JP2000297218A - Electron radiation curing resin composition and composite sheet material produced by using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electron radiation curing resin composition giving a composite sheet material having excellent slipperiness and antiblocking property and high gloss by including a specific di(meth)acrylate oligomer in an electron radiation curing organic compound at a specific ratio. SOLUTION: The objective composition is produced by mixing 100 pts.wt. of an electron radiation curing organic compound with 10-90 pts.wt. of a di(meth) acrylate oligomer having a molecular weight of 450-5,000 and containing one or more >=8C straight-chain alkyl side chain structures (S-R) expressed by the formula [R is an >=8C straight-chain alkyl; S is a spacer unit; J is a bonding unit connecting one or more (meth)acryloyl-containing structures, a main chain skeleton and the straight-chain alkyl side chain structure (S-R)]. The oligomer can be produced by reacting a monomer or polymer constituting the main chain skeleton with a side chain unit precursor compound containing the group of the formula and a compound having (meth)acryloyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an electron beam-curable resin composition and a sheet-like composite material using the same.
More specifically, the present invention relates to an electron beam-curable resin composition that provides an electron beam-curable resin having a low surface energy, and a sheet-like composite material coated with the same and having high gloss with excellent slipperiness and blocking resistance. .

[0002]

2. Description of the Related Art Conventionally, gloss coated paper called cast coated paper has a coating layer mainly composed of a pigment and an adhesive,
While it is in a plastic state containing water, it is pressed against the heated mirror surface and provided with a high gloss coating layer formed by drying and finishing, but the glossiness as a high gloss coating paper is What is not satisfactory and has higher glossiness is desired.

In order to solve this problem, a molten resin is laminated on a sheet-like support in the form of a film, and the molten resin is pressed against a smooth and high-gloss metallic cylindrical rotating body, cooled, and cooled. A coating composition containing an electron beam-curable organic compound as a main component instead of a so-called laminate coating method in which a strong glossy coating layer is formed by peeling from a cylindrical rotary member, or a molten resin in the above-mentioned laminate coating method. A cast electron beam irradiation method in which a coating liquid layer formed from the following (hereinafter referred to as an electron beam curable resin composition) is pressed against a molding surface or a metal cylindrical rotating body and irradiated with an electron beam to be cured. Thus, a sheet-like composite material having high glossiness can be obtained by these methods.

[0004] However, the sheet-like composite material (hereinafter referred to as EB sheet material) produced by the cast electron beam irradiation method as described above has a high smoothness, so that the back surface of the sheet-like support is not easily formed. Because of the high frictional resistance and poor slipperiness, for example, when performing printing or other processing using this EB sheet material, when using an automatic paper feeder or automatic folding machine, Workability such as jamming and blocking when stacking and storing has been a problem. The same applies to the case where the surfaces of the electron beam curable resin coating layers are directly in contact with each other.Since the smoothness is high, a phenomenon such as vacuum adhesion occurs, and when the frictional resistance increases, the phenomenon causes sticking. Also, once pasted, they may not be able to be easily separated and released.
This makes it difficult to develop sheet materials for various applications such as book covering, in which the cured resin layers are in direct contact with each other, packaging materials such as bags and boxes, and printing materials other than flat materials such as posters and calendars. It was one of the big factors.

Conventionally, in order to solve the above-mentioned problems, a method using a resin composition containing a silicone resin or a fluororesin has been disclosed in JP-A-63-9580 and JP-A-5-5189.
No. 7 and the like.
JP-A-1030, JP-A-8-283529, JP-A-9-21093, JP-A-9-208885 and JP-A-9-309905 disclose electron beam-curable resin compositions having a side chain. Or a coating material or a surface protection material using a thermosetting resin composition, etc., are disclosed, but simply diverting those materials,
It has not been possible to achieve the object of improving the slipperiness and blocking resistance of the EB sheet material while satisfying the required physical properties.

As a prior art in another field having a certain common point with the configuration of the present invention, for example, ED Jorda
n, Jr., J. Poly.Sci., 10, 3347 (1972), NAPalate
et al., J. Poly.Sci .: Macromol. Rev., 8, 117 (197
4), PL Magagnini et al., Macromolecules, 13, 12
(1980) and the like, JP-A-8-258038, JP-A-9-251272, JP-A-9-251273, and the like. Not only do they differ in many aspects, such as the composition, composition ratio, and method of producing a cured resin, but they also have different problems and objectives. Furthermore, neither the specification nor the teaching of the technical content of the present invention is disclosed in those specifications.

On the other hand, in order to solve the same problem in the conventional glossy coated paper, a press coating method in which a clear lacquer-like paint is applied to the surface of a semi-finished product which has been subjected to printing or other processing, and dried, It has been proposed to provide a protective layer by the above-mentioned laminate coating method, but in these methods, since a step of further processing the semi-finished product is added, not only the work becomes complicated, but also the work schedule until the product is delivered. In addition to the extra requirement, the yield is reduced, and the quality such as glossiness and aesthetics is not sufficiently satisfactory.

As described above, the above-mentioned existing technology satisfies various physical properties such as high smoothness and gloss, and at the same time, reduces the frictional resistance between the cured resin film layer covering the EB sheet material and the back surface of the support. Reduce, prevent double feed and blocking,
It provides a sufficient solution to the problem of manufacturing EB sheet materials that can withstand practical use without lowering workability and without sticking even when the cured resin film layers are in direct contact with each other. At present, no proposal has been made for a fundamental solution.

[0009]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and improves the slipperiness between an electron beam-cured resin-coated surface and the back surface of a sheet-like support, thereby enabling an automatic paper feeder and the like. Reduce double feeding and jamming in automatic folding machines, etc.
Furthermore, not only when the electron beam-cured resin-coated surface and the back surface of the sheet-shaped support are laminated and brought into contact with each other, but also when the electron-beam-cured resin-coated surfaces are laminated and brought into contact with each other, they have high gloss without blocking. It is intended to provide a sheet-like composite material.

[0010]

Means for Solving the Problems As a result of earnest studies, the present inventors have found that a specific linear alkyl side is contained in an electron beam-curable resin coating composition for forming an electron beam-curable resin coating layer. It has been found that the above problems can be solved by adding a di (meth) acrylate oligomer having a molecular weight of 450 to 5,000 having a chain, and production of a sheet-like composite material having high luster excellent in slipperiness and blocking resistance. The inventors have found that the present invention is possible, and have completed the present invention.

That is, the electron beam-curable resin composition according to the present invention comprises a linear alkyl having at least 8 carbon atoms represented by the following general formula (1) per 100 parts by weight of the electron beam-curable organic compound. It is characterized by containing 10 to 90 parts by weight of a di (meth) acrylate oligomer having at least one side chain structure (-SR) and a molecular weight of 450 to 5000.

Embedded image [Wherein R is a linear alkyl group having at least 8 carbon atoms, S is a spacer unit, and J is at least one (meth) acryloyl group-containing structure, a main chain skeleton, and a linear alkyl group. It represents a binding unit that connects the side chain structure (-SR). ]

[0012] In the electron beam-curable resin composition, the contact angle of water on the surface of a cured product obtained by irradiating an electron beam is preferably 70 ° or more.

[0013] The sheet-like composite material according to the present invention is characterized by comprising a sheet-like support and an electron beam-curable resin coating layer of the electron beam-curable resin composition formed on at least one surface thereof. Things.

Further, in the sheet-like composite material, the contact angle of water on the surface of the electron beam-curable resin coating layer is preferably 70 ° or more, and the surface of the electron beam-curable resin coating layer is based on JIS K7125. The coefficient of static friction is preferably 0.7 or less.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION A sheet-like composite material according to the present invention has a linear alkyl side chain structure (—SR) having at least 8 carbon atoms represented by the following general formula (1).
Having a molecular weight of 450 to 500 having at least one
An electron beam curable resin composition containing 0, preferably 650 to 3000 di (meth) acrylate oligomer is used.

Embedded image [Wherein R is a linear alkyl group having at least 8 carbon atoms, S is a spacer unit, and J is at least one (meth) acryloyl group-containing structure, a main chain skeleton, and a linear alkyl group. It represents a binding unit that connects the side chain structure (-SR). ]

In the formula (1), the bonding unit J is composed of a main chain skeleton and a linear alkyl side chain structure (-S
-R), and an organic structure capable of forming a structure capable of bonding to one or more atoms or molecules, and is preferably an aliphatic or aromatic hydrocarbon, an amide group, or the like;
More preferably, it is an aliphatic hydrocarbon unit represented by the following general formula (2). Here, m and n in the formula are each independently an integer of 0 to 2.

Embedded image

In the general formula (1), the spacer unit represented by S is an organic structure capable of connecting a main chain skeleton portion and a linear alkyl side chain R via a bonding unit J. And preferably one selected from an oxygen atom, a methylene group, a carbonyl group, an oxycarbonyl group, an oxycarbamoyl group and an aminocarbonyl group, and more preferably an oxygen atom, an oxycarbonyl group, an oxycarbamoyl group and an aminocarbonyl group 1 selected from
Is a seed.

Further, in the general formula (1), the linear alkyl group represented by R preferably has 8 to 50 carbon atoms, more preferably 12 to 30 carbon atoms, and particularly preferably 14 to 30 carbon atoms.
~ 22.

The electron beam-curable di (meth) acrylate oligomer having a linear alkyl side chain structure used in the present invention is represented by the following formula (1): Obtained by reacting a side chain unit precursor compound containing a linear alkyl group and a compound having a (meth) acryloyl group.

That is, the di (meth) acrylate oligomer having a linear alkyl side chain structure used in the present invention can be synthesized by a known method. Alternatively, after reacting the polymer with a precursor compound forming a joint represented by J in the general formula (1), a unit (-SR) containing a linear alkyl group is introduced, and further, This is reacted with hydroxy (meth) acrylate, or reacted with hydroxy (meth) acrylate on the reaction product of a monomer or polymer serving as a main chain skeleton and a precursor serving as a joint (J). And a unit (-SR) containing a linear alkyl group.

The compound used for introducing the linear alkyl side chain R into the di (meth) acrylate oligomer having a linear alkyl side chain structure of the present invention has 8 carbon atoms.
As long as the compound has from 50 to 50 linear alkyl groups,
There is no particular limitation, for example, octanoic acid (C ₈ ), nonanoic acid (C ₉ ), decanoic acid (C ₁₀ ), lauric acid (C ₁₂ ), tridecanoic acid (C ₁₃ ), myristic acid (C ₁₄ ), palmitic acid (C ₁₆ ), stearic acid (C ₁₈ ), behenic acid (C
₂₂ ) and the like, and their ester derivatives, acid chloride derivatives, alcohol derivatives obtained by reducing them, isocyanate derivatives thereof, and the like, preferably lauric acid (C ₁₂ ), tridecanoic acid (C _13), myristic acid (C _14), palmitic acid (C _16), stearic acid (C _18), behenic acid (C ₂₂₎
And the like, carboxylic acids thereof, acid chloride derivatives thereof, alcohol derivatives obtained by reducing them, and isocyanate derivatives thereof.

The main chain of the di (meth) acrylate oligomer having a linear alkyl side chain structure of the present invention, which is used for synthesizing the di (meth) acrylate oligomer having a linear alkyl side chain structure of the present invention. Monomer or polymer forming case part, and hydroxy (meth)
There is no particular limitation on the type of acrylate.

A monomer or a monomer which forms the main chain skeleton of the di (meth) acrylate oligomer of the present invention, which is used for synthesizing the di (meth) acrylate oligomer having a linear alkyl side chain structure of the present invention. Examples of the polymer include (1) a linear or side chain molecular weight of 50 to 300.
(2) Structure-containing organic compound of a reaction product of alkyl diol having a molecular weight of 30 to 300 and hydrogenated castor oil (3) Dimer acid structure-containing organic compound derived from a dimer of unsaturated higher fatty acid Compound (4) Organic compound having a polyether structure having a molecular weight of 100 to 3000 (5) Organic compound having a polyester structure having a molecular weight of 100 to 3000 can be exemplified.

It is necessary to react these organic compounds with a precursor compound which will later become the joint J in the general formula (1), and the molecular ends thereof are hydroxyl group, amino group, carboxylic acid group or thiol group. It is preferably substituted with a functional group such as, for example, and more preferably substituted with a hydroxyl group or a carboxylic acid group.

The above-mentioned molecular weight having a linear or side chain of 5
As the alkyl structure-containing organic compound of 0 to 3000,
Low molecular weight alkane diols and dicarboxylic acids, polyolefin diols and carboxylic acids, the dimer acid structure-containing organic compound derived from the unsaturated higher fatty acid dimer, dimer acid, or hydrogenated dimer acid diol and A dicarboxylic acid having a molecular weight of 100 to 30;
The organic compound having a polyether structure of No. 00 is a polyether diol, and has a molecular weight of 100 to 3
As the organic compound having a polyester structure of 000, polyester diols are preferable.

More specifically, the low molecular weight alkane diol or dicarboxylic acid or the polyolefin diol or carboxylic acid has a molecular weight of 50 to 50.
There is no particular limitation as long as it is in the range of 3000. Examples of the diol of the low molecular weight alkane include ethylene glycol, propylene glycol, tetramethylene glycol, butylene glycol, isobutylene glycol, hexanediol, octanediol, decanediol,
Dodecane diol, tetradecane diol, hexadecane diol, octadecane diol, eicosane diol, and the like can be given. Examples of the polyolefin diol include polyethylene diol, polypropylene diol, polybutadiene diol, hydrogenated polybutadiene diol, and polyisoprene. And the like. The dicarboxylic acids corresponding to these low molecular weight alkanediols or polyolefin diols can be mentioned as examples of the low molecular weight alkane dicarboxylic acid and the polyolefin dicarboxylic acid.

The polyether diol includes:
If its molecular weight is in the range of 100-3000,
Although not particularly limited, for example, polyethylene glycol,
1,2-polypropylene glycol, 1,3-polypropylene glycol, polytetramethylene glycol,
Examples thereof include 1,2-polybutylene glycol, polyisobutylene glycol, and polytetrahydrofuran diol, and diols of blocks and random copolymers of the polyether diol compound and other compounds.

The polyester diol is not particularly limited as long as its molecular weight is in the range of 100 to 3000. For example, 1,2-propanediol, 1,3-butanediol, 1,4- Butanediol, 1,5-pentanediol, neopentyl glycol, isoprene glycol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, hexylene glycol, Aliphatic diols such as 2,5-dimethyl-2,5-hexanediol, catechol, resorcin, hydroquinone, 4-t-butylcatechol, 2-t-butylcatechol, 1,4-dihydroxynaphthalene, p-hydroxyphenethyl Alcohol, bisphenol A, bisphenol F, bisph Aromatic diols such as Nord S, and hydrogenated bisphenol A, hydrogenated bisphenol F, and cycloaliphatic diols such as hydrogenated bisphenol S, oxalic acid, malonic acid, succinic acid, glutaric acid,
Polyester diols synthesized from aliphatic dicarboxylic acids such as adipic acid, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, or dicarboxylic acid compounds such as alicyclic dicarboxylic acids such as hydrogenated phthalic acid Alternatively, a block copolymer and a random copolymer of the polyester diol having a molecular weight in the range of 100 to 3000 and another compound are preferably used.

The hydroxy (meth) acrylate used in the synthesis of the di (meth) acrylate having a linear alkyl side chain structure of the present invention includes, for example, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. are mentioned, and among these, 2-hydroxyethyl (meth) acrylate is preferable.

The di (meth) acrylate oligomer having a specific linear alkyl group in the side chain of the present invention has a molecular weight of 450 to 5000, preferably 650 to 30.
00. If the molecular weight is less than 450, the coating film cured by electron beam irradiation becomes extremely poor in flexibility, easily cracks the coating film surface even when slightly bent, as a sheet material of the present invention If the value exceeds 5,000, the viscosity becomes extremely high, the fluidity becomes poor, and it becomes difficult to handle and coat the sheet-like support. Alternatively, the coating film cured by electron beam irradiation may have a sticky feeling due to poor curing, and may not be usable as the sheet-like composite material according to the present invention.

As described above, the di (meth) acrylate having a linear alkyl side chain structure of the present invention has a side chain unit containing a linear alkyl group, as long as it has a urethane-modified, ester-modified or epoxy-modified side chain unit. There is no problem even if the modification such as modification, the simplicity of its synthesis, and when the effect of improving the toughness of the cured product obtained by electron beam irradiation can be expected, the linear structure of the present invention It is preferable to modify a di (meth) acrylate oligomer having an alkyl side chain structure, and it can be synthesized by a known method.

For example, the polyurethane-modified di (meth) acrylate oligomer having a linear alkyl side chain structure of the present invention is obtained by adding a monomer or polymer serving as a main skeleton and J in the general formula (1). After reacting with the precursor compound forming the represented joint, a unit (-SR) containing a linear alkyl group is introduced, and after reacting with polyisocyanate, hydroxy (meth) acrylate is reacted. Alternatively, after reacting the reaction product of the monomer or polymer serving as the main skeleton with the precursor of the joint (J) with polyisocyanate, hydroxy (meth) acrylate is reacted, and finally the linear It is obtained by introducing a unit containing an alkyl group (-SR).

The type of the polyisocyanate is not particularly limited. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3
-Xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-
4,4′-diphenylmethane diisocyanate 4,
4'-biphenylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, methylene bis (4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, bis (2-isocyanatoethyl) The urethane-modified di (meth) acrylate having a linear alkyl side chain structure of the present invention is synthesized using fumarate, 6-isopropyl-1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, lysine diisocyanate, and the like. be able to.

Of these polyisocyanates, 2, 6
-Tolylene diisocyanate, isophorone diisocyanate, 4,4'-diphenylmethane diisocyanate and the like are preferably used for urethane-modifying the di (meth) acrylate having a linear alkyl side chain structure of the present invention.

In the present invention, these di (meth) acrylate oligomers having a linear alkyl side chain structure can be used alone or in combination of some of them.

The electron beam-curable resin composition for coating a sheet-like support used in the present invention is not particularly limited as long as it contains the above-mentioned di (meth) acrylate oligomer having a linear alkyl side chain structure and a molecular weight of 450 to 5000. Although the di (meth) acrylate oligomer having a linear alkyl side chain structure is a liquid or oily solid having a relatively high viscosity by itself, the handling of the di (meth) acrylate oligomer having a linear alkyl side chain structure, For the purpose of improving coatability on the body, it is preferable to incorporate the following diluent monomers.

The type of the diluent monomer used in the present invention is not particularly limited, but the following electron beam-curable compounds can be used alone or in combination.

The diluent monomers include (1) aliphatic, alicyclic and aromatic mono- to hexavalent alcohols and di (meth) acrylate compounds of polyalkylene glycols; (2) aliphatic, alicyclic and Di (meth) acrylate compounds obtained by adding a polyalkylene oxide to an aromatic 1- to 6-valent alcohol (3) poly (meth) acryloylalkyl phosphates (4) polybasic acid, polyol and (meth) Reaction product of acrylic acid (5) Reaction product of isocyanate, polyol and (meth) acrylic acid (6) Reaction product of epoxy compound and (meth) acrylic acid (7) Epoxy compound, polyol and (meth) ) Reaction products with acrylic acid. (8) N-vinyllactam compounds.

More specifically, the monofunctional diluent monomers include methyl (meth) acrylate, ethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acryloylmorpholine, Ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexyl methacrylate, dicyclohexyl (meth) acrylate,
Isobornyl (meth) acrylate, benzyl (meth)
Acrylate, ethoxydiethylene glycol (meth)
Acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl methacrylate, 2-ethylhexyl carbitol (meth)
Acrylate, ω-carboxypolycaprolactan mono (meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, acrylic acid dimer, acrylic acid-9,10-epoxidized oleyl, methacrylic acid-
9,10-epoxidized oleyl, ethylene glycol maleate mono (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth)
Acrylate, dicyclopentenyloxyethylene (meth) acrylate, (meth) acrylate of caprolactan adduct of 4,4-dimethyl-1,3-dioxolan, caprolactone of 3-methyl-5,5-dimethyl-1,3-dioxolan Adduct (meth) acrylate,
Ethylene oxide-modified phenoxylated phosphoric acid (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam and the like are used.

The polyfunctional diluent monomers include ethanediol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,14-tetradecanediol di (meth) acrylate, 1,15-pentadecanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 2-butyl-2-ethylpropanediol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, polyethylene oxide-modified bisphenol A di (meth) acrylate,
Polyethylene oxide-modified hydrogenated bisphenol A di (meth) acrylate, propylene oxide-modified bisphenol A di (meth) acrylate, polypropylene oxide-modified bisphenol A di (meth) acrylate, hydroxypivalic acid ester neopentyl glycol ester di (meth) acrylate, hydroxy Caprolactone adduct of pivalic acid ester neopentyl glycol ester di (meth) acrylate, ethylene oxide-modified isocyanuric acid di (meth) acrylate, pentaerythritol di (meth) acrylate monostearate,
1,6-hexanediol diglycidyl ether acrylic acid adduct, polyoxyethylene epichlorohydrin-modified bisphenol A di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Ethylene oxide modified trimethylolpropane tri (meth) acrylate, polyethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, polypropylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, ethylene oxide-modified isocyanuric acid tri (meth) acrylate, ethylene oxide-modified glycerol (Meth) acrylate, polyethylene oxide-modified glycerol tri (meth) acrylate, propylene oxide modified glycerol tri (meth)
Acrylate, polypropylene oxide-modified glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Examples include hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, and polycaprolactone-modified dipentaerythritol hexa (meth) acrylate.

For the purpose of imparting the physical properties of the electron beam-cured material, particularly the flexibility and toughness, to the electron beam-curable resin composition for coating the sheet-like support used in the present invention, the following electron beam-curable oligomers are used. You may mix.

The electron beam-curable oligomer used in the present invention includes: (1) a linear or side chain molecular weight of 300 to 10
(2) An oligomer having a structure of a reaction product of an alkyl diol having a molecular weight of 30 to 300 and hydrogenated castor oil (3) An oligomer having a dimer acid structure derived from a dimer of an unsaturated higher fatty acid (4) An oligomer having a polyether structure having a molecular weight of 400 to 10,000 (5) An oligomer having a polyester structure having a molecular weight of 1,000 to 10,000 can be used. If these electron beam-curable oligomers have any of the above-mentioned structures, they may be modified at any time, such as urethane modification, ester modification, and epoxy modification.

In the electron beam-curable resin composition of the present invention, di (meth) having these linear alkyl side chain structures is used.
The content of the acrylate oligomer is 10 to 90 parts by weight, preferably 20 to 80 parts by weight, per 100 parts by weight of the electron beam-curable organic compound contained in the electron beam-curable resin composition. When the content of the di (meth) acrylate oligomer having a straight-chain alkyl side chain structure exceeds 90 parts by weight in 100 parts by weight of the electron beam-curable organic compound contained in the electron beam-curable resin composition, The viscosity of the line-curable resin composition becomes too high, handling becomes difficult, and a problem that a sticky feeling remains on the surface of the cured coating film may occur. On the other hand, when the content of the di (meth) acrylate oligomer having a linear alkyl side chain structure is less than 10 parts by weight, the flexibility of the cured product is impaired, the cured product becomes brittle, and the cured coating film easily cracks. Sometimes.

In order to enhance the surface smoothness and gloss of the sheet-like composite material according to the present invention, it is preferable to manufacture the electron beam-curable resin coating layer by a cast EB method. For example, an electron beam-curable resin composition is applied on one surface of a sheet-like support to form a coating liquid layer, which is then superimposed on the surface of a metal cylindrical rotating body that is a smooth and strong glossy molded body. The multilayer body thus formed is irradiated with an electron beam to cure the coating liquid layer, and is joined to a sheet-like support to form a laminate, and the laminate is removed from the surface of the metal cylindrical rotating body. A direct coating method of peeling can be used. Further, as another manufacturing method, on one surface of the metal cylindrical rotating body, an electron beam-curable resin composition is applied to form a coating liquid layer, and a sheet-like support surface is superimposed thereon, The coating liquid layer is transferred to the surface of the support, and the multilayer body thus formed is irradiated with an electron beam to cure the coating liquid layer and to bond and laminate the electron beam cured resin coating layer and the sheet-like support. A transfer coating method in which a body is formed and the laminated body is peeled off from the surface of the metal cylindrical rotary body can also be used.

There are no particular restrictions on the type of sheet-like support used in the present invention. Although those having a thickness of about 500 μm can be used, a paper substrate is preferably used. As the paper substrate, a paper substrate having a basis weight of usually 50 to 300 g / m ² and having a smooth surface is used. The type of paper substrate used in the present invention is not particularly limited. As the pulp forming the paper base, generally, natural pulp such as softwood pulp manufactured from fir, toga, etc., hardwood pulp manufactured from maple, beech, poplar, etc., and softwood pulp mixed pulp is widely used. Bleached pulp such as kraft pulp, sulfite pulp and soda pulp can be used. Further, paper bases manufactured from pulp including synthetic fibers and synthetic pulp can also be used. The paper substrate may contain one or more kinds of usual additives such as a dry paper strength enhancer, a sizing agent, a filler, a wet paper strength enhancer, a fixing agent, and a pH adjuster.

The material of the sheet-like support used in the present invention is not particularly limited. For example, clay, talc, kaolin, calcium carbonate, hydroxide, aluminum,
Pigments such as titanium dioxide, magnesium hydroxide, and plastic pigment, and acrylic resin, polyurethane resin, ethylene-acrylic acid copolymer resin, vinyl acetate-ethylene copolymer resin, styrene-butadiene copolymer resin, vinylidene chloride resin, etc. Pigment coated paper such as coated paper, cast coated paper, art paper, etc. having a pigment coated layer containing the above synthetic resin as a main component.

Further, the use of a sheet-like support such as a plastic film or a so-called synthetic paper in place of the paper substrate used in the present invention may be used at all.
For example, a film formed by melting and extruding a thermoplastic resin composition containing a polyolefin resin such as a polypropylene resin or a polyethylene resin can be used as the sheet-like support. Also, so-called synthetic paper obtained by converting synthetic resin film into pseudo paper can be used as the sheet-like support. Plastic films used as sheet-like supports and so-called synthetic papers include pigments such as clay, talc, kaolin, calcium carbonate, titanium dioxide, magnesium hydroxide, metal soaps such as zinc stearate, and various surfactants. , And one or more kinds of colored pigments and the like.

The metal cylindrical rotary body used as the molded body is not particularly limited in its material shape, and is formed of, for example, stainless steel, copper, chrome, etc., and has a mirror-finished smooth peripheral surface. Is used. Further, in order to facilitate the separation between the electron beam curable resin coating layer and the surface of the molded body, a release aid such as silicone oil or wax can be supplied to the surface of the metal cylindrical rotating body.

On the other hand, a sheet-like material may be used as a molded body in addition to the metal cylindrical rotary body. The sheet-like material for molding used as a molded body is not particularly limited as long as it is smooth and flexible, but specifically, a plastic film such as a polyester film, a metal sheet, a resin-coated paper, a metal-deposited film Preferably, a metallized paper or the like is used, and a release aid such as silicone or wax may be supplied to the surface of the sheet material for molding in order to facilitate the release of the electron beam-curable resin coating layer. Further, the surface of the sheet material may be subjected to an appropriate treatment in advance, for example, a treatment such as a silicone treatment, so that the cured electron beam-curable resin coating layer can be easily peeled off. The sheet-like material used as a molded body may be processed into an endless belt shape. The sheet-like material used as a molded article can be used repeatedly. However, since the repeated impact of electron beam irradiation deteriorates the sheet-like material, the number of repetitive uses is limited.

Examples of the method of applying the electron beam-curable resin composition on the surface of a metal cylindrical rotary member or the surface of a sheet-like material for molding include a bar coating method, an air doctor coating method, a blade coating method, and a squeeze method. Coating method, air knife coating method, roll coating method, gravure coating method, transfer coating method, comma coating method, smoothing coating method, microgravure coating method, reverse roll coating method, multi-roll coating method, dip coating method, kiss coating method A coating method such as a gate roll coating method, a falling curtain coating method, a slide coating method, a fountain coating method, and a slit die coating method can be used. In particular, when using a metal cylindrical rotating body as a molded body, use a roll coating method using an application rubber roll or an offset gravure coating method in order not to damage the surface of the metal cylindrical rotating body. And a non-contact type fountain coater or slit die coater is advantageously used.

In the sheet-like composite material of the present invention, the coating amount of the electron beam-curable resin coating layer is 3 to 60 after curing.
g / m ² , more preferably 5 to 4 g / m ^2.
0 g / m ² . If the coating amount is less than 3 g / m ² , the resulting coated body will have insufficient smoothness, fail to achieve cosmetics, and may have a reduced gloss. Also it is 60g /
If it exceeds m ² , the effect may be saturated and the cost may increase.

In particular, when a paper substrate is used as the sheet-like support, the coating amount after curing of the electron beam-curable resin coating layer is 3
g / m ² or more, more preferably 5 g / m ² or more.
２０20 g / m ² . The coating amount of the resin coating amount is 3 g / m ²
If it is less than 3, the formation unevenness of the paper substrate cannot be filled, and the smoothness and aesthetics of the electron beam-curable resin coating layer may be impaired.

In the present invention, in order to improve the smoothness of the sheet-like composite material and to improve the adhesion between the sheet-like support and the electron beam-curable resin coating layer in contact therewith, the sheet-like support is in contact with the sheet-like support. An undercoat layer containing a synthetic resin as a main component may be provided between the protective layer and the electron beam curable resin coating layer. Examples of the synthetic resin used for the undercoat layer include alkyd resins, (meth) acrylic resins, vinyl resins, cellulose resins, urethane resins, polyester resins, and copolymer resins thereof. The solution is applied by dissolving or dispersing in a solvent-based or aqueous medium. An electron beam curable resin or an ultraviolet curable resin can also be used for forming the undercoat layer.

When the paper substrate is used as a sheet-like support, a barrier agent such as polyvinyl alcohol, hydroxyethyl cellulose, oxidized starch or the like is separately used to prevent the penetration of the electron beam-curable resin composition into the paper substrate. An undercoat layer may be provided.

As described above, providing the undercoat layer between the sheet-like support and the electron beam-curable resin coating layer in contact with the sheet-like support is achieved by coating the sheet-like support with the electron beam-curable resin composition. It is a means generally used in the field of forming an electron beam-curable resin coating layer, for example, a photographic printing paper support coated with an electron beam-curable resin composition, an electrophotographic transfer paper, a heat-sensitive base paper, It is used for process release paper, thermal transfer receiving paper, ink jet recording paper, wrapping paper, and the like.

The electron beam-curable resin composition used in the present invention contains a dispersant, a releasing agent, an antifoaming agent, a coloring agent, a dye,
Known auxiliaries, such as preservatives, can also be blended as needed.

The electron beam irradiator used for the electron beam irradiation is not particularly limited, and examples thereof include a handy-graft scanning system, a double scanning system,
An electron beam irradiation apparatus such as a broad beam method and a curtain beam method can be used. Among them, the curtain beam method, which is relatively inexpensive and provides a large output, is effectively used in the present invention.

The acceleration voltage at the time of electron beam irradiation is 100 to 30
0 kV, and the absorbed dose is 0.1 kV.
1 to 8 Mrad, preferably 0.5 to 6 Mr
ad is particularly preferred.

[0059]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

The di (meth) acrylate oligomers 1 to 9 having a specific linear alkyl side chain structure of the present invention used in Examples 1 to 14 of the preparation of the sheet-like composite material shown below are as follows. .

[0061]

Embedded image

A di (meth) acrylate oligomer having a linear alkyl side chain structure has at most two or less alkyl dimers having a linear alkyl side chain structure represented by the general formula (1) per molecule. Acrylate oligomer [molecular weight: about 1600, in the above general formula (1), J,
S and R are each _{-CH 2 CHCH 2 -, - O} (C
O)-, a linear alkyl group having an average carbon number of 17; ]

Two di (meth) acrylate oligomers having a linear alkyl side chain structure Alkyl di-chains having at most four or less linear alkyl side chain structures represented by the general formula (1) per molecule Acrylate oligomer [molecular weight of about 3600, in the general formula (1), J,
S and R are each _{-CH 2 CHCH 2 -, - O} (C
O)-, a linear alkyl group having an average carbon number of 17; ]

Di (meth) acrylate oligomer 3 having a straight-chain alkyl side chain structure Alkyl di-chain having a straight-chain alkyl side chain structure represented by the above general formula (1) of not more than 6 in the molecule. Acrylate oligomer [molecular weight of about 2600, in the general formula (1), J,
S and R are each _{-CH 2 CHCH 2 -, - O} (C
O)-, a linear alkyl group having an average carbon number of 17; ]

Di (meth) acrylate oligomer 4 having a straight-chain alkyl side chain structure Alkyl di-chain having a straight-chain alkyl side chain structure represented by the following general formula (1) of at most two in the molecule: Electron beam-curable organic compound containing an acrylate oligomer as a main component [molecular weight: about 1800;
S and R are each _{-CH 2 CHCH 2 -, - O} (C
O)-, a linear alkyl group having an average carbon number of 17; ]

5 di (meth) acrylate oligomers having a linear alkyl side chain structure A hydrogenated dimer having at most two or less linear alkyl side chain structures represented by the above general formula (1) in the molecule Acid-based diacrylate oligomer [molecular weight of about 2200, in the above general formula (1), J,
S and R are each _{-CH 2 CHCH 2 -, - O} (C
O)-, a linear alkyl group having an average carbon number of 17; ]

Di (meth) acrylate oligomer 6 having a linear alkyl side chain structure Alkyl system having at most two or less linear alkyl side chain structures represented by the above general formula (1) in the molecule Electron beam-curable organic compound containing a diacrylate oligomer as a main component [molecular weight of about 1650, J in the general formula (1),
S and R are each _{-CH 2 CHCH 2 -, - O} (C
O)-, a linear alkyl group having an average carbon number of 19; ]

Di- (meth) acrylate Oligomer 7 Having a Linear Alkyl Chain Structure Alkyl di-alkyl having a linear alkyl side chain structure represented by the following general formula (1) of at most two in the molecule: Acrylate oligomer [molecular weight of about 1700, in the general formula (1), J,
S and R are each _{-CH 2 CHCH 2 -, - O} (C
O)-is a straight-chain alkyl group having an average carbon number of 21. ]

Di (meth) acrylate oligomer 8 having a linear alkyl side chain structure A polyether type having at most two or less linear alkyl side chain structures represented by the above general formula (1) in the molecule Diacrylate oligomer [molecular weight of about 2300, and in the general formula (1), J,
S and R are each _{-CH 2 CHCH 2 -, - O} (C
O)-, a linear alkyl group having an average carbon number of 17; ]

Di (meth) acrylate oligomer 9 having a linear alkyl side chain structure At most two polyethers having a linear alkyl side chain structure represented by the above general formula (1) in the molecule Alkyl diacrylate oligomer [molecular weight of about 2600, in the above general formula (1), J,
S and R are each _{-CH 2 CHCH 2 -, - O} (C
O)-, a linear alkyl group having an average carbon number of 17; ]

The diacrylate oligomers used in Comparative Examples 1 to 5 are as follows. Unlike the di (meth) acrylate oligomer having a specific linear alkyl side chain structure of the present invention, The molecule does not contain the linear alkyl side chain structure having at least 8 carbon atoms represented by (1). Diacrylate oligomer 1

Alkyl diacrylate oligomer having no linear alkyl side chain structure [A linear alkyl side chain structure having a molecular weight of about 2,000 and having at least 8 carbon atoms represented by the above general formula (1)] Not included] (trademark: KU5
11-1B)

Diacrylate oligomer 2 Alkyl diacrylate oligomer having at most 24 linear alkyl side chain structural units having an average of 2 carbon atoms [molecular weight: about 2,000, containing a linear alkyl side chain structure in the molecule. Which does not correspond to the specific linear alkyl side chain structure of the present invention represented by the general formula (1)]
(Trademark: KU511-17B)

Diacrylate oligomer 3 A polyether diacrylate oligomer having at most 35 linear alkyl side chain structural units having an average of 1 carbon atom [molecular weight: about 2,000, having a linear alkyl side chain structure in the molecule] But it does not fall under the specific linear alkyl side chain structure of the present invention represented by the general formula (1)] (trademark: PPG2000-U)

Example 1 A sheet-like composite material was produced by the following operation. Composition 1 Component Blend Amount 50% by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 1 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) 1,9-nonane 50 parts by weight of diol diacrylate (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Preparation of sheet-like composite material The composition 1 was coated with a Meyer bar on the surface of a sheet-like support made of double-sided coated paper (trade name: OK Top Coat Dal, manufactured by Oji Paper) having a basis weight of 157 g / m ^2. The inner coating liquid layer was coated so that the coating amount after curing was 10 g / m ^2, and a thickness of 75 μm used as a molded article was formed thereon.
After the polyester film is overlaid and pressed, an acceleration voltage of 1
75kV, absorbed dose 3Mrad, oxygen concentration 500ppm
The resin coating liquid layer was cured by irradiating an electron beam under the following conditions, and simultaneously, the obtained resin coating layer and the sheet-like support were integrally bonded. Thereafter, the polyester film was peeled off from the resin coating layer to obtain a sheet-like composite material having an electron beam-curable resin coating layer.

The evaluation was performed as follows, and the evaluation results are shown in Table 1.
Shown in Test and Evaluation Method (1) Blank Paper Gloss Blank paper gloss was measured using a gloss meter VGS-1D (manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS Z8741 at 60 ° /
A gloss of 60 ° was measured. Those having a measured value of 75 or more were evaluated as having excellent gloss. (2) Slipperiness The slipperiness was evaluated in accordance with JIS K7125, and a double-sided coated paper having a basis weight of 157 g / m ² (trademark: (OK Top Coat Dall, manufactured by Oji Paper Co., Ltd.), and the static friction coefficient was measured using a small universal measuring instrument (manufactured by Tester Sangyo Co., Ltd.). Those having a measured value of 0.70 or less were evaluated as having excellent slipperiness. (3) Water contact angle The water contact angle is FIBRO 1100DAT MkII
(FIBRO), the droplets on the surface of the sheet-like composite material formed by the water droplets (5 μl) dropped from the microsyringe were photographed with a flash using a video camera,
The contact angle was measured from the obtained image. Those having a contact angle of 70 ° or more were evaluated to have sufficiently low critical surface energy and excellent slipperiness. (4) Blocking resistance The blocking resistance is determined by the electron beam-curable resin coating layer of the sheet-like composite material prepared by the above method and the back surface of the separately prepared sheet-like composite material (the surface not coated with the electron beam-curing resin). Are pressed under a load of 4.8 kg / cm ² for 3 hours using a press machine (Labo Press: manufactured by Kumagaya Riki Co., Ltd.), and after the load is released, the blocking state is visually observed. The response when peeling and separating the sheets was evaluated by sensory evaluation. ○ and △ were evaluated as acceptable, and × was evaluated as unacceptable. ○: No blocking occurred △: Mild blocking, easy sample separation ×: Severe blocking, sample not easily separated

Example 2 The same operation as in Example 1 was performed. However, the following composition 2 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 2 Component Blend Amount 65% by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 1 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) 1,9-nonane 35 parts by weight of diol diacrylate (trade name: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Example 3 The same operation as in Example 1 was performed. However, the following composition 3 was prepared and used in place of composition 1. The high gloss printing paper was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 3 Component Blending amount 50 parts by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 2 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) 1,9-nonane Diol diacrylate 50 parts by weight (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Example 4 The same operation as in Example 1 was performed. However, the following composition 4 was prepared and used in place of the composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 4 Component Blend Amount 50% by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 3 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industries, Ltd.) 1,9-nonane Diol diacrylate 50 parts by weight (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Example 5 The same operation as in Example 1 was performed. However, the following composition 5 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 5 Component Blend Amount 50% by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 4 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) 1,9-nonane Diol diacrylate 50 parts by weight (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Example 6 The same operation as in Example 1 was performed. However, the following composition 6 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 6 Component Blended amount 50 parts by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 5 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) 1,9-nonane Diol diacrylate 50 parts by weight (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Example 7 The same operation as in Example 1 was performed. However, the following composition 7 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 7 Component Blend Amount 50% by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 6 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) 1,9-nonane Diol diacrylate 50 parts by weight (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Example 8 The same operation as in Example 1 was performed. However, the following composition 8 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 8 Component Blend Amount 50% by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 7 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) 1,9-nonane Diol diacrylate 50 parts by weight (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Example 9 The same operation as in Example 1 was performed. However, the following composition 9 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 9 Component Blend Amount 50% by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 8 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) 1,9-nonane Diol diacrylate 50 parts by weight (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Example 10 The same operation as in Example 1 was performed. However, the following composition 10 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 10 Component Blend Amount 50% by weight of an electron beam-curable organic compound containing a di (meth) acrylate oligomer 9 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industries, Ltd.) 1,9-nonane Diol diacrylate 50 parts by weight (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Example 11 The same operation as in Example 1 was performed. However, the following composition 11 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 11 Component Blending amount 50 parts by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 1 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industries, Ltd.) 2-butyl-2 -50 parts by weight of ethylpropanediol diacrylate (trademark: KU-C9A, manufactured by Arakawa Chemical Industry Co., Ltd.)

Example 12 The same operation as in Example 1 was performed. However, the following composition 12 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 12 Component Blend Amount 50% by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 1 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) Dicyclopentadiene diacrylate 50 parts by weight (trademark: KAYARAD R-684, manufactured by Nippon Kayaku Co., Ltd.)

Example 13 The same operation as in Example 1 was performed. However, the following composition 13 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 13 Component Blending amount Electron beam curable organic compound containing di (meth) acrylate oligomer 1 having a linear alkyl side chain structure as a main component 50 parts by weight (Arakawa Chemical Industries, Ltd.) Isobornyl acrylate 50 Parts by weight (trademark: Light Acrylate IB-XA, manufactured by Kyoeisha Chemical Co., Ltd.)

Example 14 The same operation as in Example 1 was performed. However, the following composition 14 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 14 Component Blend Amount 50% by weight of an electron beam-curable organic compound containing di (meth) acrylate oligomer 1 having a linear alkyl side chain structure as a main component (manufactured by Arakawa Chemical Industry Co., Ltd.) Trimethylolpropane triacrylate 50 parts by weight (trademark: M309, manufactured by Toagosei Co., Ltd.)

Comparative Example 1 The same operation as in Example 1 was performed. However, the following composition 15 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 15 Component Blending amount 50 parts by weight of an electron beam-curable organic compound containing diacrylate oligomer 1 as a main component (trade name: KU511-1B, manufactured by Arakawa Chemical Industries, Ltd.) 50 parts by weight of 1,9-nonanediol diacrylate (Trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Comparative Example 2 The same operation as in Example 1 was performed. However, the following composition 16 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 16 Component Blend Amount 50 parts by weight of electron beam-curable organic compound containing diacrylate oligomer 2 as a main component (trademark: KU511-17B, manufactured by Arakawa Chemical Industries) 50 parts by weight of 1,9-nonanediol diacrylate (Trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Comparative Example 3 The same operation as in Example 1 was performed. However, the following composition 17 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 17 Component Compounding amount 50 parts by weight of electron beam-curable organic compound containing diacrylate oligomer 3 as a main component (trademark: PPG2000-U, manufactured by Arakawa Chemical Industries, Ltd.) 50 parts by weight of 1,9-nonanediol diacrylate (Trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

Comparative Example 4 The same operation as in Example 1 was performed. However, the following composition 18 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 18 Component Compounding amount Stearyl acrylate 50 parts by weight (trademark: Light acrylate SA, manufactured by Osaka Organic Co., Ltd.) 1,9-nonanediol diacrylate 50 parts by weight (trademark: New Frontier L-C9A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) )

Comparative Example 5 The same operation as in Example 1 was performed. However, the following composition 19 was prepared and used in place of composition 1. The sheet-like composite material was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results. Composition 19 Component Blending amount Electron beam-curable organic compound containing diacrylate oligomer 1 as a main component 50 parts by weight (trademark: KU511-1B, manufactured by Arakawa Chemical Industry Co., Ltd.) Stearyl acrylate 50 parts by weight (trademark: light acrylate SA) , Manufactured by Osaka Organic Co., Ltd.)

Comparative Example 6 The cast-coated surface of a single-side coated paper having a basis weight of 128 g / m ² (trade name: mirror-coated platinum, manufactured by Oji Paper) was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

[0097]

[Table 1]

As can be seen from Table 1, the sheet-like composite material according to the present invention not only has extremely high glossiness of white paper, but also has excellent slipperiness and blocking resistance (Examples 1 to 1).
4). However, the sheet-like composite material having an electron beam-curable resin coating layer that does not contain a di (meth) acrylate oligomer having a specific linear alkyl side chain structure according to the present invention has a high degree of white paper gloss, but has slipperiness and blocking resistance. An electron beam-curable resin coating layer containing an electron beam-curable organic compound which is inferior in properties (Comparative Examples 1 to 3) and has an alkyl long chain but does not fall under the specific di (meth) acrylate oligomer of the present invention is phase-separated. It is not violent, does not form a body as a sheet-like composite material, and is not practical (Comparative Examples 4 and 5). In addition, although general cast-coated paper has no problem in slipperiness,
Poor glossiness of blank paper (Comparative Example 6).

[0099]

According to the present invention, an electron beam-curable resin coating layer comprising an electron beam-curable body of an electron beam-curable resin composition is provided on at least one surface of a sheet-like support, and has excellent slipperiness. Even when stacked and stored for a long time, the surface coated with the electron beam curable resin and the uncoated surface, or the coated surfaces do not cause blocking,
Moreover, it is practically extremely useful as a technique for providing a sheet-like composite material having a high degree of white paper gloss. Further, the sheet-like composite material of the present invention has the above-described excellent characteristics, and thus is suitable as a printing material, a packaging material, and the like.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 2H023 FA04 FA12 4F100 AH00A AK25A AL05A AT00B BA02 DG10B EJ53A EJ91 GB15 JB14A JK15 JK16A JN21 YY00A 4J002 BG001 BG071 EH076 ET006 EU026 GG02 GK03 GS02

Claims (5)

[Claims] 1. An electron beam-curable organic compound having at least 8 carbon atoms represented by the following general formula (1) in 100 parts by weight:
An electron beam comprising 10 to 90 parts by weight of a di (meth) acrylate oligomer having at least one linear alkyl side chain structure (-SR) and a molecular weight of 450 to 5000. Curable resin composition. Embedded image [Wherein R is a linear alkyl group having at least 8 carbon atoms, S is a spacer unit, and J is at least one (meth) acryloyl group-containing structure, a main chain skeleton, and a linear alkyl group. It represents a binding unit that connects the side chain structure (-SR). ] 2. The electron beam curable resin composition according to claim 1, wherein the contact angle of water on the surface of the cured product obtained by irradiating the electron beam is 70 ° or more. 3. A sheet-shaped composite material comprising: a sheet-shaped support; and an electron beam-curable resin coating layer of the electron beam-curable resin composition formed on at least one surface of the substrate. 4. The sheet-like composite material according to claim 3, wherein a contact angle of the surface of the electron beam curable resin coating layer with water is 70 ° or more. 5. The JI on the surface of the electron beam-curable resin coating layer.
The sheet-like composite material according to claim 3, wherein the coefficient of static friction based on SK7125 is 0.7 or less.