JPH115809A - Electron radiation curing resin composition and sheetlike composite material obtained by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition, capable of forming an electron radiation cured resin film or coating layer excellent in flexibility and folding endurance and useful as a support for a packaging material, a printing material, etc., by including a specific monofunctional electron radiation curing organic compound and a specific di(meth)acrylate therein. SOLUTION: This composition is obtained by including (A) a component containing one or more monofunctional electron radiation curing organic compounds capable of manifesting >=20 deg.C glass transition temperature when converted into a homopolymer (e.g. acryloylmorpholine) and (B) a component containing one or more di(meth)acrylates such as a polyether polyurethane di(meth)acrylate having a polyether structure of 500-10,000 molecular weight (e.g. polyurethane diacrylate of polyethylene glycol) at (10/90) to (90/10) weight ratio of the components A/B. The objective composition is useful for cast coated paper having a high smoothness and a high glossiness.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an electron beam-curable resin composition, and an electron beam-curable resin film and a sheet-like composite material obtained by using the same. More specifically, the present invention provides an electron beam-curable resin composition that provides a highly flexible electron beam-curable resin, a flexible electron beam-curable resin film obtained therefrom, and an electron beam obtained from the composition. The present invention relates to a sheet-like composite material having a cured resin coating layer and having excellent flexibility and high gloss.

[0002]

2. Description of the Related Art Conventionally, a glossy coated sheet represented by a cast coated paper or the like has a coating layer mainly composed of a pigment and an adhesive formed on a paper substrate, which contains water. While in a plastic state, a heated glossy surface is pressed against the surface and dried to form a high gloss coating layer. However, the glossiness of a conventional glossy coated sheet as a high glossy coating material is not satisfactory, and a sheet having a higher glossiness has been desired.

In order to solve this problem, a molten resin is laminated on a sheet-like substrate in the form of a film, and the molten resin is pressed against a metal cylindrical rotary member having a smooth and high gloss to cool the substrate. A so-called laminate coating method in which a strong glossy coating layer is formed by peeling off from the metal cylindrical rotary body later, and instead of the molten resin in the above-mentioned laminate coating method, an electron beam-curable unsaturated organic compound was used as a main component. A coating liquid layer formed from a coating composition (hereinafter referred to as an electron beam-curable resin composition) is pressed against a molding surface or a metal cylindrical rotating body, and then cured by irradiating an electron beam thereto. Cast electron beam irradiation method was developed,
These methods have made it possible to obtain a sheet-like material having a high gloss.

[0004] However, the sheet-like composite material (hereinafter referred to as the “composite material”) produced by the cast electron beam irradiation method as described above.
EB sheet material) has a high gloss of the electron beam cured resin film on the surface, but the resin film itself is hard, lacks flexibility as a whole, and when folded, it becomes an electron beam cured resin coating layer. It is known that cracking occurs, which is a major disadvantage in the quality of EB sheet material.

Conventionally, an electron beam-curable resin composition containing a specific oligomer or polymer, or a specific monomer has been used (JP-A-60-178447 and JP-A-61-2).
36547), an attempt to improve the flexibility of the cured resin film was known, but the relationship between the physical properties of the resin film and the flexibility of the high-gloss EB sheet material has not been sufficiently elucidated. Therefore, sufficient results were not obtained for improving flexibility. In recent years, a method using an electron beam-curable resin composition containing a compound having a polybutadiene chain (JP-A-61-27075, JP-A-62-109046, JP-A-62-109047, JP-A-62-109047, -141541, JP-A-62-141542
JP-A-62-141543 and JP-A-6-242550) and a polyurethane-modified unsaturated organic compound having a specific molecular weight and a functional group (JP-A-60-70446).
And JP-A-63-130608 and JP-A-2-75998) have been proposed. However, even when these methods are used, the obtained electron beam cured coating film is bent. Occasionally, large cracks occur, and thus these prior arts have not yet provided a satisfactory solution.

On the other hand, a method of curing an electron beam curable resin composition using a low irradiation dose (Kusaki, Research Report of the Printing Bureau, Ministry of Finance, No. 57, 1-14 (1985)), Kawamura et al., The 41st Polymer Proceedings of the debates, 41 (10), 4316-4318 (1992), etc.), and / or
Alternatively, a method using an electron beam-curable resin composition containing a low-crosslinkable electron beam-curable unsaturated organic compound as a main component (W. Or
raby and WK Walsh, J. Appl. Poly.Sci., (23), 32
27-3242 (1979), HC Miller, Rad. Tech. '90-North
America, vol. 1, 201-210 (1990), Kobayashi, Radiation & Industry, 61, 21-25 (1994)), etc., are known to be able to ensure a certain level of flexibility of cured resin films. However, in these methods, not only the flexibility of the cured film is not sufficiently improved, but also the balance between the flexibility and other physical properties is insufficient, such that the EB sheet material cannot be practically used. . Further, printing plate materials requiring relatively strict flexibility (Japanese Patent Application Laid-Open Nos. 49-10910, 51-43374, 1-100535, and 6-20
6956, etc.) and optical fiber coating materials (JP-A-63-850)
No. 31, JP-A-63-215707, JP-A-3-166217, etc.) are also being considered, but even with these methods, improvement in flexibility is still insufficient. is there. Incidentally, in the field of adhesives, techniques capable of producing a very flexible resin cured product (JP-A-5-105857, JP-A-5-170736)
No., JP-A-7-310067) are disclosed, but those techniques also satisfy various physical properties required for the EB sheet material,
Moreover, it is still unsatisfactory in improving flexibility.

In addition to the above prior art, for example,
No. 5031, JP-A-63-215707, JP-A-1-92239, JP-A-1-100535, JP-A-3-296513, JP-A-4-288314,
JP-A-5-9899, JP-A-7-310067, and JP-A-8-59
No. 759 discloses various electron beam-curable resin compositions, but their performance, practical applicability, etc. are still unsatisfactory.

As described above, the existing technology improves the flexibility of the cured resin film and the EB sheet material, and at the same time, satisfies various physical properties such as high smoothness and glossiness, and can withstand practical use. Since a sufficient and practical solution to the problem has not been provided, the proposal of a fundamental solution to the above-mentioned problems has been awaited.

[0009]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and in particular, an electron beam-curable resin composition capable of forming an electron beam-curable resin film or coating layer having excellent flexibility. The obtained electron beam-curable resin film, and an electron beam-cured resin coating layer obtained by coating the composition on at least one surface of a sheet-like support and curing by electron beam irradiation, and having a high glossiness Another object of the present invention is to provide a sheet-like composite material having excellent flexibility without causing cracks in the electron beam-curable resin coating layer even when folded.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an electron beam-curable resin composition for forming an electron beam-curable resin coating layer contains a glass transition temperature (20 ° C. or more). It has been found that the above problems can be solved by including a monofunctional electron beam-curable organic compound forming a homopolymer having Tg) and di (meth) acrylate, and the glossiness is high and the flexibility is high. Succeeded in making it possible to produce an electron beam curable resin-coated sheet-like composite material having particularly excellent properties.

The electron beam-curable resin composition of the present invention contains at least one kind of monofunctional electron beam-curable organic compound having a glass transition temperature of at least 20 ° C. (hereinafter referred to as Tg) when formed into a homopolymer. It is characterized by comprising a first component and a second component containing at least one type of di (meth) acrylate. In the electron beam-curable resin composition of the present invention, the monofunctional electron beam-curable organic compound-containing first component comprises (1) acryloylmorpholine and (2) tricyclo [5.2.1.0 ^2,6 ]. Mono (meth) acrylate having a decane structure and represented by the following general formula (1):

[0012]

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(Where (M) A in the formula (1) represents a (meth) acryloyl group), (3) a cycloalkyl mono (meth) acrylate represented by the following general formula (2):

[0014]

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[Wherein, in the formula (2), R ⁷ represents a hydrogen atom, a methyl group, a tert-butyl group, or a cyclohexyl group;
(M) A represents a (meth) acryloyl group. ], (4)
Mono (meth) acrylate of a tertiary alcohol represented by the following general formula (3):

[0016]

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[However, in the formula (3), R ⁸ , R ⁹ and R ¹⁰
Each independently represents a methyl group or an ethyl group, and (M) A represents a (meth) acryloyl group],
(5) A (meth) acrylate having a succinimide structure and represented by the following general formula (4):

[0018]

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[Wherein, in the formula (4), R ¹¹ and R ¹² each represent a hydrogen atom, or R ¹¹ and R ¹² are bonded to each other to form a succinimide structure in which each is bonded. Forms a cyclohexane ring or a cyclohexene ring together with two carbon atoms of the ring, s represents an integer of 2 or 3, and (M) A represents a (meth) acryloyl group],
(6) Mono (meth) acrylate having a bisphenol structure represented by the following general formula (5):

[0020]

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Wherein, in the formula (5), t represents an integer of 2 or 3, and (M) A represents a (meth) acryloyl group.
(7) A (meth) acrylate having a phthalic acid structure represented by the following general formula (6):

[0022]

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[Wherein, in the formula (6), R ¹³ represents a hydrogen atom or a methyl group, the cyclic structure B represents a cyclohexane ring or a benzene ring, and (M) A represents a (meth) acryloyl group], and (8) N-vinyl lactam compound represented by the following general formula (7):

[0024]

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Wherein, in the formula (7), u represents an integer of 1 or 3, including at least one member selected from the group consisting of a 5-membered lactam ring and a 7-membered lactam ring;
And the di (meth) acrylate-containing second component is
(9) represented by the following general formula (8) and 500 to 1
Polyether structure having a molecular weight of 000:

[0026]

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[However, in the formula (8), R ¹ and R ²
Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and n represents 0 or 1 to 9
M represents an integer satisfying (n + 1) × m = 20 to 300, provided that when n represents an integer of 2 or more, a plurality of R ² groups may be the same as each other. Or (10) a polyester structure represented by the following general formula (9) and having a molecular weight of 500 to 10,000:

[0028]

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[Wherein, in the formula (9), X represents a linear, branched or cyclic aliphatic or aromatic dicarboxylic acid residue used for forming the polyester structure, and Y represents Represents a linear, branched or cyclic aliphatic or aromatic diol residue used for forming the polyester structure, and n represents an integer satisfying the molecular weight of the polyester structure of 500 to 10,000. Polyester polyurethane di (meth) acrylate, (11) the following general formula (1)
A dimer acid structure derived from a dimer of unsaturated higher fatty acid represented by 0) or (11):

[0030]

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[However, in the equations (10) and (11),
R ³ , R ⁴ , R ⁵ and R ⁶ are each independently of the other
Represents an alkyl group, k, l, p and q represents an integer of 1 or more each, independently of one another, provided that the number of carbon atoms of the R ³ group is the sum of the number of carbon atoms and k and l of the R ⁴ groups 28 And
And the number of carbon atoms of R ⁵ and the number of carbon atoms of R ⁶ , p and q
Is 34) and 500 to 10,0
Di (meth) acrylate having a molecular number of 00, (1
2) represented by the following general formula (12) and 500 to 1
Polyolefin structure having a molecular weight of 000:

[0032]

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[However, in the formula (12), R ¹⁴ and R ¹⁵ are
Each independently represents a hydrogen atom, a methyl group or an ethyl group, a represents an integer of 1 or 2, and when a represents 2, two R ¹⁵ groups may be the same as or different from each other; B represents an integer satisfying the molecular weight of the polyolefin structure satisfying 500 to 10,000], and (13) a polyether structure represented by the following general formula (13). :

[0034]

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[However, R ¹ , R ² and n are as defined above, and m is an integer satisfying (n + 1) × m = 8 to 200. When n is an integer of 2 or more, A plurality of R ² groups may be the same as or different from each other], and include at least one selected from polyether di (meth) acrylates having a molecular weight of 150 to 5000; Is preferred. Further, the electron beam-curable resin film of the present invention includes an electron beam-cured product of the above-mentioned electron beam-curable resin composition according to the present invention. Further, the sheet-like composite material of the present invention is formed on at least one surface of a sheet-like support and an electron beam-curable resin coating layer containing the electron beam-curable body of the above-mentioned electron beam-curable resin composition according to the present invention. And Further, another sheet-like composite material of the present invention has a sheet-like support and an electron beam-curable resin composite coating layer formed on at least one surface of the sheet-like support, and the electron beam-curable resin composite coating layer has at least The present invention comprises a laminated body of a plurality of resin layers including an inner resin layer adjacent to the sheet-like support and an outermost resin layer disposed on the outermost side, and at least one of the plurality of resin layers is the present invention. And an electron beam-cured body of the above-mentioned electron beam-curable resin composition.

[0036]

BEST MODE FOR CARRYING OUT THE INVENTION In order to produce an electron beam-curable resin-coated sheet-like composite material of the present invention having a high glossiness and a particularly excellent flexibility, an electron beam-curable resin-coated layer is formed by irradiation with an electron beam. A first component comprising at least one monofunctional electron beam-curable organic compound exhibiting a Tg of 20 ° C. or more as a homopolymer in the electron beam-curable resin composition to be formed; And a second component comprising (meth) acrylate. The monofunctional, electron beam curable organic compound can be selected from electron beam curable unsaturated organic compounds having only one ethylenically unsaturated carbon-carbon bond (> C = C <) per molecule. . In the electron beam-curable resin composition of the present invention, the first component containing the monofunctional electron beam-curable organic compound includes (1) acryloylmorpholine (ACMO) and (2) tricyclo [5.2.1.0 ^2,6 ]. A mono (meth) acrylate having a decane structure and represented by the general formula (1); (3) a cycloalkyl mono (meth) acrylate represented by the general formula (2); Mono- (meth) acrylate of a tertiary alcohol represented by 3), (5) Mono- (meth) acrylate having a succinimide structure and represented by the general formula (4), (6)
Mono (meth) acrylate having a bisphenol structure and represented by the general formula (5), (7) Mono (meth) acrylate having a cyclic dicarboxylic acid monoester structure and represented by the general formula (6) And (8) preferably contains at least one member selected from the N-vinyllactam compounds represented by the general formula (7), and these are used together with the di (meth) acrylate-containing second component. Thereby, particularly excellent flexibility can be imparted to the electron beam cured product of the electron beam curable resin composition.

The homopolymer has a Tg of 20 ° C.
Specific examples of the monofunctional electron beam-curable organic compound described above include, in addition to ACMO, a mono (meta) having a tricyclo [5.2.1.0 ^2,6 ] decane structure and represented by the above formula (1). Examples of the acrylate include dicyclopentenyl acrylate and dicyclopentenyl methacrylate.
Examples of the cycloalkyl mono (meth) acrylate of the formula (2) include cyclohexyl acrylate, 2-cyclohexylcyclohexyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and 4-methylcyclohexyl. There are (meth) acrylate, 2-tert-butylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate and the like, and the tertiary alcohol mono (meth) acrylate of the formula (3) is tert-butyl. -Butyl acrylate, tert-amyl (meth) acrylate and the like, and the mono (meth) acrylate of the formula (4) having a succinimide structure is N-acryloyloxy-1,2,3,6-tetrahydrophthalimide , N-acryloyloxyhexa Mud phthalimide, and N- acrylate include acryloyloxy-3,4,5,6 tetrahydrophthalimide, as mono (meth) acrylate of the formula (5) having a bisphenol structure,
There are paramyl phenol-EO modified acrylates, and the mono (meth) acrylate having a cyclic dicarboxylic acid monoester structure of the above formula (6) includes 2-acryloyloxyethyl hydrogen phthalate and 2-acryloyloxypropyl hydrogen phthalate And 2-acryloyloxypropylhexahydrohydrogen phthalate. The N-vinyllactam compound of the formula (7) includes N-vinyl-2-pyrrolidone and N-vinyl-ε.
-Caprolactam and the like. But,
Monofunctional electron beam curable organic compound used in the present invention,
It is not limited to the compounds exemplified above.

The di (meth) acrylate used as the second component in the electron beam-curable resin composition of the present invention is:
Preferably, the molecular weight represented by the general formula (8) is 500
A polyether polyurethane di (meth) acrylate having a polyether structure of up to 10,000, a polyester polyurethane di (meth) acrylate having a polyester structure having a molecular weight of 500 to 10,000 represented by the general formula (9), the general formula (10) or Di (meth) acrylate having a dimer acid structure derived from a dimer of unsaturated higher fatty acid and having a molecular weight of 500 to 10,000 represented by (11), and a polyolefin structure having a molecular weight of 500 to 10,000 represented by formula (12) A polyolefin polyurethane di (meth) acrylate having the formula: and a polyether structure represented by the general formula (13),
And polyether di (meth) acrylate having a molecular weight of 0. However, the di (meth) acrylate used in the present invention is not limited to the compounds exemplified above.

The above polyether polyurethane di (meth)
In the acrylate polyether structure represented by the general formula (8), n is 0 or an integer of 1 to 9, preferably 1 to 4, and m is (n +
1) An integer satisfying xm = 20 to 300, and preferably satisfying (n + 1) xm = 30 to 250. If the value of n exceeds 9, there is a disadvantage that the synthesis of the polyether structure itself becomes difficult and the cost increases. Also, (n
When the value of +1) × m is less than 20, a cured product obtained by irradiation with an electron beam from the obtained resin composition containing polyether polyurethane di (meth) acrylate may exhibit extremely low flexibility. The value of (n + 1) × m is
If it exceeds 300, the viscosity of the resulting polyether polyurethane di (meth) acrylate will be too high, and the flowability will be poor, so that handling may be difficult.

The molecular weight of the polyether structure of the above formula (8) is from 500 to 10,000, preferably from 600 to 5,000. When the molecular weight of the polyether structure of the formula (8) is less than 500, the flexibility of the cured product obtained by curing the obtained polyether polyurethane di (meth) acrylate-containing resin composition by electron beam irradiation is low. Therefore, when it is bent, cracks may occur on the surface of the cured product.
On the other hand, if it exceeds 10,000, the viscosity of the obtained compound becomes extremely high, the fluidity becomes poor and the handling becomes difficult, and the obtained polyether polyurethane di (meth) acrylate-containing resin composition is further irradiated with electron beam The cured product obtained by the curing has a sticky feeling due to poor curing and may not be practical.

Of the di (meth) acrylates used in the present invention, the polyether polyurethane di (meth) acrylate having a polyether structure represented by the formula (8) is a compound comprising a polyether polyol, a polyisocyanate and a (meth) acryloyl group. Can be produced by reacting the compound with That is, the polyether polyurethane di (meth) acrylate having a polyether structure of the formula (8) used in the present invention can be synthesized by the above-mentioned known method. It is obtained by reacting and further reacting with hydroxy (meth) acrylate. The types of the polyisocyanate and hydroxy (meth) acrylate used here are not particularly limited. The polyether polyol used for the synthesis of the polyether polyurethane di (meth) acrylate includes:
The compound is not particularly limited as long as it is a compound capable of giving an ether structure represented by the general formula (8), and examples thereof include polyethylene glycol, 1,2-polypropylene glycol,
1,3-polypropylene glycol, polytetramethylene glycol, 1,2-polybutylene glycol, polyisobutylene glycol, polytetrahydrofuran polyol, and the like can be used, and the block and random copolymers of the polyether polyol compound and other compounds can be used. For example, a polyol composed of a polymer can be used.

The polyisocyanate to be reacted with the polyether polyol is 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) fumarate, 6-isopropyl-
Examples thereof include 1,3-phenyl diisocyanate, 4-diphenylpropane diisocyanate, and lysine diisocyanate. Of these polyisocyanates, it is preferable to use 2,6-tolylene diisocyanate, isophorone diisocyanate, or 4,4'-diphenylmethane diisocyanate.

Examples of the hydroxy (meth) acrylate used in the synthesis of the polyether polyurethane di (meth) acrylate having a polyether structure represented by the general formula (8) include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl. (Meth) acrylate,
And 2-hydroxy-3-phenoxypropyl (meth)
Acrylate and the like. Among these, it is preferable to use 2-hydroxyethyl (meth) acrylate. The polyether polyurethane di (meth) acrylate having a polyether structure of the formula (8) that can be used in the present invention preferably has a molecular weight of 700 to 10,000, more preferably 700 to 6,000.
It is.

As the polyether polyurethane di (meth) acrylate used in the present invention, polyurethane diacrylate of polyethylene glycol, polyurethane diacrylate of polypropylene glycol, polyurethane diacrylate of tetramethylene glycol, and the like can be used. As a commercial product, CJ8
And polyether polyurethane di (meth) acrylate products such as CJ11 series (Nippon Kasei) and PPG series and PTMG series (Arakawa Chemical Industries). Of course, the polyether polyurethane di (meth) acrylate used in the present invention is not limited to these. In the present invention,
Polyurethane di (meth) acrylate having a polyether structure of the formula (8) in the molecule can be used alone or in combination of two or more thereof.

In the general formula (8) representing the polyether structure, as long as n and m satisfy the above conditions, the repeating unit of the ether structure may be separated by an aromatic polyol residue. For example, it may be divided into two or more blocks by at least one member selected from a bisphenol A residue, a bisphenol F residue, and a bisphenol S residue.

The general formula (1) representing the ether structure of the polyether di (meth) acrylate used in the present invention
In 3), n is 0 or an integer of 1 to 9, preferably an integer of 1 to 4, and (n + 1) × m ′ is 8
~ 200, more preferably 12 ~ 200.
If n exceeds 9, the synthesis of the polyether itself becomes difficult, and the cost may increase. Also, (n
When +1) × m ′ is less than 8, the flexibility of the cured product obtained by electron beam irradiation is significantly impaired. On the other hand, when it exceeds 200, the viscosity becomes too high, the fluidity is poor, and the handling is difficult. It may be. Therefore, the molecular weight of the polyether structure is from 150 to 5,000, more preferably from 250 to 1,000. When the molecular weight of the polyether structure is less than 150, a cured product obtained by curing the obtained polyether di (meth) acrylate-containing electron beam curable resin composition by electron beam irradiation has poor flexibility and is bent. In some cases, cracks may occur on the surface of the cured product. On the other hand, if it exceeds 5,000, the viscosity of the polyether di (meth) acrylate becomes extremely high, resulting in poor fluidity, which makes not only difficult handling and coating work on a sheet-like support, but also an increase in the electronic properties. The coating film cured by the irradiation of light may have a sticky feeling due to poor curing, and may not be usable as the material of the present invention. As long as n and m ′ in the general formula (13) representing the polyether structure satisfy the above conditions, the repeating unit of the ether structure may be separated by an aromatic polyol residue. It may be separated by a member selected from A residue, bisphenol F residue, bisphenol S residue and the like. In the di (meth) acrylate used in the present invention, the polyether di (meth) acrylate having an ether structure represented by the general formula (13) is the same as the general formula (13)
There is no particular limitation as long as it is a compound that can satisfy the ether structure represented by the following formula. For example, polyethylene glycol di (meth) acrylate, 1,2-polypropylene glycol di (meth) acrylate, and 1,3-polypropylene glycol Di (meth) acrylate, di (meth) acrylate of polytetramethylene glycol, 1,2-
Di (meth) acrylate of polybutylene glycol, di (meth) acrylate of polyisobutylene glycol,
Di (meth) acrylate of polytetrahydrofurandiol, di (meth) acrylate of alkylene oxide-added diol such as ethylene oxide, propylene oxide or butylene oxide adduct of bisphenol A, F or S, and having the bisphenol skeleton described above. Examples thereof include di (meth) acrylates of hydrogenated derivatives of diol compounds, and di (meth) acrylates of diols of blocks of various polyether polyol compounds and other compounds and random copolymers.

As the polyether di (meth) acrylate having an ether structure of the general formula (13) used in the present invention, diacrylate of polyethylene glycol and diacrylate of polypropylene glycol can be used. -200 series (manufactured by Toagosei), Kayarad PEG-DA series (manufactured by Nippon Kayaku), Blemmer PDE-400 (manufactured by Nippon Yushi), New Frontier PE series, New Frontier BPE series (above, Daiichi Kogyo Chemical) Polyether di (meth)
Acrylate products may be mentioned, but the invention is not limited thereto. In the present invention, the polyether di (meth) acrylate having a polyether structure represented by the formula (13) may be a single kind or two or more kinds thereof.
More than one species can be used in combination.

In the present invention, the polyester polyurethane di (meth) acrylate used as the di (meth) acrylate-containing second component has a polyester structure represented by the aforementioned general formula (9) and having a molecular weight of 500 to 10,000. It has. The molecular weight of the polyester structure represented by the general formula (9) is 500 to 10,000.
00, more preferably 1,000.
~ 5,000. Polyester structure having a molecular weight of 50
When it is less than 0, the cured product obtained by curing the obtained polyester polyurethane di (meth) acrylate-containing resin composition by electron beam irradiation is poor in flexibility, so that when it is bent, the surface thereof has cracks. May occur. On the other hand, if it exceeds 10,000, the viscosity of the obtained compound becomes extremely high, the fluidity becomes poor and the handling becomes difficult, and the resin composition containing this compound is cured by electron beam irradiation. The cured product has a sticky feeling due to poor curing and may not be practical.

The polyester polyurethane di (meth) acrylate having a polyester structure of the formula (9) used as the electron beam-curable oligomer in the present invention is
It is obtained by reacting a polyester polyol with a polyisocyanate and a compound having a (meth) acryloyl group. That is, the polyester polyurethane di (meth) acrylate having a polyester structure of the formula (9) used in the present invention can be synthesized by a known method, but is generally reacted with a polyester polyol and a polyisocyanate, Further, it is obtained by reacting hydroxy (meth) acrylate with this. The types of the polyisocyanate and hydroxy (meth) acrylate used here are not particularly limited.

The above-mentioned polyester polyurethane di (meth)
The polyester polyol used in the synthesis of the acrylate is not particularly limited as long as it is a polyol compound having an ester structure represented by the general formula (9), but is preferably an aliphatic diol (eg, ethylene glycol, 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, and 2,5-dimethyl-
2,5-hexanediol, etc.), aromatic diols (eg, catechol, resorcin, hydroquinone, 4-t
-Butyl catechol, 2-t-butyl catechol, 1,
4-dihydroxynaphthalene, p-hydroxyphenethyl alcohol, bisphenol A, bisphenol F,
And diols such as alicyclic diols (eg, hydrogenated bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S), and an aliphatic dicarboxylic acid (eg, oxalic acid). Dicarboxylic acids such as, for example, malonic acid, succinic acid, glutaric acid, and adipic acid), aromatic dicarboxylic acids (such as phthalic acid, isophthalic acid, and terephthalic acid), and alicyclic dicarboxylic acids (such as hydrogenated phthalic acid). And a polyester polyol such as a block copolymer of the polyester polyol compound and another compound and a random copolymer, and the like.

As the diol component constituting the polyester polyol, for example, ethylene glycol, 1,
3-propylene glycol, 1,4-butanediol,
It is more preferable to use an aliphatic diol such as neopentyl glycol and 1,6-hexanediol. As the dicarboxylic acid component constituting the polyester polyol, it is more preferable to use an aliphatic dicarboxylic acid, and particularly preferable to use adipic acid.

As the polyether polyurethane di (meth) acrylate having a polyester structure represented by the general formula (9) used in the present invention, urethane diacrylate of polypropylene glycol adipate, urethane diacrylate of polybutylene glycol adipate, polyneopentyl glycol adipate Urethane diacrylate and urethane diacrylate of polypropylene glycol phthalate can be used. For example, as commercial products, PG series, NP series, IP series (above, manufactured by Arakawa Chemical Industries), Diabeam UK-6000 series ( Examples thereof include polyether polyurethane di (meth) acrylate products such as Mitsubishi Rayon, but the present invention is not limited thereto. In the present invention, the polyurethane di (meth) acrylate having the specific polyester structure of the formula (9) in the molecule can be used alone or in combination of two or more.

The di (meth) acrylate-containing component used in the present invention is derived from a dimer of unsaturated higher fatty acids and has a dimer acid structure having a dimer acid structure represented by the general formula (10) or (11). ) Acrylates can be used. The general formula (1) of the above di (meth) acrylate
The dimer acid structures represented by (0) and (11) are derived from a dimer of higher unsaturated fatty acids (dimer acid), have two long-chain alkyl groups, and have a total number of carbon atoms of 3
6. Specifically, di (meth) acrylates having a dimer acid structure include, for example, conventionally known unsaturated higher fatty acids containing linoleic acid, such as safflower oil, soybean oil, linseed oil, and tall oil. It is synthesized by preparing a dimer acid by polymerizing by a method, reacting the dimer acid with an epoxy compound, and further reacting with hydroxy (meth) acrylate. The di (meth) acrylate having the dimer acid structure is obtained by reacting an epoxy compound with the dimer acid, then reacting the diisocyanate with a polyisocyanate, and further reacting the dimer acid with (meth) acrylic acid. A di (meth) acrylate of a dimer acid having a bond can be obtained. On the other hand, a urethane bond can be introduced by preparing a dimer diol by reducing the dimer acid, reacting the dimer diol with a polyisocyanate, and further reacting a hydroxy (meth) acrylate. Further, the dimer diol is reacted with a polybasic acid, and the reaction product is reacted with hydroxy (meth) acrylate, whereby a di (meth) acrylate having a dimer acid structure having an ester bond is obtained.

The dimerization reaction product derived from the above-mentioned natural unsaturated higher fatty acid is a mixture of the dimer acids of the general formulas (10) and (11). The weight composition ratio of the alicyclic polybasic acid and the branched polybasic acid of the general formula (10) is about 60/40 to 80/20. This composition varies depending on the reaction conditions during the production of dimer acid. An unsaturated bond may remain in the dimer acid after the synthesis, and in this case, the unsaturated bond may be reduced to a saturated bond. The molecular weight of the di (meth) acrylate having a dimer acid structure used in the present invention is preferably from 500 to 10,000, more preferably from 1,000 to 5,000. If the molecular weight of the di (meth) acrylate having a dimer acid structure is less than 500, the cured product cured by electron beam irradiation from a resin composition containing the same has poor flexibility, and therefore its surface is cracked when bent. May occur. On the other hand, if it exceeds 10,000, the viscosity of the obtained compound becomes extremely high, resulting in poor fluidity and difficult handling, and furthermore, it is obtained by irradiating the resin composition containing this compound with an electron beam. The cured product may have a sticky feeling due to poor curing, and may not be practical.

As the di (meth) acrylate having a dimer acid structure represented by the general formulas (10) and (11) used in the present invention, epoxy-modified dimer acid diacrylate,
Examples of the ester-modified dimer acid diacrylate include commercially available products such as dimer acid di (meth) acrylate products such as DA series (manufactured by Arakawa Chemical Industries), but the present invention is not limited thereto. It is not something to be done. In the present invention, these di (meth) acrylates having a dimer acid structure can be used alone or in combination of two or more.

In the present invention, a di (meth) acrylate-containing component represented by the general formula (12)
Polyolefin polyurethane di (meth) acrylate having a polyolefin structure having a molecular weight of 00 to 10,000 can be used. The molecular weight of the polyolefin acid structure of the formula (12) of the di (meth) acrylate used in the present invention is preferably from 500 to 10,000 in order to secure sufficient flexibility of the electron beam-cured sheet composite material.
And more preferably 1,000 to 5,000. If the molecular weight of the polyolefin structure is less than 500, the cured product obtained by irradiating the resin composition containing this di (meth) acrylate with an electron beam has poor flexibility,
Therefore, when it is bent, the surface may be cracked. On the other hand, if it exceeds 10,000, the viscosity of the obtained compound becomes extremely high, resulting in poor fluidity, making handling difficult. The cured product has a sticky feeling due to poor curing, and may not be practical. Accordingly, b in the above general formula (12) is an integer such that the molecular weight of the polyolefin structure satisfies 500 to 10,000.

The di (meth) acrylate having a polyolefin structure of the formula (12) used in the present invention is obtained by reacting a linear or branched alkyldiol with a polyisocyanate. It is synthesized by reacting hydroxy (meth) acrylic acid. Examples of the linear or branched alkyl diols include polyolefin diols selected from polyethylene, polypropylene, hydrogenated 1,2-polybutadiene, and the like.

Examples of the polyolefin polyurethane di (meth) acrylate having a polyolefin structure of the general formula (12) used in the present invention include urethane diacrylate of polyethylene diol and urethane diacrylate of hydrogenated polybutadiene diol. KU511 series (Arakawa Chemical Industries), TE
Examples include polyolefin polyurethane di (meth) acrylate products such as A1 series (manufactured by Nippon Soda), but the present invention is not limited thereto. In the present invention, these di (meth) acrylates having a polyolefin structure can be used alone or in combination of two or more.

The electron beam-curable resin composition of the present invention comprises at least one monofunctional electron beam-curable organic compound having a Tg of 20 ° C. or more when formed into a homopolymer;
The seed di (meth) acrylate has a weight composition ratio of 90/10 to
It is obtained by blending so as to be 10/90, preferably 80/20 to 20/80. Such an electron beam curable resin composition of the present invention is a cured product obtained by irradiating it with an electron beam, for example, an elongation at break of an electron beam cured film of 100.
% Or more, and particularly excellent flexibility can be imparted to the electron beam-curable resin-coated sheet-like composite material. The content of the di (meth) acrylate-containing second component is 90% by weight of the total weight of all the electron beam-curable unsaturated organic compounds contained in the electron beam-curable resin composition.
If the amount exceeds the above range, the viscosity of the obtained composition may be too high, handling may be difficult, and / or a problem such as a sticky feeling on the surface of the cured product may occur. If the content of the di (meth) acrylate-containing second component is less than 10% by weight of the total weight of the composition, the obtained electron beam cured product becomes less flexible and brittle, and the cured product, for example, cured coating In some cases, the film may be easily cracked.

In one embodiment of the electron beam-curable resin composition of the present invention, the monofunctional electron beam-curable organic compound-containing first component comprises acryloylmorpholine, and the di (meth) acrylate-containing second component comprises A polyether polyurethane di (meth) represented by the general formula (8) and having a polyether structure having a molecular weight of 500 to 10,000.
Acrylate, a polyether di (meth) acrylate having a polyether structure represented by the general formula (13) and having a molecular weight of 150 to 5,000, and a polyester structure represented by the general formula (9) and having a molecular weight of 500 to 10,000 A polyester polyurethane di (meth) acrylate having
And at least one member selected from di (meth) acrylates having a dimer acid structure derived from a dimer of unsaturated higher fatty acids represented by the general formulas (10) and (11) and having a molecular weight of 500 to 10,000. Consists of

In another embodiment of the electron beam-curable resin composition of the present invention, the first component containing a monofunctional electron beam-curable organic compound has the tricyclo [5.2.1.0 ^2,6 ] decane structure. The mono (meth) acrylate represented by the general formula (1), wherein the di (meth) acrylate-containing second
The component has a molecular weight of 500 to 1 represented by the general formula (8).
A polyether polyurethane di (meth) acrylate having a polyether structure of 000, a polyester polyurethane di (meth) acrylate having a polyester structure having a molecular weight of 500 to 10,000 represented by the general formula (9),
And a molecular weight of 500 to 10,000 expressed by the general formula (12).
It comprises at least one member selected from polyolefin polyurethane di (meth) acrylate having a polyolefin structure of 00.

In another embodiment of the electron beam-curable resin composition of the present invention, the monofunctional electron beam-curable organic compound-containing first component is a cycloalkyl mono (meth) compound represented by the general formula (2). A) a polyether polyurethane di (meth) acrylate having a polyether structure having a molecular weight of 500 to 10,000 and represented by the general formula (8), wherein the di (meth) acrylate-containing second component comprises the acrylate; ) 500 ~
A polyester polyurethane di (meth) acrylate having a polyester structure of 10,000, and the general formula (1)
It comprises at least one member selected from polyolefin polyurethane di (meth) acrylate having a polyolefin structure having a molecular weight of 500 to 10,000 and represented by 2).

In another embodiment of the electron beam-curable resin composition of the present invention, the monofunctional electron beam-curable organic compound-containing first component comprises a tertiary alcohol represented by the general formula (3). A mono (meth) acrylate, wherein the di (meth) acrylate-containing second component is a polyether polyurethane di (meth) acrylate represented by the general formula (8) and having a polyether structure having a molecular weight of 500 to 10,000; Formula (9) having a molecular weight of 500 to
A polyester polyurethane di (meth) acrylate having a polyester structure of 10,000, and the general formula (1)
It comprises at least one member selected from polyolefin polyurethane di (meth) acrylate having a molecular weight of 500 to 10,000 represented by 2).

In another embodiment of the electron beam-curable resin composition of the present invention, the monofunctional electron beam-curable organic compound-containing first component has a succinimide structure, and has the general formula (4) Wherein the di (meth) acrylate-containing second component is a polyether polyurethane di (meth) acrylate having a polyether structure represented by the general formula (8) and having a molecular weight of 500 to 10,000. A polyester polyurethane di (meth) acrylate having a polyester structure having a molecular weight of 500 to 10,000 represented by the general formula (9) and a dimer of an unsaturated higher fatty acid represented by the general formulas (10) and (11). Molecular weight with dimer acid structure derived from 50
It comprises at least one member selected from 0 to 10,000 di (meth) acrylate.

In another embodiment of the electron beam-curable resin composition of the present invention, the monofunctional electron beam-curable organic compound-containing first component has a bisphenol structure and is represented by the general formula (5). Wherein the di (meth) acrylate-containing second component is a polyether polyurethane di (meth) acrylate having a polyether structure having a molecular weight of 500 to 10,000 and represented by the general formula (8), A polyester polyurethane di (meth) acrylate having a polyester structure having a molecular weight of 500 to 10,000 represented by the general formula (9) and a polyolefin polyurethane di (meth) acrylate having a molecular weight of 500 to 10,000 represented by the general formula (12). Consisting of at least one member.

In another embodiment of the electron beam-curable resin composition of the present invention, the first component containing a monofunctional electron beam-curable organic compound has a cyclic dicarboxylic acid monoester structure, 6) wherein the di (meth) acrylate-containing second component is a mono (meth) acrylate represented by the following general formula (8):
Polyether polyurethane di (meth) acrylate having a polyether structure of 10,000, and the general formula (9)
And at least one member selected from polyester polyurethane di (meth) acrylate having a polyester structure having a molecular weight of 500 to 10,000 represented by

In another embodiment of the electron beam-curable resin composition of the present invention, the first component containing the monofunctional electron beam-curable organic compound is an N-vinyl lactam compound represented by the general formula (7) Wherein the di (meth) acrylate-containing second component is a polyether polyurethane di (meth) acrylate having a polyether structure having a molecular weight of 500 to 10,000 and represented by the general formula (8); A polyester polyurethane di (meth) acrylate having a polyester structure having a molecular weight of 500 to 10,000 and a dimer acid structure derived from a dimer of an unsaturated higher fatty acid represented by the general formula (10) or (11) It comprises at least one member selected from 500 to 10,000 di (meth) acrylates.

In still another embodiment of the electron beam-curable resin composition used in the present invention, a homofunctional polymer having a monofunctional electron beam-curable organic compound having a Tg of 20 ° C. or higher is used. ACMO is used as one component, and a di (meth) acrylate-containing second component is represented by the general formula (1)
When the polyether di (meth) acrylate having a polyether structure of 3) is used, its weight composition ratio is 90/1.
0 to 51/49, particularly preferably 85/1.
5 to 51/49. When the above components are used at such a mixing ratio, the elongation at break of the electron beam-curable resin film forming the electron beam-curable resin coating layer can be set to 50% or more, and sufficient flexibility for practical use is obtained. It can be applied to a wire-cured resin-coated sheet-like composite material. The content of the polyether di (meth) acrylate in the electron beam-curable resin composition of the present invention is defined as the total weight of all the electron beam-curable unsaturated organic compounds contained in the electron beam-curable resin composition.
If the content exceeds 49% by weight, the Young's modulus and the elongation at break of the electron beam-curable resin film obtained by electron beam irradiation decrease, and the mechanical properties are extremely lowered, which may cause a practical problem. If the content of the polyether di (meth) acrylate is less than 10% by weight, the cured resin film may have low flexibility, become brittle, and easily crack.

In the present invention, as described above, the monofunctional electron beam-curable organic compound having a homopolymer Tg of 20 ° C. or higher includes, as described above, ACMO and tricyclohexane.
[5.2.1.0 ^2,6 ] Mono (meth) acrylate of the general formula (1) having a decane structure, cycloalkyl mono (meth) acrylate of the general formula (2), and tertiary compound of the general formula (3) Alcohol mono (meth) acrylate, mono (meth) acrylate of general formula (4) having a succinimide structure, mono (meth) acrylate of general formula (5) having a bisphenol structure, and cyclic dicarboxylic acid monoester structure It is preferable to use a mono (meth) acrylate of the above general formula (6), an N-vinyllactam compound of the above general formula (7), or the like. These may be used alone or as a mixture of two or more compounds. can do.

The di (meth) acrylate used in the present invention together with the monofunctional electron beam-curable organic compound having a homopolymer having a Tg of 20 ° C. or higher is, as described above, Polyether polyurethane di (meth) acrylate having a polyether structure of the formula (8), polyester polyurethane di (meth) acrylate having a polyester structure of the formula (9), and a dimer of the formulas (10) and (11) Use of di (meth) acrylate having an acid structure, polyolefin polyurethane di (meth) acrylate having a polyolefin structure of the general formula (12), and polyether di (meth) acrylate having a polyether structure of the general formula (13) Are preferred, and these may be used alone or as a mixture of two or more. Can be used.

Further, two or more kinds of the monofunctional electron beam-curable organic compounds and the di (meth) acrylate 2
Even when used in combination of more than one type, when they are blended so that the weight composition ratio of each total amount is preferably 90/10 to 10/90, more preferably 80/20 to 20/80. Thus, the sheet-like composite material of the present invention can be given sufficient flexibility.

However, among the monofunctional electron beam curable organic compounds, the highly hydrophilic ACMO, the mono (meth) acrylate of the general formula (4) having a succinimide structure, or the general formula (4) When the N-vinyllactam compound of 7) is used, it is preferable to select and use di (meth) acrylate having as low a hydrophobicity as possible or di (meth) acrylate having a highly hydrophilic substituent. However, when a combination of a highly hydrophobic di (meth) acrylate, such as polyolefin di (meth) acrylates, and a highly hydrophilic, monofunctional electron beam-curable organic compound is unavoidably used, the resin composition From the viewpoint of the compatibility and uniformity of the product, and the compatibility and uniformity of the cured product, in addition to those components, selected from the monofunctional electron beam-curable organic compounds, and have a relatively high hydrophobicity. It is preferable to use one or more kinds and / or one or more kinds selected from the di (meth) acrylates and having relatively low hydrophobicity.

Further, the electron beam-curable resin composition of the present invention comprises a monofunctional electron beam-curable organic compound having a Tg of less than 20 ° C. when formed into a homopolymer, and a tri- or higher functional (meth) acrylate. One or more selected from the above may be blended within a range in which the obtained electron beam cured body has sufficient flexibility, but the blending amount is based on 100 parts by weight of the electron beam curable resin composition. It is preferably at most 10 parts by weight.

The sheet-like composite material of the present invention comprises a sheet-like support and an electron beam-curable resin formed on at least one surface thereof and comprising the electron beam-curable body of the electron beam-curable resin composition of the present invention. And a coating layer. This electron beam curable resin coating layer preferably has a breaking elongation of 50% or more.

Further, another sheet composite material of the present invention has a sheet-like support and an electron beam-curable resin composite coating layer formed on at least one surface of the sheet-like support. An inner resin layer adjacent to at least the sheet-like support, and a laminate of a plurality of resin layers including an outermost resin layer disposed on the outermost side, and at least one of the plurality of resin layers is It includes an electron beam cured body of the electron beam curable resin composition of the present invention.

In the sheet-like composite material of the present invention, the resin film forming the resin layer containing the electron beam-curable resin preferably has an elongation at break of 50% or more.

In order to enhance the surface smoothness and gloss of the sheet-like composite material of the present invention, it is preferable to manufacture the electron beam-curable resin coating layer by a cast EB method. , On one side of the support,
A coating liquid layer is formed by applying an electron beam curable resin composition for forming a resin coating layer, and the coating liquid layer is formed of a metal-made rotary cylindrical molded body having a smooth and high gloss, or a high smoothness. Laminate on the surface of the glossy sheet material, irradiate the multilayer body formed by it with electron beam to cure the coating liquid layer, and join the cured product to the support to form a laminate Then, a method of peeling the laminate from the surface of the molded body, that is, a direct coating method can be used. Further, as another manufacturing method, an electron beam curable resin composition for forming a resin coating layer is applied on a molding surface of the molded body to form a coating liquid layer, and the coating liquid layer is formed on the surface of the support. Are laminated, and the multilayer body thus formed is irradiated with an electron beam to cure the coating liquid layer and join the obtained resin coating layer and the support to form a laminate. A method of peeling the body from the surface of the molded body, that is, a transfer coating method can be used.

The type of the sheet-like support used in the present invention is not particularly limited, and may be paper (for example, high quality paper), plastic film, cloth, non-woven fabric, aluminum foil, or the like having a thickness of about 6 to 500 μm. Although a relatively thin one 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. There is no particular limitation on the type of paper substrate used in the present invention. As the pulp forming the paper substrate, generally, those containing natural pulp as a main component such as softwood pulp manufactured from fir, toga, etc., hardwood pulp manufactured from maple, beech, poplar, etc., and softwood hardwood mixed pulp are widely used. Bleached pulp such as kraft pulp, sulfite pulp and soda pulp can be used. A paper substrate made from pulp containing synthetic fibers or synthetic pulp can also be used as the sheet-like support. 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. Further, the sheet-like support used in the present invention may be, for example, clay, talc, kaolin, calcium carbonate, aluminum hydroxide, titanium dioxide, magnesium hydroxide, or plastic pigment on one or both sides of a paper substrate such as woodfree paper. And a synthetic resin such as a pigment, an acrylic resin, a polyurethane resin, an ethylene-acrylic acid copolymer resin, a vinyl acetate-ethylene copolymer resin, a styrene-butadiene copolymer resin, or a vinylidene chloride resin as a main component. Pigment coated paper such as coated paper, cast coated paper, art paper, or the like, on which a pigment coated layer is formed, or laminating with a polyolefin resin such as polyethylene on one or both sides of a paper substrate. Laminated paper may be used.

Further, instead of the paper substrate used in the present invention, a plastic film or a sheet-like support such as so-called synthetic paper may be used. For example, a film formed from a thermoplastic resin composition containing a polyolefin resin such as a polypropylene resin or a polyethylene resin by a melt extrusion method can be used as a 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 paper include clay, talc, kaolin, calcium carbonate, titanium dioxide, pigments such as magnesium hydroxide, metal soaps such as zinc stearate, and various surfactants. And the like, and one or more kinds of colored pigments and the like.

In the direct or transfer coating method, a sheet material for molding used as a molded body (sheet for molding)
The material is not 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,
A metal-deposited paper or the like is preferable, and a release aid such as silicone or wax may be supplied to the surface of the paper to facilitate the release of the resin coating layer. Further, the surface of the molding sheet is subjected to an appropriate treatment (for example, silicone treatment) in advance,
The cured resin coating layer may be easily separated. Also,
The molding sheet can be processed into an endless belt shape and used repeatedly.

The metal cylindrical rotating body used as a molded body in the direct or transfer coating method is not particularly limited in its material shape.
A mirror-finished smooth surface formed of copper, chromium, or the like is used. In order to facilitate separation between the resin coating layer and the surface of the molded body, a separation aid such as silicone oil or wax can be supplied to the surface of the metal cylindrical rotary member.

Examples of the method of applying the electron beam curable resin composition on the surface of the metal cylindrical rotating body or the surface of the support include bar coating, air doctor coating, blade coating, squeeze coating, and the like. 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, gate roll Coating methods such as a 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 a metal cylindrical rotating body is used as a molded body, it is preferable to use a roll coating method using an application rubber roll or an offset gravure coating method in order to prevent the surface from being damaged. A contact-type fountain coater, slit die coater or the like 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 g / cured after curing.
is preferably m ^2, more preferably 5 ~40g / m ^2. If the coating amount is less than 3 g / m ² , the resulting coated body will have insufficient smoothness, fail to provide aesthetics, and may have a reduced gloss. If it exceeds 60 g / m ² , the effect may be saturated and the cost may increase. When a paper substrate is used as the sheet-like support, the coating amount after curing of the resin coating layer is preferably 3 g / m ² or more, more preferably 5 to 20 g / m ² . 3g resin coating
If it is less than / m ² , the formation unevenness of the paper substrate may not be filled.

Further, when a paper substrate is used as the sheet-like support, it is preferable that the electron beam-curable resin coating layer has a laminated structure of two or more layers. More preferably, an electron beam-curable resin layer obtained from the composition is provided adjacent to the paper substrate. 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 and the electron beam-curable contact therewith are improved. An undercoat layer containing a synthetic resin as a main component may be provided between the 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 a paper substrate is used as the sheet-shaped support, polyvinyl alcohol, hydroxyethyl cellulose are separately provided on the paper substrate in order to prevent the electron beam-curable resin composition from penetrating into the paper substrate. Alternatively, the undercoat layer may be provided with a barrier agent such as oxidized starch. Providing the undercoat layer between the sheet-like support and the electron beam-curable resin coating layer in contact with the sheet-like support, as described above, comprises coating the sheet-like support with the electron beam-curable resin composition and forming a resin coating layer. Is a means commonly used in the field of forming photographic printing paper, for example, a support for photographic printing paper coated with an electron beam-curable resin composition, an electrophotographic transfer paper, a heat-sensitive base paper, a process release paper, and a thermal transfer. It is used in receiving paper, ink jet recording paper, wrapping paper and the like.

Further, in order to improve the whiteness of the sheet-like composite material of the present invention, a white inorganic and / or organic pigment can be blended in the electron beam-curable resin composition. The type of this pigment is not particularly limited, and inorganic pigments such as clay, kaolin, talc, magnesium hydroxide, aluminum hydroxide, calcium carbonate, titanium dioxide (anatase type and rutile type), zinc white, barium sulfate,
And organic pigments such as polystyrene known as plastic pigments. These pigments may be untreated on the surface, but in order to improve dispersibility in the electron beam-curable resin composition, siloxane, alumina, alcohol, a silane coupling agent , Rosin acid, fatty acid or the like. Also, these pigments
One type or a mixture of two or more types may be used. Further, the pigment can be blended in an addition amount within a range that does not impair the flexibility of the electron beam curable resin. It is preferably from 10 to 50 parts by weight, more preferably from 20 to 40 parts by weight. If the amount of the pigment is less than 10 parts by weight, the concealability of the pigment may be poor,
When the amount is more than 50 parts by weight, the viscosity of the obtained electron beam-curable resin composition becomes excessively high, the fluidity becomes poor, and the coating operation on the sheet-like support may become difficult.

The electron beam-curable resin composition of the present invention may contain an inorganic
In order to disperse the organic pigment, a three-roll mill (three-roll mill), a two-roll mill (two-roll mill), a Cowles dissolver, a homomixer, a sand grinder, a planetary mixer, or an ultrasonic disperser may be used. it can. The electron beam-curable resin composition of the present invention may also contain a known auxiliary agent such as a dispersant, a release agent, an antifoaming agent, a coloring agent, a dye, or a preservative, if necessary. Can be blended within a range in which is not impaired.

The electron beam irradiator used for electron beam irradiation is not particularly limited.
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 during electron beam irradiation is 10
It is preferably 0 to 300 kV.
It is preferably from 0.1 to 8 Mrad, particularly preferably from 0.5 to 6 Mrad.

[0089]

The present invention will be further described with reference to the following examples, but the scope of the present invention is, of course, not limited thereto. In addition, in the indication of the components of each electron-curable resin composition, the measured value of the glass transition temperature (Tg) of a homopolymer obtained by radically polymerizing the compound (in Seiko Denshi, DSC 22C).

Example 1 A sheet-like composite material having excellent flexibility was produced by the following steps. One component of electron beam curable resin composition (parts by weight) Diacrylate 25 of polyethylene glycol (molecular weight 600) (trademark: Kayarad PEG600-DA, manufactured by Nippon Kayaku) Acryloylmorpholine (Tg = 140 ° C) (trademark: ACMO) 75 Co., Ltd. 75
At 0 rpm, the mixture was dispersed and mixed for 20 minutes to prepare an electron-curable resin composition 1.

Preparation of Sheet Composite Material The above composition 1 was coated on a coated paper having a basis weight of 145 g / m ² (trade name: OK).
A coating liquid layer was coated on the surface of a sheet-like support made of Topcoat Dall, manufactured by Oji Paper Co., Ltd. using a Mayer bar so that the coating amount after curing was 10 g / m ² . On this coating liquid layer, a 75 μm-thick polyester film 1 to be used as a molded body was superimposed and pressed, and an electron beam was absorbed into the formed multilayer body from the back of the polyester film 1 at an acceleration voltage of 175 kV and an absorption voltage of 175 kV. Irradiation was performed under the conditions of a dose of 3 Mrad and an oxygen concentration of 500 ppm or less to cure the resin coating liquid layer, and simultaneously bond the obtained resin coating layer and the sheet-like support together. Thereafter, the polyester film was peeled off from the resin coating layer to produce a sheet-like composite material having an electron beam-curable resin coating layer.

Test and evaluation method (1) Measurement of flexibility of sheet-like composite material A sample of the above-mentioned sheet-like composite material was bent at an angle of 180 ° so that the resin coating layer was on the outside, and the resin coating layer was cracked. Was visually evaluated. Table 1 shows the test results. The test results were displayed as follows. ×: The resin coating layer is completely broken △: The resin coating layer is slightly cracked ○: No crack is generated in the resin coating layer but wrinkles remain ◎: No crack is generated in the resin coating layer The ones and the circles are practically excellent, and the triangles are practical, but the range of use is limited, and the crosses are not practical. Table 1 shows the test results.

(2) Measurement of Glossiness of Blank Paper The glossiness of blank paper of the sample was measured according to JIS Z8741 using a gloss meter VGS-1D (manufactured by Nippon Denshoku Industries Co., Ltd.) at a gloss of 60 ° / 60 °. . The measured value is 7
Those with 5 or more are excellent in glossiness. Table 1 shows test results
Shown in (3) Measurement of elongation at break of electron beam-curable resin film An electron beam-curable resin film corresponding to the electron beam-curable resin coating layer of the sheet-like composite material obtained as described above was used, and the composition 1 was a polyester film. Using a Mayer bar on one side of (Film 1), the coated amount after curing was 10 g / m ^2.
Is formed, and one surface of another polyester film (film 2) used as the surface of the molded body is overlaid and pressed on the coating liquid layer. The coating liquid layer is cured by irradiating the applied liquid under the conditions of an acceleration voltage of 175 kV, an absorbed dose of 3 Mrad, and an oxygen concentration of 500 ppm or less. Subsequently, the cured coating film is peeled off from both polyester films. The degree was measured using a tensile tester (trade name: STROGRAPH M-2, manufactured by Toyo Seiki) in accordance with JIS P8113. In the tensile test, the distance between the grips of the measurement sample (the length of the measurement portion of the sample) was 10 mm, and the pulling speed was 5 mm / min. The size of the measurement sample is 10 width.
mm, the length was 20 mm, the temperature of the measurement atmosphere was 20 ± 2 ° C., and the relative humidity was 65 ± 5% RH. When the elongation at break of the cured resin film is 50% or more, the sheet-like composite material obtained by coating the same has flexibility that does not hinder practical use,
Furthermore, when the elongation at break is 100% or more, the sheet-like composite material obtained by coating it exhibits extremely excellent flexibility in practice and can withstand severe use conditions sufficiently.
Table 1 shows the test results.

Example 2 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 2 was prepared and used in place of the electron beam curable composition 1. 2 components (parts by weight) of electron beam curable resin composition Diacrylate of polyethylene glycol (molecular weight 270) (trademark: Kayarad PEG300-DA, manufactured by Nippon Kayaku) 25 acryloylmorpholine (Tg = 140 ° C.) (trademark: ACMO) , Manufactured by Kojin Co., Ltd. 75 Table 1 shows the test results.

Example 3 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 3 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylate (trade name: CJ-8-1, manufactured by Nippon Kasei) of the three components (parts by weight) of the electron beam-curable resin composition polypropylene glycol (molecular weight: 2800) 50 Acryloylmorpholine (Tg = 140 ° C.) (trade name: (ACMO, manufactured by Kojin Co., Ltd.) 50 Table 1 shows the test results.

Example 4 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 4 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates of the electron beam curing resin composition 4 Ingredients Amounts (parts by weight) of polypropylene glycol (molecular weight 1000) (Trademark: PPG1000-U, Arakawa Chemical Industries, Ltd.) 50 acryloylmorpholine (Tg = 140 ° C.) (Trademark: ACMO Table 1 shows the test results.

Example 5 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 5 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 5 Ingredients Amounts polyurethane diacrylate 50 (parts by weight) of polypropylene glycol (molecular weight 2100) (Trademark: PPG2000-U, Arakawa Chemical Industries, Ltd.) acryloyl morpholine (Tg = 140 ° C.) (Trademark: ACMO Table 1 shows the test results.

Example 6 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 6 was prepared and used in place of the electron beam curable composition 1. Poly urethane diacrylate of electron beam-curable resin composition 6 Ingredients Amounts (parts by weight) of polypropylene glycol (molecular weight 4200) (Trademark: CJ-11-3, manufactured by Nippon Kasei Chemical Co.) 50 acryloylmorpholine (Tg = 140 ° C.) (TM : ACMO, manufactured by Kojin Co., Ltd. 50 Table 1 shows the test results.

Example 7 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 7 was prepared and used in place of the electron beam curable composition 1. 7 components of electron beam-curable resin composition (parts by weight) Polyurethane glycol (molecular weight: 700) polyurethane diacrylate (trademark: PPG700-MD, manufactured by Arakawa Chemical Industries) 50 Acryloylmorpholine (Tg = 140 ° C.) (trademark: ACMO) Table 1 shows the test results.

Example 8 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 8 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylate of polytetramethylene glycol (molecular weight: 650) blended amount (parts by weight) of 8 components of the electron beam-curable resin composition (trade name: PTMG650-U, manufactured by Arakawa Chemical Industries) 50 Acryloylmorpholine (Tg = 140 ° C.) (trademark) : ACMO, manufactured by Kojin Co., Ltd. 50 Table 1 shows the test results.

Example 9 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 9 was prepared and used in place of the electron beam curable composition 1. 9 components of electron beam curable resin composition (parts by weight) Polyurethane glycol (molecular weight: 1000) polyurethane diacrylate (trademark: K-7553, manufactured by Nippon Kasei) 50 acryloylmorpholine (Tg = 140 ° C) (trademark: ACMO, Table 1 shows the test results.

Example 10 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 10 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates of the electron beam-curable resin composition 10 Ingredients Amounts (parts by weight) of polypropylene glycol (molecular weight 2100) (Trademark: PPG2000-U, Arakawa Chemical Industries, Ltd.) 75 acryloylmorpholine (Tg = 140 ° C.) (Trademark: ACMO Table 25 shows the test results.

Example 11 A sheet composite was prepared and tested in the same manner as in Example 1. However, the following composition 11 was prepared and used in place of the electron beam curable composition 1. 11 components of electron beam-curable resin composition (parts by weight ) Polyurethane diacrylate (molecular weight: 1000) composed of propylene glycol and adipic acid (trade name: PGAA1000, manufactured by Arakawa Chemical Industries, Ltd.) 50 Acryloylmorpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 50 The test results are shown in Table 1.

Example 12 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 12 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates 60 of the electron beam-curable resin composition 12 Ingredients Amounts (parts by weight) polyester of propylene glycol and adipic acid (molecular weight 2000) (Trademark: PGAA2000, manufactured by Arakawa Chemical Industries, Ltd.) acryloyl morpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 40 The test results are shown in Table 1.

Example 13 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 13 was prepared and used in place of the electron beam curable composition 1. 13 components of electron beam-curable resin composition (parts by weight ) Polyurethane diacrylate 60 (molecular weight: 2,000) composed of ethylene glycol and adipic acid (trademark: EGAA2000, manufactured by Arakawa Chemical Industry Co., Ltd.) Acryloylmorpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 40 The test results are shown in Table 1.

Example 14 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 14 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates 60 of the electron beam-curable resin composition 14 Ingredients Amounts (parts by weight) Polyester composed of tetramethylene glycol and adipic acid (molecular weight 2000) (Trademark: BGAA2000, manufactured by Arakawa Chemical Industries, Ltd.) acryloyl morpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 40 Table 1 shows the test results.

Example 15 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 15 was prepared and used in place of the electron beam curable composition 1. 15 components of electron beam curable resin composition (parts by weight ) Polyurethane diacrylate 60 of polyester (molecular weight 1000) composed of methylpentanediol and adipic acid (trademark: MPAA1000, manufactured by Arakawa Chemical Industries, Ltd.) Acryloyl morpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 40 Table 1 shows the test results.

Example 16 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 16 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates 60 of the electron beam-curable resin composition 16 Ingredients Amounts (parts by weight) Polyester composed of hexanediol and adipic acid (molecular weight 1000) (Trademark: HGAA1000, manufactured by Arakawa Chemical Industries, Ltd.) acryloyl morpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 40 The test results are shown in Table 1.

Example 17 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 17 was prepared and used in place of the electron beam curable composition 1. 17 components of electron beam curable resin composition (parts by weight ) Polyurethane diacrylate 60 of polyester (molecular weight: 1000) composed of neopentyl glycol and adipic acid (trademark: NPAA1000, manufactured by Arakawa Chemical Industries, Ltd.) Acryloyl morpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 40 Table 1 shows the test results.

Example 18 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 18 was prepared and used in place of the electron beam curable composition 1. Polyethylene diacrylate 75 (trademark: NPAA1000, manufactured by Arakawa Chemical Industries, Ltd.) of 18 components of electron beam curable resin composition (parts by weight) composed of neopentyl glycol and adipic acid Acryloylmorpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 25 The test results are shown in Table 1.

Example 19 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 19 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates 25 of the electron beam-curable resin composition 19 Ingredients Amounts (parts by weight) Polyester composed of neopentyl glycol and adipic acid (molecular weight 1000) (Trademark: NPAA1000, manufactured by Arakawa Chemical Industries, Ltd.) acryloyl morpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 75 The test results are shown in Table 1.

Example 20 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 20 was prepared and used in place of the electron beam curable composition 1. Polyepoxy diacrylate 50 (trade name: DA1B, manufactured by Arakawa Chemical Industry Co., Ltd.) of 20 components of electron beam curable resin composition (parts by weight) dimer acid (molecular weight: about 1000) Acryloylmorpholine (Tg = 140 ° C.) (Trademark: ACMO, manufactured by Kojin Co., Ltd.) 50 Table 1 shows the test results.

Example 21 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 21 was prepared and used in place of the electron beam curable composition 1. Polyepoxy diacrylate 50 with 21 components of electron beam curable resin composition (parts by weight) dimer acid (molecular weight: about 2,000) (trademark: DA7B, manufactured by Arakawa Chemical Industries, Ltd.) acryloyl morpholine (Tg = 140 ° C.) ( (Trademark: ACMO, manufactured by Kojin Co., Ltd.) 50 Table 1 shows the test results.

Example 22 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 22 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylate 50 containing 22 components (parts by weight) of dimer acid (molecular weight: about 2,000) of the electron beam curable resin composition (trademark: DA10HB, manufactured by Arakawa Chemical Industries, Ltd.) Acryloylmorpholine (Tg = 140 ° C.) (trademark) : ACMO, manufactured by Kojin Co., Ltd. 50 Table 1 shows the test results.

Example 23 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 23 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 23 Ingredients Amounts (parts by weight) Polyurethane diacrylates 50 of polytetramethylene glycol (molecular weight 650) (Trademark: PTMG650-U, Arakawa Chemical Industries, Ltd.) dicyclopentanyl acrylate (Tg = 91 ° C. ) 50 (trademark: FA-513A, manufactured by Hitachi Chemical Co., Ltd.) The test results are shown in Table 1.

Example 24 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 24 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates 50 of the electron beam-curable resin composition 24 Ingredients Amounts (parts by weight) of polypropylene glycol (molecular weight 1000) (Trademark: PPG1000-U, Arakawa Chemical Industries, Ltd.) dicyclopentanyl acrylate (Tg = 91 ° C.) 50 (Trademark: FA-513A, manufactured by Hitachi Chemical Co., Ltd.) The test results are shown in Table 1.

Example 25 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 25 was prepared and used in place of the electron beam curable composition 1. 25 components (parts by weight) of electron beam curable resin composition Polyurethane diacrylate 50 of hydrogenated polybutadiene diol (molecular weight: 1000) (trademark: TEAI-1000, manufactured by Nippon Soda) Dicyclopentanyl acrylate (Tg = 91 ° C.) 50 (trademark: FA-513A, manufactured by Hitachi Chemical Co., Ltd.) The test results are shown in Table 1.

Example 26 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 26 was prepared and used in place of the electron beam curable composition 1. Polyurethane diol (trade name: KU511-1B, manufactured by Arakawa Chemical Industry) of 26 components (parts by weight) of polyolefin diol ( part by weight) of the electron beam curable resin composition 50 Dicyclopentanyl acrylate (Tg = 91 ° C.) 50 (Trademark: FA513-A, manufactured by Hitachi Chemical Co., Ltd.) The test results are shown in Table 1.

Example 27 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 27 was prepared and used in place of the electron beam curable composition 1. 50 polyurethane diacrylate electron beam-curable resin composition 27 Ingredients Amounts (parts by weight) Polyester polyol obtained from neopentyl glycol and adipic acid (molecular weight 1000) (Trademark: NPAA-1000, manufactured by Arakawa Chemical Industries, Ltd.) dicyclo Pentanyl acrylate (Tg = 91 ° C.) 50 (trademark: FA513-A, manufactured by Hitachi Chemical Co., Ltd.) The test results are shown in Table 1.

Example 28 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 28 was prepared and used in place of the electron beam curable composition 1. 50 polyurethane diacrylate electron beam-curable resin composition 28 Ingredients Amounts (parts by weight) of propylene glycol and polyester polyols obtained from adipic acid (molecular weight 1000) (Trademark: PGAA-1000, manufactured by Arakawa Chemical Industries, Ltd.) dicyclopenta Nyl acrylate (Tg = 91 ° C.) 50 (trademark: FA513-A, manufactured by Hitachi Chemical Co., Ltd.) The test results are shown in Table 1.

Example 29 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 29 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates 50 of the electron beam-curable resin composition 29 Ingredients Amounts (parts by weight) of polypropylene glycol (molecular weight 1000) (Trademark: PPG1000-U, Arakawa Chemical Industries, Ltd.) cyclohexyl acrylate (Tg = 40 ° C.) 50 (trademark: (Viscort # 155, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 1.

Example 30 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 30 was prepared and used in place of the electron beam curable composition 1. 30 components of electron beam curable resin composition (parts by weight ) 50 Polyurethane diacrylate (trade name: NPAA-1000, manufactured by Arakawa Chemical Industries) of polyester polyol (molecular weight: 1000) obtained from neopentyl glycol and adipic acid Cyclohexyl acrylate (Tg = 40 ° C.) 50 (trademark: VISCOAT # 155, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 1.

Example 31 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 31 was prepared and used in place of the electron beam curable composition 1. 31 components of electron beam curable resin composition (parts by weight) Polyurethane diacrylate (trade name: TEAI-1000, manufactured by Nippon Soda ) of hydrogenated polybutadiene diol (molecular weight: 1000) 50 Cyclohexyl acrylate (Tg = 40 ° C.) 50 (trademark) : VISCOAT # 155, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 1.

Example 32 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 32 was prepared and used in place of the electron beam curable composition 1. Polyethylene glycol (molecular weight: 1000) polyurethane diacrylate 50 (trademark: PPG1000-U, manufactured by Arakawa Chemical Industries) tert-butyl acrylate (Tg = 41 ° C.) 50 ( Electron beam curable resin composition 32 components blending amount (parts by weight)) (Trademark: TBA, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 1.

Example 33 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 33 was prepared and used in place of the electron beam curable composition 1. 50 polyurethane diacrylate electron beam-curable resin composition 33 Ingredients Amounts (parts by weight) of neopentyl glycol and polyester polyols obtained from adipic acid (molecular weight 1000) (Trademark: NPAA-1000, manufactured by Arakawa Chemical Industries) tert Butyl acrylate (Tg = 41 ° C.) 50 (trademark: TBA, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 1.

Example 34 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 34 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 34 Ingredients Amounts (parts by weight) polyurethane diacrylate hydrogenated polybutadiene diol (molecular weight 1000) (Trademark: TEAI-1000, manufactured by Nippon Soda Co.) 50 tert-butyl acrylate (Tg = 41 ° C.) 50 (Trademark: TBA, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 1.

Example 35 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 35 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylate 50 (trade name: PPG700-U, manufactured by Arakawa Chemical Industries) of 35 components of electron beam curable resin composition (parts by weight) polypropylene glycol (molecular weight: 700) N-acryloyloxyethyl hexahydrophthalimide (Tg = 39 ° C) (trademark: Aronix TO-1429, manufactured by Toagosei Co., Ltd.) 50 The test results are shown in Table 1.

Example 36 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 36 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 36 Ingredients Amounts (parts by weight) 50 polyurethane diacrylate neopentyl glycol and polyester polyols obtained from adipic acid (molecular weight 1000) (Trademark: NPAA-1000, manufactured by Arakawa Chemical Industries) N- Acryloyloxyethyl hexahydrophthalimide (Tg = 39 ° C.) 50 (trademark: Alonix TO-1429, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 1.

Example 37 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 37 was prepared and used in place of the electron beam curable composition 1. Polyepoxy diacrylate 50 of 37 components of electron beam curable resin composition (parts by weight) dimer acid (molecular weight: about 2,000) (trade name: DA7B, manufactured by Arakawa Chemical Industry Co., Ltd.) N-acryloyloxyethyl hexahydrophthalimide 50 (Tg = 39 ° C.) (trademark: Alonix TO-1429, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 1.

Example 38 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 38 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 38 Ingredients Amounts polyurethane diacrylate 50 (parts by weight) of polypropylene glycol (molecular weight 1000) (Trademark: PPG1000-U, Arakawa Chemical Industries, Ltd.) p-cumylphenol EO-modified acrylate 50 (Tg = 35 ° C. ) (Trade name: Alonix TO-1210, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 2.

Example 39 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 39 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylate (trade name: NPAA-1000, manufactured by Arakawa Chemical Industry Co., Ltd.) of polyester polyol (molecular weight: 1000) obtained from neopentyl glycol and adipic acid 39 components (parts by weight) of the electron beam-curable resin composition Phenol EO-modified acrylate 50 (Tg = 35 ° C.) (trademark: Alonix TO-1210, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 2.

Example 40 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 40 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylate (trade name: TEAI-1000, manufactured by Nippon Soda ) of hydrogenated polybutadiene diol (molecular weight: 1000) 50 components (parts by weight) of electron beam curable resin composition 50 Paramylphenol EO-modified acrylate 50 (Tg = 35) ° C) (trademark: Alonix TO-1210, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 2.

Example 41 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 41 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates 50 of the electron beam-curable resin composition 41 Ingredients Amounts (parts by weight) of polypropylene glycol (molecular weight 1000) (Trademark: PPG1000-U, Arakawa Chemical Industries, Ltd.) 2-acryloyloxypropyl hydrogencarbonate phthalate 50 (Tg = (158 ° C.) (trademark: Viscort # 2100, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 2.

Example 42 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 42 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 42 Ingredients Amounts (parts by weight) 50 polyurethane diacrylate neopentyl glycol and polyester polyols obtained from adipic acid (molecular weight 1000) (Trademark: NPAA-1000, manufactured by Arakawa Chemical Industries) 2- Acryloyloxypropyl hydrogen phthalate 50 (Tg = 158 ° C.) (trade name: Biscoat # 2100, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 2.

Example 43 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 43 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates 50 of the electron beam-curable resin composition 43 Ingredients Amounts (parts by weight) of polypropylene glycol (molecular weight 1000) (Trademark: PPG1000-U, Arakawa Chemical Industries, Ltd.) N- vinyl-2-pyrrolidone (Tg = 135 ° C. ) (Trademark: V-Pyrol, manufactured by ISP) 50 Test results are shown in Table 2.

Example 44 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 44 was prepared and used in place of the electron beam curable composition 1. 44 Polyurethane diacrylate (trade name: NPAA-1000, manufactured by Arakawa Chemical Industry Co., Ltd.) of a polyester polyol (molecular weight: 1000) obtained from neopentyl glycol and adipic acid, 44 components (parts by weight) of the electron beam-curable resin composition Vinyl-2-pyrrolidone (Tg = 135 ° C.) (trademark: V-Pyrol, manufactured by ISP) 50 The test results are shown in Table 2.

Example 45 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 45 was prepared and used in place of the electron beam curable composition 1. 45 parts of electron beam-curable resin composition (parts by weight) Polyepoxy diacrylate 50 (trade name: DA7B, manufactured by Arakawa Chemical Industry Co., Ltd.) N-vinyl-2-pyrrolidone (Tg) = 135 ° C) 50 (trademark: V-Pyrol, manufactured by ISP) The test results are shown in Table 2.

Example 46 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 46 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylates 50 of the electron beam-curable resin composition 46 Ingredients Amounts (parts by weight) of polypropylene glycol (molecular weight 700) (Trademark: PPG700-U, Arakawa Chemical Industries, Ltd.) N- vinyl -ε- caprolactam (Tg = 85 ° C. ) (Trademark: V-Cap, manufactured by ISP) 50 The test results are shown in Table 2.

Example 47 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 47 was prepared and used in place of the electron beam curable composition 1. 47 components of electron beam curable resin composition (parts by weight ) 50 Polyurethane diacrylate (trade name: NPAA-1000, manufactured by Arakawa Chemical Industries) of polyester polyol (molecular weight: 1000) obtained from neopentyl glycol and adipic acid N- Vinyl-ε-caprolactam (Tg = 85 ° C.) (trademark: V-Cap, manufactured by ISP) 50 The test results are shown in Table 2.

Example 48 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 48 was prepared and used in place of the electron beam curable composition 1. 48 components of electron beam curable resin composition (parts by weight) polyepoxy diacrylate 50 (trade name: DA7B, manufactured by Arakawa Chemical Industry Co., Ltd.) N-vinyl ε-caprolactam (Tg = 85 ° C) (trademark: V-Cap, manufactured by ISP) 50 Table 2 shows the test results.

Example 49 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 49 was prepared and used in place of the electron beam curable composition 1. Urethane diacrylate 25 of the electron beam-curable resin composition 49 Ingredients Amounts (parts by weight) of polypropylene glycol (molecular weight 1000) (Trademark: PPG1000-U, Arakawa Chemical Industries, Ltd.) Polyurethane diacrylates polypropylene glycol (molecular weight 4200) (Trademark : CJ-11-3, manufactured by Nippon Kasei) 25 Acryloylmorpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 50 The test results are shown in Table 2.

Example 50 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 50 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 50 Ingredients Amounts (parts by weight) Polyurethane diacrylates polytetramethylene glycol (molecular weight 650) 20 (trademark: PTMG650-U, Arakawa Chemical Industries, Ltd.) Polyurethane diacrylates polypropylene glycol (molecular weight 2000) 40 (trademark: PPG2000-U, manufactured by Arakawa Chemical Industries) Acryloylmorpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 40 The test results are shown in Table 2.

Example 51 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 51 was prepared and used in place of the electron beam curable composition 1. 51 components of electron beam curable resin composition (parts by weight ) 30 polyurethane diacrylate of polyester (molecular weight 1000) composed of propylene glycol and adipic acid (trade name: PGAA-1000, manufactured by Arakawa Chemical Industry Co., Ltd.) neopentyl glycol 30 Polyurethane (molecular weight 1000) polyurethane diacrylate (trade name: NPAA-1000, manufactured by Arakawa Chemical Industries, Ltd.) consisting of acryloyl morpholine (Tg = 140 ° C.) (trade name: ACMO, manufactured by Kojin Co., Ltd.) Table 2 shows the test results.

Example 52 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 52 was prepared and used in place of the electron beam curable composition 1. Polyurethane diacrylate (trade name: PPG700-U, manufactured by Arakawa Chemical Co., Ltd.) of 52 components (parts by weight) of polypropylene glycol (molecular weight: 700) 25 components of electron beam curable resin composition Polyester composed of neopentyl glycol and adipic acid (molecular weight: 1000) ) 25 Polyurethane diacrylate (trademark: NPAA-1000, manufactured by Arakawa Chemical Industry Co., Ltd.) Paramylphenol EO-modified acrylate 50 (Tg = 35 ° C.) (trademark: Alonix TO-1210, manufactured by Toagosei Co., Ltd.) Test Table 2 shows the results.

Example 53 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 53 was prepared and used in place of the electron beam curable composition 1. 53 components of electron beam curable resin composition (parts by weight ) 25 polyurethane diacrylate of polyester (molecular weight 1000) consisting of neopentyl glycol and adipic acid (trade name: NPAA-1000, manufactured by Arakawa Chemical Industry Co., Ltd.) Hydrogenation Polybutadienediol (molecular weight: 1000) 25 polyurethane diacrylate (trademark: TEAI-1000, manufactured by Nippon Soda Co., Ltd.) Dicyclopentanyl acrylate (Tg = 91 ° C.) 50 (trademark: FA513-A, manufactured by Hitachi Chemical Co., Ltd.) Table 2 shows the test results.

Example 54 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 54 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 54 Ingredients Amounts (parts by weight) 50 Polyurethane diacrylates polypropylene glycol (molecular weight 1000) (Trademark: PPG1000-U, Arakawa Chemical Industries, Ltd.) acryloyl morpholine (Tg = 140 ° C.) (Trademark: ACMO , Manufactured by Kojin Co., Ltd. 25 Dicyclopentanyl acrylate (Tg = 91 ° C.) 25 (trademark: FA-513A, manufactured by Hitachi Chemical Co., Ltd.) The test results are shown in Table 2.

Example 55 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 55 was prepared and used in place of the electron beam curable composition 1. 55 components of electron beam-curable resin composition (parts by weight ) 60 Polyurethane diacrylate (trade name: NPAA-1000, manufactured by Arakawa Chemical Industry Co., Ltd.) composed of neopentyl glycol and adipic acid Acryloylmorpholine (Tg = 140 ° C.) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 20 N-acryloyloxyethyl hexahydrophthalimide (Tg = 39 ° C.) (trademark: Alonix TO-1429, manufactured by Toagosei Co., Ltd.) 20 Test Table 2 shows the results.

Example 56 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 56 was prepared and used in place of the electron beam curable composition 1. 56 components (parts by weight) of the electron beam curable resin composition 50 Polyurethane diacrylate of hydrogenated polybutadiene diol (molecular weight: 1000) (trade name: TEAI-1000, manufactured by Nippon Soda Co., Ltd.) Dicyclopentanyl acrylate (Tg = 91 ° C.) 25 (trademark: FA-513A, manufactured by Hitachi Chemical Co., Ltd.) Cyclohexyl acrylate (Tg = 40 ° C.) 25 (trademark: Viscoat # 155, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 2.

Example 57 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 57 was prepared and used in place of the electron beam curable composition 1. Polyurethane 14 diacrylate electron beam-curable resin composition 57 Ingredients Amounts (parts by weight) of polytetramethylene glycol (molecular weight 650) (Trademark: PTMG650-U, Arakawa Chemical Industries, Ltd.) Polyurethane 28 polypropylene glycol (molecular weight 2000) di Acrylate (trademark: PPG2000-U, manufactured by Arakawa Chemical Industry) Acryloylmorpholine (Tg = 140 ° C) (trademark: ACMO, manufactured by Kojin Co., Ltd.) 28 Calcium carbonate (trademark: TP-121MC, manufactured by Okutama Kogyo) 30 Test results Are shown in Table 2.

Comparative Example 1 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 58 was prepared and used in place of the electron beam curable composition 1. 58 components of electron beam curable resin composition (parts by weight) Polyurethane 50 diacrylate of polypropylene glycol (molecular weight 2100) (trademark: PPG2000-U, manufactured by Arakawa Chemical Industries) Methoxytriethylene glycol acrylate (Tg = -50 ° C.) 50 (trademark: New Frontier ME-3, manufactured by Daiichi Kogyo Seiyaku) The test results are shown in Table 2.

Comparative Example 2 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 59 was prepared and used in place of the electron beam curable composition 1. 59 components of electron beam-curable resin composition (parts by weight ) 50 Polyurethane diacrylate (trade name: PGAA-1000, manufactured by Arakawa Chemical Industries, Ltd.) of polyester (molecular weight: 1000) obtained from propylene glycol and adipic acid Phenoxypolyethylene Glycol acrylate (Tg = -8 ° C.) 50 (trademark: light acrylate P-200A, manufactured by Kyoeisha Chemical Co., Ltd.) The test results are shown in Table 2.

Comparative Example 3 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 60 was prepared and used in place of the electron beam curable composition 1. 60 components of electron beam curable resin composition (parts by weight) Hydrogenated polybutadienediol (molecular weight: 1000) 50 Polyurethane diacrylate (trade name: TEAI-1000, manufactured by Nippon Soda Co., Ltd.) Lauryl acrylate (Tg = 15 ° C.) 50 (trademark: LA, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 2.

Comparative Example 4 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 61 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 61 Ingredients Amounts polyepoxy diacrylate 50 (parts by weight) of dimer acid (molecular weight: about 2000) (Trademark: DA7B, manufactured by Arakawa Chemical Industries, Ltd.) nonylphenol EO-modified acrylate (Tg = 17 ° C. ) 50 (trademark: Aronix M-111, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 2.

Comparative Example 5 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 62 was prepared and used in place of the electron beam curable composition 1. 62 components (parts by weight) of the electron beam-curable resin composition 50 Polyurethane diacrylate (trade name: NPAA-1000, manufactured by Arakawa Chemical Industry Co., Ltd.) of polyester (molecular weight: 1000) obtained from neopentyl glycol and adipic acid Propylene glycol diacrylate (Tg = 90 ° C.) 50 (trademark: M-220, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 2.

Comparative Example 6 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 63 was prepared and used in place of the electron beam curable composition 1. 50 Polyurethane diacrylate (trade name: PPG2000-U, manufactured by Arakawa Chemical Industries, Ltd.) of 63 components (parts by weight) of polypropylene glycol (molecular weight: 2100) of the electron beam-curable resin composition Trimethylolpropane triacrylate (Tg> 250) ° C) 50 (trademark: M-309, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 2.

Comparative Example 7 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 64 was prepared and used in place of the electron beam curable composition 1. 64 components (parts by weight) of electron beam-curable resin composition General-purpose polyester tetraacrylate 50 (trademark: EB810, manufactured by Daicel UCB) Acryloylmorpholine (Tg = 140 ° C.) (trademark: ACMO, Table 2 shows the test results.

Comparative Example 8 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 65 was prepared and used in place of the electron beam curable composition 1. Polyurethane hexaacrylate (trade name: HIHA, manufactured by Arakawa Chemical Industry Co., Ltd.) of 65 components (parts by weight) of hydrogenated castor oil (molecular weight: 1000) of the electron beam-curable resin composition 50 Paramylphenol EO-modified acrylate (Tg = 35) C) 50 (trademark: Aronix TO-1210, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 2.

Comparative Example 9 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 66 was prepared and used in place of the electron beam curable composition 1. Electron beam-curable resin composition 66 Ingredients Amounts (parts by weight) polyurethane hexaacrylate polyolefin diol (molecular weight 2000) (Trademark: KU511-13D, Arakawa Chemical Industries, Ltd.) 50 dicyclopentenyl acrylate (Tg = 91 ° C.) 50 ( Trademark: FA-513A, manufactured by Hitachi Chemical Co., Ltd. The test results are shown in Table 2.

Comparative Example 10 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 67 was prepared and used in place of the electron beam curable composition 1. Polyurethane hexaacrylate (composition: KUP2001, manufactured by Arakawa Chemical Industries) of 67 components of electron beam curable resin composition (parts by weight) polypropylene glycol (molecular weight: 2000) 50 N-vinylpyrrolidone (Tg = 135 ° C.) (trademark: V -Pyrol, manufactured by ISP) 50 Table 2 shows the test results.

Comparative Example 11 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 68 was prepared and used in place of the electron beam curable composition 1. 68 components (parts by weight) of electron beam-curable resin composition Tetraacrylate 50 of general-purpose polyester (trademark: EB810, manufactured by Daicel UCB) Methoxytriethylene glycol acrylate (Tg = -50 ° C.) 50 ( (Trademark: New Frontier ME-3, manufactured by Daiichi Kogyo Seiyaku) The test results are shown in Table 2.

Comparative Example 12 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 69 was prepared and used in place of the electron beam curable composition 1. Polyurethane hexaacrylate (trade name: KUP2001, manufactured by Arakawa Chemical Industries) of 69 components of electron beam curable resin composition (parts by weight) polypropylene glycol (molecular weight: 2000) 50 Phenoxy polyethylene glycol acrylate (Tg = -8 ° C.) 50 (trademark) : Light acrylate P-200A, manufactured by Kyoeisha Chemical Co., Ltd.) The test results are shown in Table 2.

Comparative Example 13 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 70 was prepared and used in place of the electron beam curable composition 1. Polyurethane hexaacrylate (trade name: KU511-13D, manufactured by Arakawa Chemical Co., Ltd.) of 70 components (parts by weight) of polyolefin diol ( part by weight) of the electron beam-curable resin composition 50 Lauryl acrylate (Tg = 15 ° C.) 50 (trademark: (LA, manufactured by Osaka Organic Co., Ltd.) The test results are shown in Table 2.

Comparative Example 14 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 71 was prepared and used in place of the electron beam curable composition 1. Polyurethane hexaacrylate (trade name: KUP2001, manufactured by Arakawa Chemical Industries) of 71 components of electron beam curable resin composition (parts by weight) polypropylene glycol (molecular weight: 2000) 50 Tripropylene glycol diacrylate (Tg = 90 ° C.) 50 (trademark) : M-220, manufactured by Toagosei Co., Ltd.) The test results are shown in Table 2.

Comparative Example 15 A sheet-like composite material was prepared and tested in the same manner as in Example 1. However, the following composition 72 was prepared and used in place of the electron beam curable composition 1. 72 components (parts by weight) of electron beam-curable resin composition General-purpose polyester tetraacrylate 50 (trademark: EB810, manufactured by Daicel UCB) Trimethylolpropane triacrylate (Tg> 250 ° C.) (trademark: (M-309, manufactured by Toagosei Co., Ltd.) 50 Table 2 shows the test results.

Comparative Example 16 A cast surface of cast coated paper having a basis weight of 128 g / m ² (trade name: Mirror Coated Gold, manufactured by Oji Paper Co., Ltd.) was subjected to the same test as in Example 1. Table 2 shows the test results.

[0166]

[Table 1]

[0167]

[Table 2]

As is clear from Tables 1 and 2, in the sheet-like composite material according to the present invention, the elongation at break of the electron beam-curable resin film forming the coating layer was 50% or more, High glossiness and high glossiness of white paper (Examples 1 to 57). However, in contrast, when a monofunctional electron beam-curable organic compound having a glass transition temperature of less than 20 ° C. when converted into a homopolymer was used in the electron beam-curable resin composition (Comparative Example 1) 4), when a polyfunctional electron beam-curable organic compound is used (Comparative Examples 5 and 6) or when a trifunctional or higher acrylate is used in the electron beam-curable resin composition (Comparative Examples 7 to 10). Alternatively, do not use the monofunctional electron beam-curable organic compound used in the present invention, which has a glass transition temperature of 20 ° C. or higher when formed into a homopolymer, and use the di (meth) acrylate used in the present invention. Without preparing the electron beam-curable resin composition (Comparative Examples 11 to 15), the elongation at break of the electron beam-curable resin film forming the coating layer of the obtained sheet-like composite material was 100%. Is much smaller than However, the flexibility deteriorates, and it cannot be put to practical use. In addition, general cast-coated paper has very low blank gloss (Comparative Example 16).

Example 58 By the following steps, a sheet-like composite material having an electron beam-curable resin coating layer having a laminated structure and excellent in flexibility was produced. Electron beam curable resin composition 73 (for forming outermost resin coating layer) Component blending amount (parts by weight) Electron beam curable unsaturated organic compound containing bifunctional urethane-modified polyether acrylate as a main component (trademark: KU511-23B) Arakawa Chemical Industries) 65 2-butyl-2-ethylpropanediol diacrylate (trademark: KU-C9A, Arakawa Chemical Industries) 35 A mixture of the above composition was prepared using a Cowles dissolver.
The mixture was dispersed and mixed at 00 rpm for 20 minutes to prepare an electron-curable resin composition 73. Further, the electron-curable resin composition 3 described in Example 3 was used for forming the inner resin coating layer.

Preparation of sheet-like composite material The composition 7 was coated on the surface of a 75 μm-thick polyester film used as a molded product by using a Mayer bar.
3 was applied so that the coating amount after curing was 5 g / m ² , to form an outermost coating liquid layer. Separately, the composition 3
Is a sheet-like support made of coated paper having a basis weight of 128 g / m ² (trademark: OK Top Coat Dal, manufactured by Oji Paper).
Using a Mayer bar on the surface, the coating amount after curing is 10
g / m ² to form an inner coating liquid layer,
The inner coating liquid layer and the outermost coating liquid layer are superimposed so that they are directly overlapped, and the superposed outermost and inner coating liquid layers are accelerated from the back of the polyester film at an accelerating voltage of 175 kV, an absorbed dose of 3 Mrad, The inner coating layer and the outermost coating layer are cured by irradiating an electron beam under an oxygen concentration of 500 ppm or less, and the inner resin coating layer, the outermost resin coating layer, and the sheet-like support obtained at the same time are integrally bonded. I let it. Thereafter, the polyester film was peeled off from the outermost resin coating layer to obtain a sheet-like composite material having an electron beam-curable resin coating layer having a laminated structure.

Evaluation Method Measurement of Flexibility of Sheet-like Composite Material A sample of the above-mentioned sheet-like composite material was bent at an angle of 180 ° so that the resin coating layer was located outside, and the degree of cracking of the resin coating layer was measured. A visual test was performed. The results are shown below. ：: No cracks are formed in the resin coating layer at all. △: Some cracks are formed in the resin coating layer. ×: The resin coating layer is completely cracked. It is judged not to be practical. Table 3 shows the results of the above test.

Example 59 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, the composition 5 described in Example 5 was used in place of the electron beam curable resin composition 3 for forming the inner resin coating layer. Table 3 shows the test results of the obtained sheet composite material.

Example 60 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, the composition 21 described in Example 21 was used instead of the electron beam-curable resin composition 3 for forming the inner resin coating layer. Table 3 shows the test results of the obtained sheet composite material.

Example 61 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, in order to form the inner resin coating layer, the composition 25 described in Example 25 was used instead of the electron beam curable resin composition 3. Table 3 shows the test results of the obtained sheet composite material.

Example 62 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, the composition 36 described in Example 36 was used instead of the electron beam curable resin composition 3 to form the inner resin coating layer. Table 3 shows the test results of the obtained sheet composite material.

Example 63 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, the composition 49 described in Example 49 was used in place of the electron beam curable resin composition 3 to form the inner resin coating layer. Table 3 shows the test results of the obtained sheet composite material.

Example 64 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, in order to form an inner resin coating layer, the composition 55 described in Example 55 was used instead of the electron beam-curable resin composition 3. Table 3 shows the test results of the obtained sheet composite material.

Comparative Example 17 In the same manner as in Example 58, a sheet-like composite material having an electron-beam cured coating layer laminated thereon was produced. However, in order to form the inner resin coating layer, the composition 58 described in Comparative Example 1 was used instead of the electron beam curable resin composition 3. Table 3 shows the test results of the obtained sheet composite material.

Comparative Example 18 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, in order to form the inner resin coating layer, the composition 59 described in Comparative Example 2 was used instead of the electron beam curable resin composition 3. Table 3 shows the test results of the obtained sheet composite material.

Comparative Example 19 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, the composition 62 described in Comparative Example 5 was used in place of the electron beam curable resin composition 3 to form the inner resin coating layer. Table 3 shows the test results of the obtained sheet composite material.

Comparative Example 20 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, in order to form the inner resin coating layer, the composition 6 of Comparative Example 4 was used instead of the electron beam-curable resin composition 3.
4 was used. Table 3 shows the test results of the obtained sheet composite material.

Comparative Example 21 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, in order to form the inner resin coating layer, the composition 6 of Comparative Example 9 was used instead of the electron beam-curable resin composition 3.
6 was used. Table 3 shows the test results of the obtained sheet composite material.

Comparative Example 22 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, the composition 70 of Comparative Example 13 was used instead of the electron beam curable resin composition 3 to form the inner resin coating layer. Table 3 shows the test results of the obtained sheet composite material.

Comparative Example 23 A sheet-like composite material was prepared and tested in the same manner as in Example 58. However, the composition 72 described in Comparative Example 15 was used in place of the electron beam curable resin composition 3 to form the inner resin coating layer. Table 3 shows the test results of the obtained sheet composite material.

[0185]

[Table 3]

As clearly shown in Table 3, the sheet-like composite material according to the present invention having an electron beam-cured resin coating layer having a laminated structure in which a flexible electron beam-cured material was disposed on the inner coating layer was entirely used. It is practically preferable because the surface of the electron beam curable resin coating layer does not crack even when bent (Examples 58 to 6).
4). However, in contrast, when the homopolymer is used in the electron beam-curable resin composition for forming the inner coating layer, 20
When a monofunctional electron beam-curable organic compound having a glass transition temperature of less than 0 ° C. is used (Comparative Examples 17 to 18), and when a polyfunctional electron beam-curable organic compound is used (Comparative Example 1)
9) Or, when a trifunctional or higher acrylate is used in the electron beam curable resin composition for forming the inner coating layer (Comparative Examples 20 and 21), or to form the inner coating layer, When an electron beam-curable resin composition was prepared without using a monofunctional electron beam-curable organic compound exhibiting a glass transition temperature of 20 ° C. or more and without using di (meth) acrylate In Examples 22 and 23), a flexible electron beam-curable resin coating layer was not formed, which deteriorated the flexibility of the resulting sheet-like composite material as a whole, and caused the electron beam-curable resin coating layer to be unfolded when folded. Cracks are generated on the surface and the aesthetics are greatly impaired, so that they cannot be put to practical use.

[0187]

According to the present invention, the electron beam-curable resin composition is cured by irradiation with an electron beam to form a flexible and highly breakable film. Further, in the sheet-like composite material of the present invention, on at least one surface of the sheet-like support, an electron beam-curable resin coating layer made of a cured resin film by electron beam irradiation of the electron beam-curable resin composition is provided. Therefore, the sheet-shaped composite material of the present invention has excellent flexibility as a whole, does not cause cracks in the electron beam-curable resin coating layer even when folded, and has a high degree of white paper gloss. It is extremely useful. Further, according to the present invention, the cured resin film forming the electron beam cured resin coating layer can have a breaking elongation of 100% or more, and this characteristic is extremely important for obtaining a flexible sheet-like composite material. is there. Further, since the sheet-like composite material of the present invention is excellent in white paper gloss and rich in flexibility as described above, it is suitable as a support for packaging materials and printing materials.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 226/10 C08F 226/10 299/02 299/02 C08J 5/18 CER C08J 5/18 CER C09D 4/00 C09D 4/00

Claims (18)

[Claims] 1. A first component comprising at least one monofunctional electron beam-curable organic compound exhibiting a glass transition temperature of 20 ° C. or higher (hereinafter referred to as Tg) when formed into a homopolymer, and at least one diamine. An electron beam-curable resin composition comprising: a second component containing (meth) acrylate. 2. The composition contains the monofunctional electron beam-curable organic compound.
The first component is (1) acryloyl morpholine, (2) tricyclo [5.2.1.0^2,6] Decane structure
Mono (meth) a represented by the following general formula (1)
Crylate:[However, (M) A in the formula (1) is a (meth) acryloyl group
(3) cycloalkyl represented by the following general formula (2)
Mono (meth) acrylate:[However, in the formula (2), R⁷Represents a hydrogen atom, a methyl group,
Represents a tyl group or a cyclohexyl group, and (M) A is
T) represents an acryloyl group. And (4) a tertiary alcohol represented by the following general formula (3).
Mono (meth) acrylate:[However, in the formula (3), R⁸, R⁹And R^TenRespectively
Each independently represents a methyl group or an ethyl group;
Represents a (meth) acryloyl group], (5) having a succinimide structure, and represented by the following general formula (4)
(Meth) acrylate represented:[However, in the formula (4), R¹¹And R¹²Is the hydrogen source
Represents a child or R¹¹And R¹²Are combined with each other, it
Two carbons of the succinimide structural ring to which each is bonded
Cyclohexane ring or cyclohexene ring with atoms
Wherein s represents an integer of 2 or 3, and (M) A
Represents a (meth) acryloyl group], (6) having a bisphenol structure, and represented by the following general formula (5)
Mono (meth) acrylate represented by:[However, in the formula (5), t represents an integer of 2 or 3, and (M)
A represents a (meth) acryloyl group], (7) having a cyclic dicarboxylic acid monoester structure,
Mono (meth) aclay represented by general formula (6)
G:[However, in the formula (6), R¹³Is a hydrogen atom or a methyl group
Wherein cyclic structure B is a 5- to 8-membered saturated or unsaturated fat
(MA) represents (meth) acryloyl
And (8) N-vinyl lac represented by the following general formula (7)
Tam compound:[However, in the formula (7), u represents an integer of 1 or 3.
And at least one member selected from the group consisting of
(9) The (meth) acrylate-containing second component is represented by the following general formula (8):
Polyether structure with a molecular weight of 000:[However, in the formula (8), R¹And R^TwoRespectively
Each independently has a hydrogen atom or 1 to 5 carbon atoms
N represents 0 or an integer of 1 to 9
M is an integer satisfying (n + 1) × m = 20 to 300.
Represents a number, provided that when n represents an integer of 2 or more,
R^TwoThe groups may be identical to each other or different from each other.
Polyether polyurethane having
Di (meth) acrylate, (10) represented by the following general formula (9), and
Polyester structure having a molecular weight of 10,000:[However, in the formula (9), X represents the formation of the polyester structure.
Linear, branched or cycloaliphatic,
Represents an aromatic dicarboxylic acid residue, and Y represents the polyester
Linear, branched or cyclic fats used to form the structure
Represents a group or aromatic diol residue, and n is a polyester structure.
Integers satisfying a molecular weight of 500 to 10,000
Polyester polyurethane di (meth) having
Acrylate, (11) represented by the following general formula (10) or (11)
Dimer acid structures derived from dimers of unsaturated higher fatty acids
Structure:[However, in the formulas (10) and (11), R^Three, R^Four,
R^FiveAnd R⁶Are each independently an alkyl group
And k, l, p and q are each independently 1 or more
, Where R^ThreeThe number of carbon atoms in the group^FourBase charcoal
The sum of the number of elementary atoms, k and l is 28, and R^Fivebase
Number of carbon atoms and R⁶And the sum of p and q is 3
4, and the number of molecules is 500 to 10,000.
(12) a di (meth) acrylate having the following general formula (12), and
Polyolefin structure having a molecular weight of up to 10,000:[However, in the formula (12), R¹⁴And R^FifteenAre each other
Independently represents a hydrogen atom, a methyl group or an ethyl group;
Represents an integer of 1 or 2, and when a represents 2, two R
^FifteenThe groups may be identical or different from each other
B is a polyolefin structure having a molecular weight of 500 to 1
Represents an integer satisfying 0000]
Fin polyurethane di (meth) acrylate, and (13) a polyether represented by the following general formula (13)
Structure:[However, R¹, R^TwoAnd n are as defined above.
m ′ is an integer satisfying (n + 1) × m ′ = 8 to 200
And when n represents an integer of 2 or more, a plurality of R ^TwoBase
May be identical to each other or different from each other
Having a molecular weight of 150 to 5000.
Liether di (meth) acrylate, a small number selected from
2. The electron beam-curable resin according to claim 1, comprising at least one kind.
Composition. 3. The monofunctional electron beam-curable organic compound-containing first component comprises acryloyl morpholine, and the di (meth) acrylate-containing second component has a molecular weight of 500 to 500 represented by the general formula (8). Polyether polyurethane di (meth) acrylate having a polyether structure of 10,000, polyether di (meth) acrylate having a polyether structure represented by the above formula (13) and having a molecular weight of 150 to 5,000, and represented by the above formula (9) Polyester polyurethane di (meth) acrylate having a polyester structure having a molecular weight of 500 to 10,000, and a molecular weight having a dimer acid structure derived from a dimer of unsaturated higher fatty acids represented by the above general formulas (10) and (11)
The electron beam-curable resin composition according to claim 2, comprising at least one member selected from 500 to 10,000 di (meth) acrylate. 4. The method according to claim 1, wherein the monofunctional electron beam-curable organic compound-containing first component is a tricycloalkyl compound represented by the general formula (1).
[5.2.1.0 ^2,6 ] a mono (meth) acrylate having a decane structure, wherein the di (meth) acrylate-containing second component has a polyether structure represented by the general formula (8) and having a molecular weight of 500 to 10,000. Polyether polyurethane di (meth) acrylate having a molecular weight of 500 represented by the general formula (9)
A polyester polyurethane di (meth) acrylate having a polyester structure of up to 10,000;
The electron beam curable resin composition according to claim 2, comprising at least one member selected from the group consisting of polyolefin polyurethane di (meth) acrylate having a polyolefin structure having a molecular weight of 500 to 10,000 and represented by 2). 5. The second component containing a cycloalkyl mono (meth) acrylate represented by the general formula (2), wherein the first component containing a monofunctional electron beam-curable organic compound is a dialkyl (meth) acrylate. Is a polyether polyurethane di (meth) acrylate having a polyether structure having a molecular weight of 500 to 10,000 represented by the general formula (8), and a molecular weight of 500 to 10,000 represented by the general formula (9).
And at least one member selected from the group consisting of a polyester polyurethane di (meth) acrylate having a polyester structure of the following and a polyolefin polyurethane di (meth) acrylate having a polyolefin structure having a molecular weight of 500 to 10,000 and represented by the general formula (12). 3. The electron beam curable resin composition according to 2. 6. The monofunctional electron beam-curable organic compound-containing first component is a tertiary alcohol mono (meth) acrylate represented by the general formula (3); Two components are a polyether polyurethane di (meth) acrylate having a polyether structure having a molecular weight of 500 to 10,000 represented by the general formula (8) and a molecular weight of 500 represented by the general formula (9).
A polyester polyurethane di (meth) acrylate having a polyester structure of up to 10,000;
3. The electron beam-curable resin composition according to claim 2, comprising at least one member selected from the group consisting of polyolefin polyurethane di (meth) acrylates having a polyolefin structure and a molecular weight of 500 to 10,000. 7. The monofunctional electron beam-curable organic compound-containing first component comprises a mono (meth) acrylate having a succinimide structure represented by the general formula (4), and contains the di (meth) acrylate. The second component is a polyether polyurethane di (meth) acrylate having a polyether structure having a molecular weight of 500 to 10,000 represented by the general formula (8) and a molecular weight of 500 represented by the general formula (9).
A polyester polyurethane di (meth) acrylate having a polyester structure of up to 10,000;
(0) and (11) having a dimer acid structure derived from a dimer of unsaturated higher fatty acids represented by the following formula:
The electron beam-curable resin composition according to claim 2, comprising at least one member selected from among di (meth) acrylates of 000. 8. The monofunctional electron beam-curable organic compound-containing first component comprises a mono (meth) acrylate having a bisphenol structure represented by the general formula (5), and the di (meth) acrylate-containing second component comprises The component is a polyether polyurethane di (meth) acrylate having a polyether structure having a molecular weight of 500 to 10,000 represented by the general formula (8) and a molecular weight of 500 represented by the general formula (9).
A polyester polyurethane di (meth) acrylate having a polyester structure of up to 10,000;
The electron beam-curable resin composition according to claim 2, comprising at least one member selected from the group consisting of polyolefin polyurethane di (meth) acrylates having a molecular weight of 500 to 10,000 represented by 2). 9. The monofunctional electron beam-curable organic compound-containing first component comprises a mono (meth) acrylate having a cyclic dicarboxylic acid monoester structure represented by the general formula (6); The acrylate-containing second component is a polyether polyurethane di (meth) acrylate having a polyether structure having a molecular weight of 500 to 10,000 represented by the general formula (8), and a molecular weight represented by the general formula (9)
The electron beam-curable resin composition according to claim 2, comprising at least one member selected from polyester polyurethane di (meth) acrylate having a polyester structure of 500 to 10,000. 10. The monofunctional electron beam-curable organic compound-containing first component comprises an N-vinyl lactam compound represented by the general formula (7), and the di (meth) acrylate-containing second component comprises: A polyether polyurethane di (meth) acrylate having a polyether structure having a molecular weight of 500 to 10,000 represented by the general formula (8), and a molecular weight of 500 represented by the general formula (9)
A polyester polyurethane di (meth) acrylate having a polyester structure of up to 10,000, and a molecular weight of 500 having a dimer acid structure derived from a dimer of unsaturated higher fatty acids represented by the above general formulas (10) and (11)
The electron beam curable resin composition according to claim 2, comprising at least one member selected from di (meth) acrylates of up to 10,000. 11. The weight ratio of the first component containing the monofunctional electron beam-curable organic compound to the second component containing the di (meth) acrylate is 10/90 to 90/10.
The electron beam-curable resin composition according to any one of items 10 to 10. 12. The monofunctional electron beam-curable organic compound-containing first component is composed of acrylomorpholine, and the di (meth) acrylate-containing second component is a polyether represented by the general formula (13). The polyether di (meth) acrylate having a molecular weight of 150 to 5,000 having the following structure: wherein the weight composition ratio of the acryloyl morpholine and the polyether di (meth) acrylate is 51
3. The electron beam-curable resin composition according to claim 2, wherein the ratio is from / 49 to 90/10. 13. An electron beam-curable resin film comprising an electron beam-cured product of the electron beam-curable resin composition according to any one of claims 1 to 12. 14. The electron beam-curable resin film according to claim 13, which has an elongation at break of 100% or more. 15. An electron beam-curable sheet-like support and an electron beam-curable resin composition comprising the electron beam-curable resin composition according to claim 1 and formed on at least one surface thereof. A sheet-shaped composite material having a resin coating layer. 16. The sheet-like composite material according to claim 15, wherein the electron beam cured body has a breaking elongation of 50% or more. 17. It has a sheet-like support, and an electron beam-curable resin composite coating layer formed on at least one surface thereof,
The electron beam-curable resin composite coating layer is composed of a laminate of a plurality of resin layers including at least an inner resin layer adjacent to the sheet-like support and an outermost resin layer disposed on the outermost side, and Claim 1 wherein at least one of the resin layers is
A sheet-like composite material comprising an electron beam-cured body of the electron beam-curable resin composition according to any one of Items 1 to 12. 18. The sheet-like composite material according to claim 17, wherein the electron beam cured product of the electron beam curable resin composition has a breaking elongation of 50% or more.