 1 mm.

Inner curl test

A coating film 5 cm square from the laminated film 1 was cut out to obtain a test piece. The four pieces of the test piece were measured for lifting from the horizontal and evaluated by the average value (mm). The smaller the value, the smaller the curl and the better the curl.

Impact resistance test

The test was conducted with reference to JIS K5600-5-3. Specifically, it is as follows.

[Device]

Chu: The jelly-containing steel ball (mass 300.0 ± 0.5g, diameter of 25.40㎜, grade 60) specified in JIS B 1501 "Steel Shaft"

Forced stand: A horizontal stand of 300 mm in length, 200 mm in width and 30 mm in thickness on a concrete floor.

[Operation]

1. The surface of the cured coating film of the laminated film 1 was fixed on the upper face of the forcing base.

2. A weight was hanged at a position where the distance from the surface of the laminated film 1 to the lower end of the weight was 50 mm, and it was confirmed whether the vibration or rotation stopped, and then dropped onto the laminated film 1.

3. The laminated film 1 after the drop test was allowed to stand in the room for 1 hour, and the damage in the drawing was examined.

4. The distance from the surface of the laminated film 1 to the lower end of the weight was dropped by 10 mm, and the test was continued to evaluate the maximum distance at which cracking and peeling of the cured coating film did not occur.

Adhesion test

The curable composition was coated on an acrylic film having a thickness of 60 mu m by a bar coater and dried at 80 DEG C for 2 minutes. Subsequently, ultraviolet rays were irradiated at 50 mJ / cm 2 using a 80 W high-pressure mercury lamp in a nitrogen atmosphere to obtain a laminated film 2 having a cured coating film having a thickness of 5 탆 on an acrylic film.

Slits were cut with a cutter knife on the surface of the cured coating film of the laminated film 2, and 100 pieces of base boards with a size of 1 mm x 1 mm were formed, and a cellophane adhesive tape was stuck thereon and then peeled rapidly , And the number of remaining base without peeling was counted and evaluated according to the following evaluation criteria.

A: More than 80 residues

B: More than 50 residues of the foundation tree

C: More than 30 residues in the base tree

D: The number of residues in the base tree is 29 or less

Claims (10)

A urethane (meth) acrylate resin having a polyisocyanate compound (A) having an aromatic ring or alicyclic structure in a molecule and dipentaerythritol (meth) acrylate (B) as essential reaction materials. The method according to claim 1,
Wherein the polyisocyanate compound (A) is represented by the following structural formulas (A1-1) to (A1-3)

(Wherein R ¹ is each independently an alkyl group of 1 to 4 carbon atoms and j is 0 or an integer of 1 to 4. R ² independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms One)
(A1) or a urethane (meth) acrylate resin as a modified polyisocyanate compound. The method according to claim 1,
Wherein the polyisocyanate compound (A) is represented by the following structural formula (A2-1) or (A2-2)

(Wherein l is an integer of 0 or 1 or more and m is 1 or 2. R ³ each independently represents an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, Methylene group, k is 0, 1 or 2, and n is 0 or an integer of 1 to 8,
A polyisocyanate compound (A2) represented by any one of the following formulas or a urethane (meth) acrylate resin as a modified polyisocyanate compound. The method of claim 3,
Wherein the polyisocyanate compound (A) has the following structural formulas (A2-3) to (A2-5)

(Wherein R ⁴ is independently an alkyl group having 1 to 4 carbon atoms, k is 0, 1 or 2, and n is 0 or an integer of 1 to 8)
(Meth) acrylate resin as a polyisocyanate compound. The method according to claim 1,
Wherein the polyisocyanate compound (A) is isophorone diisocyanate or a modified product thereof (A3) and the dipentaerythritol (meth) acrylate (B) is dipentaerythritol tetra (meth) (Meth) acrylate resin (b1) containing dipentaerythritol penta (meth) acrylate (b1) and dipentaerythritol penta (meth) acrylate . The method according to claim 1,
The urethane (meth) acrylate resin wherein the hydroxyl value of the dipentaerythritol (meth) acrylate (B) is in the range of 50 to 140 mgKOH / g. The method of claim 3,
The urethane (meth) acrylate resin wherein the dipentaerythritol (meth) acrylate (B) contains dipentaerythritol tetra (meth) acrylate (b1) and the content thereof is in the range of 1 to 30%. A curable composition comprising the urethane (meth) acrylate resin according to any one of claims 1 to 7 and a photopolymerization initiator. 9. A cured product of the curable composition according to claim 8. A laminated film having the layer comprising the cured product according to claim 9 and other plastic film layers.