JP2017171794A - Ultraviolet-curable coating agent composition and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-curable coating agent composition of a paper base material and a transparent film base material capable of forming a cured coating film having bending resistance, curability, impact resistance, abrasion resistance and fingerprint resistance.SOLUTION: An ultraviolet-curable coating agent composition which is used in a base material having a printing ink layer in at least a part thereof and does not use a solvent, and contains 20-70 wt.% of a trifunctional or more acrylate compound (A) having an addition mole number of alkylene oxide of 4-20, 0-45 wt.% of an urethane acrylate compound (B) being a reactant of an aliphatic and/or alicyclic diisocyanate compound (b1) and a compound (b2) having one hydroxyl group and two or more (meth)acrylate groups, 10-50 wt.% of a trifunctional or more acrylate compound (C) having no alkyleneoxy group in 100 wt.% of the total amount of an ultraviolet-curable compound in the coating agent composition and a benzophenone-based polymerization initiator (D).SELECTED DRAWING: None

Description

The present invention relates to an ultraviolet curable coating agent composition and a laminate obtained by coating and curing the composition on a paper substrate having a printing ink layer. More specifically, the present invention relates to an ultraviolet curable coating composition capable of forming a cured film having both friction resistance and post-processing appropriateness (resistance to cracking during bending, recoatability, and slipperiness).

Active energy ray curable coating varnish is practically almost solvent-free, and it can be cured by irradiation of active energy rays in a very short time without any heat drying process, making it useful for toys, paper containers, food packaging and cosmetics. Widely used in the field of packaging printing. Protects the printed surface by improving friction resistance, abrasion resistance, and blocking resistance, and at the same time gives gloss or matte feeling, and is applied to the printed matter for higher quality and cosmetics, but the package surface including the inclusion In some cases, scratches may occur due to friction between packages during product transportation or impact of collision, and scratches that impair the value of the product may occur depending on the shape and material of the package and the weight and hardness of the inclusion. However, if the crosslink density is increased to improve the friction resistance and wear resistance, the flexibility is lowered and the brittleness is made. Therefore, in the package application in which the active energy ray curable coating varnish application surface is creased, There is a problem that cracking tends to occur.

As the active energy ray-curable resin composition having excellent resistance to friction and cracking during bending, an active energy ray-curable compound having three or more (meth) acryloyl groups and a polyalkyleneoxy group, By adjusting a pentaerythritol derivative having 3 or more (meth) acryloyl groups and an active energy ray-curable compound having 6 or more (meth) acryloyl groups at a predetermined ratio, appropriate scratch resistance, Active energy ray-curable composition (Patent Document 1) capable of obtaining a cured coating film having flexibility, ratio of acryloyl group or methacryloyl group contained in resin composition, and predetermined ratio of compound having polyalkyleneoxy The resin composition which can adjust the resin hardened | cured material which has moderate hardness and a softness | flexibility by adjusting (patent document 2) (Meth) acrylate obtained by adding 1 to 20 moles of alkylene oxide having 2 to 4 carbon atoms to (meth) acrylate having one hydroxyl group and three or more (meth) acryloyl groups in the molecule, and polyisocyanate Active energy rays that have a self-healing property and a low cure shrinkage can be obtained by adjusting urethane (meth) acrylate obtained by reacting with polyfunctional (meth) acrylate at a predetermined ratio A curable composition (Patent Document 3) and the like have been proposed.

However, in the technique described in Patent Document 1, the bending resistance of the obtained coating film is not sufficiently flexible because the coating film is cracked when the mandrel diameter is about 3 mm in the evaluation by the cylindrical mandrel method. On the other hand, Patent Document 2 discloses a resin composition for producing an optical component that is capable of adjusting a fine concavo-convex structure having excellent hardness and pressure resistance and having flexibility. However, the friction resistance of the cured film is a load of about 100 g in a friction test using steel wool, and more excellent friction resistance is required. Furthermore, since the technology of Patent Document 3 has a high viscosity of urethane acrylate, it is difficult to reduce the viscosity so that it can be used in various printing machines without a solvent.

JP 2013-163765 A JP 2009-286953 A JP 2012-180487 A

Therefore, the present invention is an ultraviolet curable coating composition for paper substrates and transparent film substrates, which has excellent bending resistance and can form a cured coating film having curability, impact resistance, friction resistance and fingerprint resistance. The purpose is to provide.

As a result of intensive studies on the above problems, the present inventor has found that the problem can be solved by using the ultraviolet curable coating composition described below, and has reached the present invention.

The present invention is an ultraviolet curable coating composition that does not use a solvent and is used in a paper base material having a printing ink layer at least partially, and is characterized by the following (1) and (2): To do.
In the total amount of 100% by weight of the ultraviolet curable compound in the coating agent composition,
20 to 70% by weight of trifunctional or higher acrylate compound (A) having 4 to 20 added moles of alkylene oxide,
A urethane acrylate compound (B) which is a reaction product of an aliphatic and / or alicyclic diisocyanate compound (b1) and a compound (b2) having one hydroxyl group and two or more (meth) acrylate groups is converted to 0 to 45. weight%,
It contains 10 to 50% by weight of a trifunctional or higher functional acrylate compound (C) having no alkyleneoxy group.
(However, (A) and (C) exclude the case of (B).)
(2) Contains a benzophenone photopolymerization initiator (D).

Moreover, this invention is the said ultraviolet-ray whose glass transition temperature after hardening of acrylate compound (A) is -40-10 degreeC, and whose glass transition temperature after hardening of acrylate compound (C) is 100 degreeC or more. The present invention relates to a curable coating agent composition.

In the present invention, the acrylate compound (A) is an ethylene oxide and / or propylene oxide addition acrylate of at least one compound selected from the group consisting of pentaerythritol, dipentaerythritol, trimethylolpropane, and glycerin. The ultraviolet curable coating agent composition characterized by the above.

In addition, the present invention relates to the ultraviolet curable coating agent composition, wherein the acrylate compound (A) is trimethylolpropane ethylene oxide and / or propylene oxide addition acrylate.

In the present invention, the compound (b2) is selected from the group consisting of pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane di (meth) acrylate, and glyceryl di (meth) acrylate. The present invention relates to the ultraviolet curable coating composition, which is at least one selected.

The present invention further relates to the ultraviolet curable coating agent composition characterized by containing a hydrogenated oil (E).

The present invention further relates to the ultraviolet curable coating agent composition comprising resin fine particles (F) having an average particle size of 1.0 to 10.0 μm.

Moreover, this invention relates to the laminated body which has a coating layer formed from the said ultraviolet curable coating agent composition on the paper base material which has a printing ink layer in part at least.

It was possible to provide an ultraviolet curable coating composition that is excellent in bending resistance and can form a cured coating film having curability, impact resistance, friction resistance and fingerprint resistance.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. The content is not limited.

The present invention is an ultraviolet curable coating composition that does not use a solvent and is used in a paper base material having a printing ink layer at least partially, and is characterized by the following (1) and (2): To do.
In the total amount of 100% by weight of the ultraviolet curable compound in the coating agent composition,
20 to 70% by weight of trifunctional or higher acrylate compound (A) having 4 to 20 added moles of alkylene oxide,
A urethane acrylate compound (B) which is a reaction product of an aliphatic and / or alicyclic diisocyanate compound (b1) and a compound (b2) having one hydroxyl group and two or more (meth) acrylate groups is converted to 0 to 45. weight%,
It contains 10 to 50% by weight of a trifunctional or higher functional acrylate compound (C) having no alkyleneoxy group.
(However, (A) and (C) exclude the case of (B).)
(2) Contains a benzophenone photopolymerization initiator (D).

The ultraviolet curable coating agent composition of the present invention comprises the acrylate compound (A), the urethane acrylate compound (B) and the acrylate compound (C) as main components, and a benzophenone photopolymerization initiator (D) as an essential component. . In the cured coating film, the acrylate compound (A) is the flexibility of the coating film, the urethane acrylate compound (B) is the flexibility of the coating film, the acrylate compound (C) is the hardness of the cured coating film, and the total amount of the ultraviolet curable compound In 100% by weight, when (A) is 20 to 70% by weight, (B) is 0 to 45% by weight, and (C) is 10 to 50% by weight, bending resistance, impact resistance, and friction resistance are improved. Achieve. (A) / (B) / (C) is preferably 20 to 70% / 10 to 45% / 10 to 50% (% by weight), more preferably 30 to 60% / 20 to 45% / 15 to 45% (% by weight).

When the amount of (A) is less than 20% by weight in 100% by weight of the total amount of the UV curable compound, the cured coating film is too hard and the bending resistance is deteriorated. Sex is reduced. When the urethane acrylate compound (B) exceeds 45% by weight, the bending resistance and the friction resistance of the cured coating film cannot be compatible. When the acrylate compound (C) is less than 10% by weight, the friction resistance of the cured coating film decreases, and when it exceeds 50% by weight, the bending resistance of the cured coating film decreases. Moreover, when photoinitiators other than a benzophenone type photoinitiator (D) are used, sclerosis | hardenability and the abrasion resistance of a cured coating film are inferior.

The total of (A), (B), and (C) in 100% by weight of the total amount of the ultraviolet curable compound is not particularly limited as long as it can solve the problems of the present application, but is preferably 80% or more, more preferably 90%. % Or more.

In this specification, the glass transition temperature (hereinafter sometimes referred to as Tg) is an endothermic curve in the vicinity of the glass transition temperature when measured using a differential scanning calorimeter (DSC) at a temperature rising temperature of 10 ° C./min. Indicates the temperature at the midpoint of the tangent line.

<Acrylate compound (A)>
The acrylate compound (A) is a tri- or higher functional acrylate compound (A) having 4 to 20 added moles of alkylene oxide, and has a glass transition temperature of -40 ° C after being cured by irradiation with ultraviolet rays or electron beams. It is preferable that it is -10 degreeC. The alkyleneoxy group significantly reduces Tg after curing of the acrylate compound (A). When the Tg of the acrylate compound (A) is within the above range, the cured film made of the ultraviolet curable coating composition is excellent in flexibility, bending resistance, and friction resistance. The Tg of the acrylate compound (A) is more preferably -35 ° C to 0 ° C.

Examples of the alkyleneoxy group include an ethyleneoxy group, a propyleneoxy group, a trimethyleneoxy group, and a tetramethyleneoxy group, and these may be combined arbitrarily. An ethyleneoxy group or a propyleneoxy group is preferable, and the added mole number is preferably 6 to 15. Increasing the molecular weight of the acrylate compound (A) by increasing the number of added moles reduces the penetration of the ultraviolet curable coating agent composition into the paper substrate. Further, as will be described later, when the addition amount of alkylene oxide is within the above range, the curability and physical properties are specifically improved when the benzophenone photopolymerization initiator (D) is used.

In the present specification, the number of added moles refers to the number of moles of an alkylene oxide group added to one mole of the basic structure (penterythritol, trimethylolpropane, etc. described below). In addition trimethylolpropane triacrylate, 9 mol of ethylene oxide is added to 1 mol of trimethylolpropane. Therefore, since trimethylolpropane has three hydroxyl groups, when the three hydroxyl groups and ethylene oxide have the same reactivity, an ethyleneoxy group is added with an average addition number of 3 mol.

In the following description, (meth) acryl or (meth) acrylate means methacryl and acryl, methacrylate and acrylate, respectively.

Among the acrylate compounds (A), those having a glass transition temperature of −40 ° C. to 10 ° C.
Ethylene oxide-added trimethylolpropane tri (meth) acrylate (n = 6), ethylene oxide-added trimethylolpropane tri (meth) acrylate (n = 9), ethylene oxide-added trimethylolpropane tri (meth) acrylate (n = 15) , Ethylene oxide-added trimethylolpropane tri (meth) acrylate (n = 20),
Ethylene oxide-added pentaerythritol tri / tetra (meth) acrylate (n = 6), ethylene oxide-added pentaerythritol tri / tetra (meth) acrylate (n = 9), ethylene oxide-added pentaerythritol tri / tetra (Meth) acrylate (n = 15), ethylene oxide-added pentaerythritol tri / tetra (meth) acrylate (n = 20),
Ethylene oxide-added dipentaerythritol penta / hexa (meth) acrylate (n = 6), ethylene oxide-added dipentaerythritol penta / hexa (meth) acrylate (n = 9), ethylene oxide-added dipentaerythritol Penta / hexa (meth) acrylate (n = 15), ethylene oxide-added dipentaerythritol penta / hexa (meth) acrylate (n = 20),
Ethylene oxide-added glycerin tri (meth) acrylate (n = 6), ethylene oxide-added glycerin tri (meth) acrylate (n = 9), ethylene oxide-added glycerin tri (meth) acrylate (n = 12), ethylene oxide-added glycerin tri (Meth) acrylate (n = 18), ethylene oxide-added glycerin tri (meth) acrylate (n = 20),
Propylene oxide-added trimethylolpropane tri (meth) acrylate (n = 6), propylene oxide-added trimethylolpropane tri (meth) acrylate (n = 9), propylene oxide-added trimethylolpropane tri (meth) acrylate (n = 15) ,
Ethylene oxide-added isocyanuric acid tri (meth) acrylate (n = 6),
Propylene oxide-added pentaerythritol tetra (meth) acrylate (n = 9), propylene oxide-added dipentaerythritol hexa (meth) acrylate (n = 12),
Examples include propylene oxide-added pentaerythritol tetra (meth) acrylate (n = 4) and propoxylated dipentaerythritol hexa (meth) acrylate (n = 12).
In addition, “/” in the notation of the above compound means “or”, and parentheses indicate the added mole number of alkylene oxide contained in the compound. For example, “(n = 3)” means that the number of added moles of alkylene oxide contained in the compound is 3. Among them, those having a molecular weight of 500 to 2000 are preferable because penetration into the paper base material is suppressed. Among them, the basic structure is trimethylolpropane, pentaerythritol, dipentaerythritol, in terms of glass transition temperature and molecular weight. Glycerin-based, alkylene oxide is preferably ethylene oxide or propylene oxide, and ethylene oxide-added trimethylolpropane tri (meth) acrylate is most preferable.

<Urethane acrylate compound (B)>
The urethane acrylate compound (B) is a reaction product of an aliphatic and / or alicyclic diisocyanate compound (b1) and a compound (b2) having one hydroxyl group and two or more (meth) acrylate groups. The urethane acrylate compound (B) needs to have two or more (meth) acrylate groups in order to increase the crosslink density and increase the hardness, and at the same time flexibility must be imparted, so that urethane bonding groups are included in the structure. is necessary. Since diisocyanate compound (b1) is not aliphatic and / or alicyclic, that is, aromatic, there is a concern of yellowing, which is not preferable.

Examples of the aliphatic and / or alicyclic diisocyanate compound (b1) include, as aliphatic diisocyanates, butane-1,4-diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, isopropylene diisocyanate, ethylene diisocyanate, 2 2,4-trimethylhexamethylene diisocyanate, and the like.
As alicyclic diisocyanates, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, hydrogenated Examples include xylylene diisocyanate and hydrogenated m-tetramethyl xylylene diisocyanate.
Hexamethylene diisocyanate and isophorone diisocyanate are preferable, and they may be trimers and have an isocyanurate ring, or may be, for example, an adduct of trimethylolpropane.

Examples of the diisocyanate trimer having an isocyanurate ring include, for example, isocyanurate-modified isophorone diisocyanate (for example, Desmodur Z4470 manufactured by Sumika Bayer Urethane Co., Ltd.), isocyanurate-modified hexamethylene diisocyanate (for example, Sumika). Sumijour N3300 manufactured by Bayer Urethane Co., Ltd., Duranate TPA-100, MFX-90X manufactured by Asahi Kasei Kogyo Co., Ltd., and the adduct of trimethylolpropane are trimethylolpropane adduct hexamethylene diisocyanate (for example, Sumika Bayer). Sumijoule HT manufactured by Urethane Co., Ltd., and Duranate P-301-75E manufactured by Asahi Kasei Kogyo Co., Ltd.).

Examples of the compound (b2) having one hydroxyl group and two or more (meth) acrylate groups include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane di (meth) acrylate, glyceryl di (Meth) acrylate etc. are mentioned.
In addition, the product which can be industrially obtained as “pentaerythritol tri (meth) acrylate” may be a mixture of pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate. When such a mixture is used, pentaerythritol tetra (meth) acrylate does not react with the diisocyanate compound (b1) because it does not have a hydroxyl group, but pentaerythritol tetra (meth) acrylate is coated as an acrylate compound (C) described later. It may be included in the agent composition. The urethane acrylate compound (B) is preferably a reaction product of hydroxyl group / isocyanate group = 1 to 1.2, and preferably has no isocyanate group.

Examples of the method for producing the urethane acrylate compound (B) include an aliphatic and / or alicyclic diisocyanate compound (b1), a compound having one hydroxyl group and two or more (meth) acrylate groups (b2). Is reacted for 3 to 6 hours in an oxygen atmosphere in the presence of a polymerization terminator with isocyanate group: hydroxyl group = 1: 1. A weight average molecular weight preferable as the urethane acrylate compound (B) is 500 to 2,000.

<Acrylate compound (C)>
Since the acrylate compound (C) plays a role of imparting hardness in the ultraviolet curable coating composition of the present invention, it is necessary to have at least three acrylate groups in the molecule, and the glass transition after UV or electron beam curing. It is preferable that temperature is 100 degreeC or more. When Tg is 100 ° C. or higher, the friction resistance is excellent. Preferably it is 200 degreeC or more.

Examples of the acrylate compound (C) having a Tg of 100 ° C. or higher include, for example, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, and glyceryl tri (meth). Examples include acrylate, ditrimethylolpropane tetra (meth) acrylate, and diglyceryl tetra (meth) acrylate. Of these, pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

<Benzophenone-based photopolymerization initiator (D)>
The ultraviolet curable coating composition of the present invention essentially comprises a benzophenone photopolymerization initiator (D). The polymer is not particularly limited as long as it has a benzophenone structure and a radical is generated by hydrogen abstraction and the polymerization reaction proceeds. Preferred examples include benzophenone, 4-methylbenzophenone, and 4,4′-bis (dimethylamino). Benzophenone, 4,4′-bis (diethylamino) benzophenone, methyl-o-benzoylbenzoate, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3, Examples include 3-dimethyl-4-methoxybenzophenone. Of these, 4-methylbenzophenone is preferable.

The benzophenone photopolymerization initiator (D) is an initiator in which a radical is generated by hydrogen abstraction and a polymerization reaction proceeds. The acrylate compound (A) having an alkyleneoxy group and a benzophenone photopolymerization initiator (D ), The benzophenone photopolymerization initiator (D) extracts hydrogen derived from the alkyleneoxy group and proceeds with the curing reaction by ultraviolet irradiation, so the curing speed is improved compared to the case without the alkyleneoxy group. It is thought to do. This effect becomes more remarkable as the number of added alkyleneoxy groups increases. At the same time, the UV curable coating composition of the present invention has various physical properties such as bending resistance, friction resistance and impact resistance in the coating film after UV curing by using the benzophenone photopolymerization initiator (D). There is an effect of improving, and these effects cannot be obtained when other photopolymerization initiators are used. In addition, since a hardening rate becomes still faster by the combination with the amine photosensitizer mentioned later, it is still more preferable to use a benzophenone photopolymerization initiator (D) together with an amine photosensitizer.

The benzophenone photopolymerization initiator (D) is preferably contained in an amount of 1% to 20%, more preferably 5% to 15%, in 100% by weight of the ultraviolet curable coating agent composition.

In addition, the ultraviolet curable coating composition of the present invention may be used in combination with a photopolymerization initiator other than the benzophenone photopolymerization initiator (D) as necessary, as long as the above effects are not impaired.

Examples of the photopolymerization initiator include acetophenone photopolymerization initiators such as 4-phenoxydichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4 -Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl- [4- (Methylthio) phenyl] -2-morpholino-1-propanone, 2,2-dimethoxy-2-phenylacetophenone and the like.

Examples of the alkylphenone photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane. -1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2 -Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl]- - [4- (4-morpholinyl) phenyl] -1-butanone, and the like.

Examples of the benzoin photopolymerization initiator include benzoin, benzoin methyl ether, benzoin isoethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

As thioxanthone photopolymerization initiators, thioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropyl Examples include thioxanthone.

Examples of the anthraquinone photopolymerization initiator include α-acyloxime ester, benzyl, methylbenzoylformate (“Biacure 55”), 2-ethylanthraquinone, and the like.

Examples of acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (“Lucirin TPO”), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“IRGACURE819”) and the like. Is mentioned.

(Photosensitizer)
In the ultraviolet curable coating composition of the present invention, an amine photosensitizer is preferably used as a photosensitizer. The amine photosensitizer accelerates the hydrogen abstraction reaction of the benzophenone photopolymerization initiator (D) and improves the curing reaction rate. Specific examples of the amine photosensitizer include, for example, aliphatic amines such as trimethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, aniline, N-methylaniline, and N, N-dimethyl. Examples include aromatic amines such as aniline, amine-based (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and acryloylmorpholine, amine-based polyester acrylates, and amine-based acrylate oligomers. Of these, N-methyldiethanolamine is preferably used because of particularly good compatibility with the composition of the present invention and good photosensitization. The amine photosensitizer is preferably used in the range of 0.1 to 20% by weight, more preferably in the range of 1 to 5% by weight, in the total 100% by weight of the photocurable composition.

The ultraviolet curable coating composition of the present invention may contain a sensitizer other than the amine photosensitizer, for example, biphenyl, 1,4-dimethylnaphthalene, 9-fluorenone, fluorene, phenanthrene. , Triphenylene, anthracene, 9,10-diphenylanthracene, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, benzophenone, 4,4′- Dimethoxybenzophenone, acetophenone, 4-methoxyacetophenone, benzaldehyde and the like can be used.

<Hydrogenated oil (E)>
The ultraviolet curable coating composition in the present invention preferably contains a hydrogenated oil (E). The oil (E) has an effect of developing a fingerprint-resistant function by being applied to the coating film surface after being coated with a coating agent and UV-cured. Oils and fats that are hydrogenated are preferred because there are no double bonds derived from unsaturated fatty acids and they do not affect the crosslinking density of the coating composition. Fats and oils are different in fatty acid components depending on the plant or animal from which they are derived, but any of them may be used. Examples thereof include palm oil, soybean oil, tall oil, castor oil, and various other oils, and those modified with an ethyleneoxy group or a propyleneoxy group are also preferably used. From the compatibility with the mixture of an acrylate compound (A), a urethane acrylate compound (B), and an acrylate compound (C), hydrogenated palm oil and hydrogenated castor oil are preferable, and it is more preferable to use these in combination. As the hydrogenated castor oil, an ethylene oxide adduct is preferable.

<Resin fine particles (F)>
Moreover, it is preferable that the ultraviolet curable coating agent composition of this invention contains the resin fine particle (F) whose average particle diameter is 1.0-10.0 micrometers further. In addition, an average particle diameter shows the value of the integrated value 50% (D50) in the particle size distribution calculated | required by the laser diffraction / scattering method here. The resin fine particles (F) are mainly used for the purpose of imparting slipperiness, and prevent damage on the production line during the production of the laminate described later. Further, it has an effect of slightly roughening the surface of the cured film of the ultraviolet curable coating agent composition to prevent the reflection of a fluorescent lamp or the like, and an effect of intentionally giving glare and giving design.

The resin fine particles (F) may be of any resin type, for example, polyurethane resin type, polynylon resin type, polyacrylic resin type, polysilicone resin type, polystyrene resin type, melamine resin type, polyurethane acrylic resin type, polyester resin type. , Polyethylene resin and the like, and two or more of these may be used in combination. Among them, urethane type and acrylic type are preferable, and acrylic resin fine particles are most preferable. The addition amount of the resin fine particles (F) is preferably 0.05 to 5.0% by weight in 100% by weight of the ultraviolet curable coating agent composition.

(solvent)
The ultraviolet curable coating agent composition of the present invention preferably does not use an organic solvent and / or water as a solvent. The term “solvent” as used herein does not correspond to a very small amount of organic solvent or water derived from the raw material used, but means a solvent that is intentionally used for the purpose of dilution, viscosity reduction, or the like. By not using organic solvent, it contributes to environmental conservation by preventing scattering of organic solvent (low VOC) and power saving by reducing drying process.

In the ultraviolet curable coating composition of the present invention, when an organic solvent is unavoidably used, it is preferably used to the minimum as long as the coating performance and the printing / coating performance are not hindered. As the organic solvent that can be used, known organic solvents can be used, for example, alcohol solvents such as methanol, ethanol, and isopropanol, ester solvents such as ethyl acetate and propyl acetate, glycol ether solvents such as propylene glycol monomethyl ether, and acetone. And ketone solvents such as methyl ethyl ketone, aromatic solvents such as toluene and xylene, and mixtures thereof.

The preferred viscosity of the ultraviolet curable coating composition of the present invention is 50 to 3000 mPa · s / 25 ° C., more preferably 100 to 2000 mPa · s / 25 ° C. with a B-type viscometer. Viscosity suitable for coating with.

(Other acrylic monomers)
The ultraviolet curable coating agent composition of the present invention may contain other acrylate compounds as long as the effect is not impaired.

Examples of other acrylate compounds include acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and pentyl (meth) acrylate. Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic acid Examples include tetradecyl, hexadecyl (meth) acrylate, and octadecyl (meth) acrylate.

The acrylic monomer may have a hydroxyl group. Examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth). Such as 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, etc. ) Acrylic acid hydroxyalkyl ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, glycol mono (meth) acrylate such as 1,4-cyclohexanedimethanol mono (meth) acrylate, caprolactone modified (meth) Acrylate and hydroxyethyl acrylamide.

Other acrylic monomers containing amino groups include, for example, (meth) acryloylmorpholine, monomethylaminoethyl (meth) acrylate, monoethylaminoethyl (meth) acrylate, monomethylaminopropyl (meth) acrylate, ( And (meth) acrylic acid monoalkylamino esters such as (meth) acrylic acid monoethylaminopropyl.

Other acrylic monomers may have a polyether structure. For example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, ethoxypolyethylene glycol (meth) acrylate, methoxypolypropylene Examples include glycol (meth) acrylate, ethoxypolypropylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and phenoxypolypropylene glycol (meth) acrylate.

Other acrylic monomers may contain two acryloyl groups. For example, ethylene glycol di (meth) acrylate, hexamethylene glycol di (meth) acrylate, nonanediol di (meth) acrylate, decanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate , Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) Acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,6-hexanediol ethylene oxide modified di (meth) acrylate, glycerin di ( (Meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, hydroxypivalic acid modified neopentyl Glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified diacrylate, 2- (meth) acryloyloxyethyl acid phosphate diester, etc. It is.

The ultraviolet curable coating composition of the present invention can appropriately contain known additives as additives, for example, other than leveling agents, polymerization inhibitors, ultraviolet absorbers, light stabilizers, and amine photosensitizers. Sensitizers, curing agents, plasticizers, wetting agents, adhesion aids, antifoaming agents, antistatic agents, trapping agents, antiblocking agents, wax components, silica particles, resin particles, preservatives, etc. can be used. . Furthermore, oil, flame retardant, filler, stabilizer, reinforcing agent, matting agent, abrasive, organic fine particles, inorganic fine particles, polymer compounds (acrylic resin, polyester resin, polyurethane (urea) resin, vinyl chloride-acetic acid Vinyl copolymer resin, etc.).

As the leveling agent, a known general leveling agent can be used as long as it has a wettability imparting action to the base material of the coating liquid and a surface tension reducing action. For example, a silicone-modified resin, a fluorine-modified resin, An alkyl-modified resin or the like can be used.

Examples of the polymerization inhibitor include p-benzoquinone, naphthoquinone, tolquinone, 2,5-diphenyl-p-benzoquinone, hydroquinone, 2,5-di-t-butylhydroquinone, methylhydroquinone, hydroquinone monomethyl ether, mono-t- Examples thereof include butyl hydroquinone, pt-butyl catechol, and p-methoxyphenol.

As said ultraviolet absorber, metal oxide microparticles | fine-particles, such as titanium dioxide, zinc oxide, iron oxide, cerium oxide, thallium oxide, lead oxide, a zirconium oxide, can be used as an inorganic type ultraviolet absorber, for example. Examples of organic UV absorbers include benzotriazole UV absorbers, triazine UV absorbers, benzoxazine UV absorbers, salicylic acid ester UV absorbers, diphenylmethanone UV absorbers, and 2-cyanopropenoic acid. Ester UV absorber, Anthranilate UV absorber, Cinnamic acid derivative UV absorber, Camphor derivative UV absorber, Benzalmalonate derivative UV absorber, Resorcinol UV absorber, Oxalinide UV absorber In addition, a coumarin derivative-based ultraviolet absorber or the like can be used. Of these, benzotriazole-based ultraviolet absorbers are preferred.

Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-t-octylphenyl) -benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) -benzotriazole, 2, 2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6 [(2H-benzotriazol-2-yl) phenol]], 2- (2H-benzotriazol-2-yl) -4 -(1,1,3,3-tetramethylbutyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol, etc. Can do. Of these, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) -benzotriazole are particularly preferable.

Examples of the triazine ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4,6-tris- (Diisobutyl-4′-amino-benzalmalonate) -s-triazine, 4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine, 2- (2-hydroxy- 4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hi Proxy-4-dodecyloxy-phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like.

Examples of the diphenylmethanone UV absorber include diphenylmethanone, methyldiphenylmethanone, 4-hydroxydiphenylmethanone, 4-methoxydiphenylmethanone, 4-octoxydiphenylmethanone, 4-decyloxydiphenylmethanone. 4-dodecyloxydiphenylmethanone, 4-benzyloxydiphenylmethanone, 4,2 ′, 4′-trihydroxydiphenylmethanone, 2′-hydroxy-4,4′-dimethoxydiphenylmethanone, 4- (2 -Ethylhexyloxy) -2-hydroxy-diphenylmethanone, methyl o-benzoylbenzoate, benzoin ethyl ether and the like.

Examples of the 2-cyanopropenoic acid ester ultraviolet absorber include ethyl α-cyano-β, β-diphenylpropenoic acid ester, isooctyl α-cyano-β, β-diphenylpropenoic acid ester, and the like.

Examples of the salicylic acid ester UV absorber include isocetyl salicylate, octyl salicylate, glycolic salicylate, and phenyl salicylate.

Examples of the anthranilate ultraviolet absorber include menthyl anthranilate.

Cinnamic acid derivative-based ultraviolet absorbers include, for example, ethylhexyl methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate, diisopropylmethyl cinnamate, glyceryl-ethylhexanoate dimethoxycinnamate, methyl-α-carbomethoxycinnamate Methyl-α-cyano-β-methyl-p-methoxycinnamate and the like.

Examples of the camphor derivative ultraviolet absorber include benzylidene camphor, benzylidene camphor sulfonic acid, camphor benzalkonium methosulfate, terephthalylidene dicamphor sulfonic acid, polyacrylamide methyl benzylidene camphor, and the like.

Examples of the resorcinol-based ultraviolet absorber include dibenzoyl resorcinol, bis (4-tert-butylbenzoyl resorcinol), and the like.

Examples of the oxalinide ultraviolet absorber include 4,4′-di-octyloxyoxanilide, 2,2′-diethoxyoxyoxanilide, 2,2′-di-octyloxy-5,5′-. Di-tert-butyl oxanilide, 2,2'-di-dodecyloxy-5,5'-di-tert-butyl oxanilide, 2-ethoxy-2'-ethyl oxanilide, N, N'- Bis (3-dimethylaminopropyl) oxanilide, 2-ethoxy-5-tert-butyl-2'-ethoxy oxanilide, etc. are mentioned.

Examples of the coumarin derivative-based ultraviolet absorber include 7-hydroxycoumarin.

The light stabilizer captures radicals generated by photodegradation, for example, radical scavengers such as thiol-based, thioether-based, hindered amine-based compounds, and ultraviolet absorbers such as benzophenone-based and benzoate-based compounds, etc. These may be used alone or in combination of two or more. Especially, it is preferable to use a hindered amine type compound from a viewpoint which can improve compatibility and light stability more.

Examples of the hindered amine compound include cyclohexane and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro-1,3,5-triazine. Reaction product of 2-aminoethanol with reaction product (trade name: Tinuvin 152 (manufactured by BASF Corp.)), bis (2,2,6,6-tetramethyl-1- (octyloxy) decanoate -4-piperidinyl) ester (trade name: Tinuvin 123 (manufactured by BASF Corporation)), 1,1-dimethylethyl hydroperoxide and a reaction product of octane, hindered amine compounds having an amino ether group, N-acetyl- 3-Dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione (trade name: Hostav n3058 (manufactured by Clariant Japan Co., Ltd.)) and the like, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name: Sanol LS765 (BASF Japan Co., Ltd.) Product)), bis (1,2,2,6,6, -pentamethyl-4-piperidyl) {[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl} butyl malonate Name: Tinuvin (registered trademark) 144 (manufactured by BASF Japan Ltd.)), dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol polymer (trade name: Tinuvin ( Registered trademark) 622LD (manufactured by BASF Japan Ltd.)), Probandioic acid [{4-methoxyphenyl} Tylene] -bis (1,2,2,6,6-pentamethyl-4-piperidyl) ester (trade name: Hostavin (registered trademark) PR-31 (manufactured by Clariant Japan KK)) N-alkyl-based hindered amine compound Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, poly [{6- (1,1,3, 3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6 , 6-tetramethyl-4-piperidyl) imino}], 2,2′-thiobis (4-tert-octylphenolate) alkylamine nickel, dibutylamine, 1,3,5-triazi N, N-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine) N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine And the like. Among them, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl sebacate are preferable.

As the curing agent, polyisocyanate compounds typified by tolylene diisocyanate, adducts derived from hexamethylene diisocyanate, and nurate, polyfunctional epoxy compounds, melamine compounds, metal chelates, etc. should be used. Can do.

Moreover, the ultraviolet curable coating agent composition of the present invention may contain other additives in addition to those described above. Other additives include, for example, thixotropic agents, curing accelerators, tackifiers, heat stabilizers, fluorescent brighteners, foaming agents, thermoplastic resins, thermosetting resins, conductivity-imparting agents, and improved moisture permeability. Agent, water repellent, hollow foam, crystal water-containing compound, water absorbent, moisture absorbent, deodorant, foam stabilizer, antifungal agent, algaeproof agent, hydrolysis inhibitor, organic and inorganic water-soluble compounds, etc. Can be used.

As a method for producing the ultraviolet curable coating agent composition of the present invention, the acrylate compound (A), the urethane acrylate compound (B), the acrylate compound (C) and the benzophenone photopolymerization initiator (D) are stirred with a disper or the like. It can be produced by stirring for about 30 minutes to 3 hours. In the case where mixing is difficult and viscosity is likely to be nonuniform, a roller mill, a ball mill, a pebble mill, an attritor, a sand mill, or the like may be used.

When bubbles or unexpectedly coarse particles are included in the ultraviolet curable coating composition of the present invention, it is preferably removed by filtration or the like in order to reduce the quality of the printed matter. A conventionally well-known filter can be used.

<Laminated body>
The ultraviolet curable coating agent composition of the present invention is effectively used as a curable composition for forming a coating film which is a coating layer (topcoat layer) on various substrates having a printed layer. Alternatively, it is possible to obtain a laminate having excellent curability with little adhesion and cracking of the coating layer even when the base material is bent, adhesion to the printed layer, and friction resistance.

The production method of the laminate of the present invention is not particularly limited, but preferably, the printing ink composition is printed on a substrate, dried or ultraviolet-cured to form a printed layer, and the ultraviolet-curing type of the present invention is further formed thereon. The coating agent composition can be produced by printing and ultraviolet curing.

<Paper base material>
Paper is preferable as the substrate, and it is normal paper or corrugated cardboard. The film thickness is not particularly specified, but a film having a thickness of 0.2 mm to 1.0 mm can be used, and the printing surface may be corona-treated. The surface of the paper substrate may be vapor-deposited with a metal such as aluminum for the purpose of imparting design properties, and surface coating with an acrylic resin, urethane resin, polyester resin, polyolefin resin or other resin. Further, surface treatment such as corona treatment may be applied. Examples thereof include coated cardboard and mary coated paper, and the UV curable coating composition of the present invention is more suitable for the use of a paper substrate for improving physical properties such as folding resistance.

<Transparent plastic substrate>
The ultraviolet curable coating composition of the present invention may be used for a transparent plastic substrate. Examples of such a transparent plastic substrate include a primer-coated polypropylene, a polyethylene terephthalate substrate, and the like, and can be used in the same manner as the paper substrate.

<Printing ink composition>
Examples of the printing ink composition include a gravure ink composition, a flexographic ink composition, an ultraviolet curable flexographic ink composition, an offset ink composition, an ultraviolet curable offset ink composition, and other ink compositions. A printing ink composition may be used. In particular, when the ultraviolet curable offset ink composition and the ultraviolet curable flexographic ink composition are laminated with the ultraviolet curable coating agent composition of the present invention, the ultraviolet curing reaction also occurs between the layers, so that the adhesion is improved. Therefore, an ultraviolet curable offset ink composition and an ultraviolet curable flexographic ink composition are more preferable.

The gravure ink composition, flexographic ink composition or offset ink composition is composed of a pigment, a binder, an additive, a solvent, water, or the like. Examples of the binder include fiber materials such as nitrocellulose, cellulose acetate propionate, Chlorinated polypropylene, vinyl chloride-vinyl acetate copolymer, polyester, acrylic, polyurethane and acrylic urethane, polyamide, polybutyral, cyclized rubber, chlorinated rubber, rosin modified phenolic resin, alkyd Resin system etc. are mentioned, and these may be used together as appropriate.
The ultraviolet curable offset ink composition and the ultraviolet curable flexo ink composition include a urethane acrylate compound resin, diallyl phthalate (DAP) resin, other inert resin having no double bond, and the like, and further contains a monomer. Examples of the monomer include monofunctional (meth) acrylic monomers, polyfunctional (meth) acrylic monomers, and other monomers, and it is preferable to include a trifunctional or higher polyfunctional (meth) acrylic monomer.

There is no restriction | limiting in particular as a pigment used for a printing ink composition, The organic and inorganic pigment currently used for general ink, a coating material, a recording agent, etc. can be used together. Organic pigments include azo, phthalocyanine, anthraquinone, perylene, perinone, quinacridone, thioindigo, dioxazine, isoindolinone, quinophthalone, azomethine azo, dictopyrrolopyrrole, isoindoline, etc. These pigments are mentioned. Further, although not limited to the following examples, for example, carmine 6B, lake red C, permanent red 2B, disazo yellow, pyrazolone orange, carmine FB, chromophthal yellow, chromophthal red, phthalocyanine blue, phthalocyanine green, dioxazine violet Quinacridone magenta, quinacridone red, indanthrone blue, pyrimidine yellow, thioindigo Bordeaux, thioindigo magenta, perylene red, perinone orange, isoindolinone yellow, aniline black, diketopyrrolopyrrole red, daylight fluorescent pigment, etc. Can be mentioned.

Examples of the white inorganic pigment as the pigment in the printing ink composition include titanium oxide, zinc oxide, zinc sulfide, barium sulfate, calcium carbonate, chromium oxide, and silica. It is preferable to use titanium oxide for the pigment of the white ink in terms of coloring power, hiding power, chemical resistance, and weather resistance. From the viewpoint of printing performance, the titanium oxide is treated with silica and / or alumina and / or polyol. Those that have been subjected to are preferred.

Non-white inorganic pigments are not limited to the following examples, but include, for example, carbon black, aluminum powder, mica (mica), bronze powder, chrome vermillion, chrome lead, cadmium yellow, cadmium red, ultramarine, and bitumen. , Bengara, yellow iron oxide, iron black, titanium oxide, zinc oxide, etc., and aluminum is in the form of a powder or paste, but it is preferably used in the form of a paste from the viewpoint of handling and safety. Whether to use leafing is appropriately selected from the viewpoint of brightness and density.

In the production of the printing ink composition used in the present invention, known additives such as pigment derivatives, pigment dispersants, wetting agents, adhesion assistants, leveling agents, antifoaming agents, antistatic agents are used as necessary. , Trapping agents, antiblocking agents, wax components, silica particles, polymerization inhibitors, color separation inhibitors, and the like can be used.

<Lamination method>
As a printing method of the printing ink composition, a known method can be used. For example, a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, etc. are mentioned. The thickness of the ink layer is preferably 0.1 μm to 15 μm. If the thickness is less than 0.1 μm, ink coloring is insufficient, while if it exceeds 15 μm, the ink layer becomes brittle.
The printing ink composition may be any of an oil-based ink composition, a water-based ink composition, and an ultraviolet curable ink composition, and can be dried or ultraviolet-cured after printing to form a printed layer.

The coating method of the ultraviolet curable coating composition is not particularly limited, and examples thereof include spraying, showering, dipping, flow coating, gravure printing, flexographic printing, rolls, spins, dispensers, inkjet printing, screen printing, and the like. Such a wet coating method may be mentioned.

Examples of ultraviolet rays for curing the ultraviolet curable coating agent composition include far ultraviolet rays, ultraviolet rays, and near ultraviolet rays. On the other hand, it is also possible to use an electron beam or a proton beam. In this case, curing can be performed without using a photopolymerization initiator. Curing by is preferred.

As a method of curing by ultraviolet irradiation, using a high pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, an LED, etc. 30~5000mJ / cm ^2, may be preferably 100~1000mJ / cm ² irradiation. After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

The film thickness (film thickness after curing) when applying the ultraviolet curable coating composition is usually preferably 1 to 20 μm, particularly preferably 2 to 10 μm. Within this range, there is no inhibition of curing, the ultraviolet irradiation time can be shortened, and the productivity is good.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In the present invention, parts and% represent parts by weight and% by weight unless otherwise noted.
As the weight average molecular weight in the examples, GPC (gel permeation chromatography) “ShodexGPCSystem-21” manufactured by Showa Denko KK was used. GPC is liquid chromatography that separates and quantifies substances dissolved in a solvent based on the difference in molecular size. Tetrohydrofuran is used as a solvent, and the weight average molecular weight is determined in terms of polystyrene.

In this specification, the glass transition temperature of the cured film formed by the acrylate compound (A) and the acrylate compound (C) was measured using a differential scanning calorimeter (DSC) for the film after UV curing. The average particle diameter in the resin fine particles (F) is a particle diameter at an integrated value of 50% (D50) in the particle size distribution obtained by the laser diffraction / scattering method.

<Production of mixture of urethane acrylate compound (B) and acrylate compound (C)>
[Synthesis Example 1]
A flask equipped with a stirring blade, a thermometer, a reflux condenser, and a gas introduction tube was blown with air at a temperature of 90 ° C., 25.4 parts of hexamethylene diisocyanate (hereinafter referred to as “HDI”), and about pentaerythritol triacrylate A mixture of 45% by weight / pentaerythritol tetraacrylate about 55% by weight (trade name: “Aronix M303” manufactured by Toagosei Co., Ltd.) was reacted for 6 hours while stirring at 250 rpm. Note that NCO / OH in the mixture was 1/1. After confirming disappearance of the isocyanate group by IR spectrum, the mixture was cooled to room temperature to obtain a mixture of UA1 and pentaerythritol tetraacrylate. The compound UA1 which is a urethane acrylate compound (B): pentaerythritol tetraacrylate which is an acrylate compound (C) = 50: 50 (weight ratio), and the weight average molecular weight of UA1 was 800.

[Synthesis Examples 2 to 5]
A mixture of UA2 to UA5 and an acrylate compound (C) was obtained in the same manner as in Synthesis Example 1 with the raw materials and blending ratios (molar ratios) described in Table 1.
In Table 1,
"IPDI" represents isophorone diisocyanate,
“Isocyanurate-modified HDI” represents a compound in which hexamethylene diisocyanate is trimerized to form an isocyanurate ring,
"PET3A" represents pentaerythritol triacrylate, "PET4A" represents pentaerythritol tetraacrylate,
“DPPA” represents dipentaerythritol pentaacrylate, and “DPHA” represents dipentaerythritol hexaacrylate.
In Synthesis Examples 3 and 4, as in Synthesis Example 1, a mixture of about 45% by weight of pentaerythritol triacrylate / about 55% by weight of pentaerythritol tetraacrylate (trade name: “Aronix M303” manufactured by Toagosei Co., Ltd.) was used as a reaction. In Synthesis Example 2, a mixture of about 45% by weight of dipentaerythritol pentaacrylate / about 55% by weight of dipentaerythritol hexaacrylate (trade name: “Aronix M400” manufactured by Toagosei Co., Ltd.) was used for the reaction. A mixture of about 25% by weight of pentaerythritol triacrylate / 75% by weight of pentaerythritol tetraacrylate (trade name: “Aronix M452” manufactured by Toagosei Co., Ltd.) was used in the reaction.

(Example 1: Production of UV curable coating composition S1)
47 parts of oligomer (product name SR499, manufactured by Sartomer, Tg-8 ° C.) of ethylene oxide-added trimethylolpropane triacrylate (hereinafter referred to as “TMP-EO-TA”) having 6 moles added and urethane acrylate UA1: PET4A = 40 parts of a 1: 1 mixture, 10 parts of p-methylbenzophenone and 3 parts of N-methyldiethanolamine were mixed and stirred with a disper for 40 minutes to obtain an ultraviolet curable coating composition S1.

(Examples 2 to 19: Production of UV curable coating agent compositions S2 to S19)
Ultraviolet curable coating agent compositions S2 to S19 were obtained in the same manner as in Example 1 with the blending ratios of the raw materials shown in Table 2-1.

(Comparative Examples 1 to 11: Production of UV-curable coating agent compositions T1 to T11)
Ultraviolet curable coating agent compositions T1 to T11 were obtained in the same manner as in Example 1 with the blending ratios of the raw materials shown in Table 2-2.

The compounds described in Table 2-1 and Table 2-2 are as follows.
TMP-EO-TA (3 mol): 3 mol of ethylene oxide added tolmethylolpropane triacrylate, product name Miramer M3130, manufactured by MIWON, Tg 40 ° C.
TMP-EO-TA (9 mol): 9 mol of ethylene oxide added tolmethylolpropane triacrylate, product name SR499, manufactured by Sartomer, Tg-19 ° C
-TMP-EO-TA (15 mol): 15 mol of ethylene oxide added tolmethylolpropane triacrylate, product name SR502, manufactured by Sartomer, Tg-32 ° C
TMP-PO-TA (6 mol): Propylene oxide 6 mol addition tolmethylolpropane triacrylate, product name SR499, manufactured by Sartomer, Tg-2 ° C
Glycerin-PO-TA (5.5 mol): 5.5 mol propylene oxide addition glycerin triacrylate, product name CD9021, manufactured by Sartomer, Tg-11 ° C.
The Tg represents a catalog value.
Further, J-5P and J-7P manufactured by Negami Kogyo Co., Ltd. were used as acrylic fine particles having an average particle diameter of 3 μm and 6 μm. Further, MM-120T manufactured by Negami Kogyo Co., Ltd. was used as urethane fine particles having an average particle diameter of 3 μm.
Further, the hydrogenated castor oil EO modified product is a product obtained by adding hydrogenated castor oil with ethylene oxide, and EMALEX HC-30 manufactured by Nippon Emulsion Co., Ltd. was used.
As photopolymerization initiators other than the benzophenone photopolymerization initiator (D), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Irgacure 1173 manufactured by Ciba Japan), 1-hydroxy-cyclohexyl-phenyl -Ketone (Irgacure 184 manufactured by Ciba Japan) and 2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651 manufactured by Ciba Japan) were used.

(Example 20)
<Production of laminate>
In Example 1 on a paper base material pre-printed with UV offset ink (FD Carton X Black M: manufactured by Toyo Ink Co., Ltd., containing a trifunctional or higher polyfunctional (meth) acrylic monomer) on coated cardboard The obtained S1 was coated with a bar coater # 3 to a film thickness of 5.0 μm and cured under the condition of one 160 W / cm high-pressure mercury lamp, an irradiation distance of 10 cm and an integrated light quantity of 300 mj / cm ² . To obtain a laminate SS1. The UV offset ink was printed using a simple color developing machine RI tester, printed so that the film thickness of the FD Carton X ink M was 1.0 μm, one high-pressure mercury lamp, and an integrated light quantity of 100 mj / cm ^2. And cured.

(Examples 21 to 38)
By the same method as in Example 21, laminates SS2 to SS19 were obtained using the ultraviolet curable coating agent compositions S2 to S19 described in Table 2-1.

(Comparative Examples 12-22)
By the same method as Example 21, laminates TT1 to TT11 were obtained using ultraviolet curable coating agent compositions T1 to T11 described in Table 2-2.

<Examples 21 to 38 and Comparative Examples 12 to 22>
UV-curing coating agent compositions S1 to S19, T1 to T11 with a viscosity at 25 ° C. (using a B-type viscometer), laminates SS1 to SS19 (Examples), and laminates TT1 to TT11 (Comparative Examples) Curing speed (integrated light quantity), friction test, slip test, bending resistance test, etc. were conducted and are shown in Table 3-1 and Table 3-2.

<Viscosity at 25 ° C>
The viscosity at 25 ° C. of the ultraviolet curable coating agent compositions S1 to S19 and T1 to T11 was measured with a B-type viscometer. The determination criteria are as follows.
-A numerical value of 100-1500 mPa.s has no practical problem, and a numerical value of 200-700 mPa.s is preferably low viscosity.
-If the viscosity is less than 100 mPa · s, bleeding into the paper substrate may occur, which is not preferable.
-When viscosity exceeds 1500 mPa * s, since viscosity is too high, coating is difficult.

<Curing property>
The UV curable coating agent compositions S1 to S19 and T1 to T11 were coated on a glass plate with an applicator to a film thickness of 250 μm, and only the integrated light quantity (mj / cm ² ) was changed under the same conditions as in Example 21. After curing, the film surface was strongly pressed with a nail, and the integrated light amount when no trace remained was determined. In the practical range, the integrated light quantity is 200 mj / cm ² or less.

<Friction resistance test>
The laminates SS1 to SS19 (Examples) and the laminates TT1 to TT11 (Comparative Examples) were set in a Gakushin tester and applied to each other (face-to-face coating) or using steel wool No. 0000, load 800g Swayed 10 times. About the taken-out coating material, the degree of damage | wound was judged visually by the following five steps.
○ ・ ・ ・ ・ ・ ・ No scratches at all.
○ △ …… Slightly scratched.
Δ ··························· Although there are scratches, the substrate is not visible.
Δ × ············································· Parts are peeled off
× ·····························································································
○ and ○ △ are ranges where there is no practical problem.

<Slipperiness>
The laminates SS1 to SS19 (Examples) and the laminates TT1 to TT11 (Comparative Examples) were tested with a slip angle measuring machine.
○ The slip angle is 20 ° or less.
○ Δ ······· Slip angle is 20 to 25 °.
Δ: Slip angle is 25 to 30 °.
Δ × ··· Slip angle is 30 to 35 °.
X: The slip angle is 35 ° or more.
○ and ○ △ are ranges where there is no practical problem.

<Fingerprint resistance test>
A fingerprint resistance test was performed on the laminates SS1 to SS19 (Examples) and the laminates TT1 to TT11 (Comparative Examples). The contact area of the finger and the sample: 1 to 2 cm ^2, the force pushing the sample with a finger: evaluated at about 3.0 × ¹⁰ 3 Pa, were evaluated fingerprint resistance.
○ ··········· No fingerprints.
○ △ …… ・ Fingerprint remains 5% or less.
Δ: 5-30% of fingerprints remain.
△ × …… ・ 30 to 60% of fingerprints remain.
× ············· More than 60% of fingerprints remain.
○ and ○ △ are ranges where there is no practical problem.

<Bending resistance>
Regarding the laminated bodies SS1 to SS19 (Examples) and the laminated bodies TT1 to TT11 (Comparative Examples) (integrated light amount 300 mj / cm ² ), bend back 180 ° toward the non-coated surface, and further bend 180 ° at the same site in the coated surface direction. The fold line portion was visually evaluated.
○ ・ ・ ・ ・ ・ Break at the fold line and no whitening.
○ △ ・ ・ ・ ・ Fracture of the fold line part is less than 20% and slightly whitened.
Δ ······················· 20 to 60% of cracks in the fold line part, all whitened.
Δ × ······· 60 to 80% of cracks in the fold line portion, all whitened.
× ··········· A range where there is no practical problem in the circles where the bend line portion is 100% cracked and the pieces fall off.

From the evaluation results, it is an ultraviolet curable coating agent composition for forming a coating layer for protecting a substrate having a printing layer on at least a part of the surface, and the added mole number of alkylene oxide is 4 to 20. 20 to 70% by weight of a tri- or higher functional acrylate compound (A), an aliphatic and / or alicyclic diisocyanate compound (b1), a compound having one hydroxyl group and two or more (meth) acrylate groups (b2) 0-45% by weight of a urethane acrylate compound (B), which is a reaction product with), and 10-50% by weight of a tri- or higher functional acrylate compound (C) having no alkyleneoxy group, and starting benzophenone photopolymerization The UV curable coating composition containing the agent (D) has an appropriate viscosity, and the cured film has bending resistance, friction resistance, fingerprint resistance, and gloss. It has been found that is.

Claims (8)

An ultraviolet curable coating composition that does not use a solvent and is used in a substrate having a printing ink layer at least partially, and is characterized by the following (1) and (2).
(1) 100% by weight of the total amount of the ultraviolet curable compound in the coating composition,
20 to 70% by weight of trifunctional or higher acrylate compound (A) having 4 to 20 added moles of alkylene oxide,
A urethane acrylate compound (B) which is a reaction product of an aliphatic and / or alicyclic diisocyanate compound (b1) and a compound (b2) having one hydroxyl group and two or more (meth) acrylate groups is converted to 0 to 45. weight%,
It contains 10 to 50% by weight of a trifunctional or higher functional acrylate compound (C) having no alkyleneoxy group.
(However, (A) and (C) exclude the case of (B).)
(2) Contains a benzophenone photopolymerization initiator (D). The ultraviolet curable type of Claim 1 whose glass transition temperature after hardening of an acrylate compound (A) is -40-10 degreeC, and whose glass transition temperature after hardening of an acrylate compound (C) is 100 degreeC or more. Coating agent composition. The acrylate compound (A) is an ethylene oxide and / or propylene oxide addition acrylate of at least one compound selected from the group consisting of pentaerythritol, dipentaerythritol, trimethylolpropane, and glycerin. 3. The ultraviolet curable coating composition according to 1 or 2. The ultraviolet curable coating composition according to any one of claims 1 to 3, wherein the acrylate compound (A) is an ethylene oxide and / or propylene oxide addition acrylate of trimethylolpropane. The compound (b2) is at least one selected from the group consisting of pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane di (meth) acrylate, and glyceryl di (meth) acrylate. The ultraviolet curable coating agent composition according to any one of claims 1 to 4, wherein the composition is an ultraviolet curable coating agent composition. Furthermore, hydrogenated fats and oils (E) are contained, The ultraviolet curable coating agent composition in any one of Claims 1-5 characterized by the above-mentioned. The ultraviolet curable coating composition according to any one of claims 1 to 6, further comprising resin fine particles (F) having an average particle size of 1.0 to 10.0 µm. The laminated body which has the coating layer formed from the ultraviolet curable coating agent composition in any one of Claims 1-7 on the base material which has a printing ink layer in part at least.