JP6677047B2 - Alicyclic polyfunctional (meth) acrylate compounds - Google Patents

Description

  The present invention relates to an alicyclic polyfunctional (meth) acrylate compound, and more specifically, it can be used as a raw material of a curable resin or a raw material such as an acrylic crosslinking agent, and can be used as an optical material, a paint, a reactive diluent, The present invention relates to an alicyclic polyfunctional (meth) acrylate compound useful for various uses in addition to a surfactant raw material, an intermediate for the production of medical and agricultural chemicals, a resist raw material and the like. The present invention also relates to a cured product containing a structural unit derived from the alicyclic polyfunctional (meth) acrylate compound, and a laminate having a hard coat layer made of the cured product on a substrate.

  A polyfunctional (meth) acrylate compound is a compound that has two or more (meth) acryloyloxy groups to exhibit polyfunctionality due to a plurality of double bonds, and is a (meth) acrylic curable resin composition Widely used to obtain cured products from Further, it is used as a raw material for various chemical products as a (meth) acrylic crosslinking agent. As described above, by using a polyfunctional (meth) acrylate compound, a structure in which two or more polymer chains are crosslinked can be formed. For example, a high curing rate or high hardness may be imparted to the curable resin composition. When required, a trifunctional or higher polyfunctional (meth) acrylate compound is often used. When the number of functional groups is increased, physical properties such as curability and hardness can be increased. However, usually, an appropriate number of functional groups is selected depending on required performance and the like.

  In a curable resin in which a polyfunctional (meth) acrylate compound is used, various properties such as fast curing, high hardness, transparency, and scratch resistance are required. Further, in recent years, non-polar materials such as cycloolefin polymers and acrylic resins have been used as optical materials, and curable resins that adhere to these materials have been desired. Further, in the case of transparent material applications such as lenses and displays, a material that does not contain an aromatic ring structure having an absorption band in a wavelength region of ultraviolet light or visible light is often required from the viewpoint of light transmission and light resistance. Furthermore, in the field of optical films such as retardation films, there is a tendency that moisture permeability is insufficient as the thickness of the film is reduced, and resins capable of imparting moisture permeability prevention properties have been desired.

  However, it has been difficult for conventional polyfunctional (meth) acrylate compounds to coexist these properties and functions at a high level.

  That is, many conventional polyfunctional (meth) acrylate compounds have a structure in which two or more (meth) acryloyloxy groups are bonded to a linear hydrocarbon group, an aromatic ring, or the like. Since it has a high ratio of functional groups and a flexible chemical structure, there is room for improvement in terms of hygroscopicity and weather resistance.

  DPHA (dipentaerythritol hexaacrylate) and TCDDA (tricyclodecane dimethanol diacrylate) are known as those in which a plurality of (meth) acryloyloxy groups are bonded to a branched hydrocarbon group or an alicyclic structure. When a curable resin is prepared using DPHA to form a cured coating film, high performance can be obtained in basic physical properties such as fast curing, high hardness, transparency, and scratch resistance, Sufficient performance cannot be obtained in the functions of adhesion to non-polar materials and moisture permeability prevention, which are required in recent years.

  In addition, when a curable resin is prepared using TCDDA to form a cured coating film, it is possible to obtain high performance in terms of physical properties such as transparency and moisture permeation prevention properties. In this case, it is difficult to use as a curable resin because sufficient performance cannot be obtained. Further, the adhesiveness to a non-polar material is not sufficient. Furthermore, since the viscosity is low, although the moisture permeation prevention performance is high, there is a problem that the film cannot be made thick to secure a sufficient moisture permeation prevention property.

  For these reasons, the polyfunctional (meth) acrylate compound used as the curing component can be used in various applications requiring high performance, and can exhibit all of various properties and functions at a high level. An acrylate compound has been demanded, and various studies have been made on the application of an alicyclic polyfunctional (meth) acrylate compound as one of such polyfunctional (meth) acrylate compounds.

  Conventionally, an alicyclic diester compound having a (meth) acryloyloxy group and an alicyclic olefin residue is produced by reacting an alicyclic diolefin with acrylic acid as an alicyclic polyfunctional (meth) acrylate compound. And a compound in which two (meth) acryloyloxy groups are bonded to a 5-membered, 6-membered, 8-membered, or heterocyclic alicyclic hydrocarbon group. 1) With this compound, the ratio of the polar functional group is high, the compound cannot be easily synthesized in production, or the quick-hardness, hardness, and adhesion to a non-polar material are not sufficient. There is a problem.

  Further, one acryloyloxy group represented by the following general formula (in the following general formula, R represents a hydrogen atom or a methyl group) is bonded to an 8-membered alicyclic hydrocarbon group via a carbon bond. Although the disclosed acrylate compound is disclosed (Patent Document 2), even with this compound, it is not possible to obtain a sufficiently satisfactory fast curing property, hardness, viscosity and the like.

  As a solution to the problem of these alicyclic polyfunctional (meth) acrylate compounds, an alicyclic polyfunctional (meth) acrylate compound represented by the following general formula (1) has been proposed (Patent Document 3). ) Even with this compound, it was not possible to sufficiently satisfy the required characteristics such as moisture permeability prevention and adhesion to non-polar materials when used as a curing component.

(In the formula, R ¹ is the same or different and represents a hydrogen atom or a methyl group. R ² is the same or different and represents a hydroxyl group or a monovalent organic group. M represents an integer of 2 to 10.) N represents an integer of 0 to 10. X represents an alicyclic hydrocarbon group, and when m is 2, represents an alicyclic hydrocarbon group having a monocyclic 9 to 40-membered ring. )

JP-A-4-316536 JP-A-2004-43347 JP 2013-166733 A

  The present invention is intended to solve the above-mentioned conventional problems, and has fast curing, high hardness, transparency, abrasion resistance, moisture barrier properties, excellent adhesion to non-polar materials, and curability. An object is to provide an alicyclic polyfunctional (meth) acrylate compound that can be suitably used as a raw material such as a resin raw material.

  The present inventor has conducted intensive studies on polyfunctional (meth) acrylate compounds, and as a result, has found that alicyclic polyfunctional (meth) acrylate compounds have a rapid curing property, a high hardness, transparency, abrasion resistance, and non-polar materials. It has been found that it is suitable as a curable resin having all functions such as adhesion and a raw material of a cured product thereof. Furthermore, it has been found that by interposing a carbon bond between the alicyclic skeleton and the (meth) acryloyloxy group, the polarity can be reduced and the moisture permeability can be effectively prevented.

  That is, the structure necessary for coexistence of the above functions was extracted and the monomer structure was designed. In order to achieve high hardness and scratch resistance, it was a polyfunctional (meth) acrylate, and the ring structure was It is necessary to have a non-aromatic ring, that is, an alicyclic ring in order to improve the curability of the film at the time of curing by ultraviolet rays, and to prevent moisture permeation and adherence to a non-polar material. To realize this, it has been found that it is necessary to have a ring having 9 or more carbon atoms in order to lower the concentration of the polar group. Further, an alicyclic polyfunctional compound having two or more (meth) acryloyloxy groups bonded to an alicyclic skeleton via a carbon bond to further reduce the polar group concentration and enhance the moisture permeability preventing property ( A (meth) acrylate compound could be obtained.

  The alicyclic polyfunctional (meth) acrylate compound of the present invention can be used in various kinds of curable compositions using the polyfunctional (meth) acrylate compound as a curing component or a reactive diluent by designing such a monomer structure. All of the characteristics and functions are exhibited at a high level, and the gist is as follows.

[1] An alicyclic polyfunctional (meth) acrylate compound represented by the following general formula (I).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydroxyl group or a monovalent organic group, and X represents an alicyclic hydrocarbon group having a 9 to 40-membered ring structure. However, when R ² is a monovalent organic group, two or more R ² may combine with each other to form a fused ring containing ring X. l represents an integer of 1 or 2, and m represents 2 to 2 Represents an integer of 10, and n represents an integer of 0 to 10. However, when the number of carbon atoms constituting the ring X is x, 2x ≧ m + n.)

[2] A cured product containing a structural unit derived from the alicyclic polyfunctional (meth) acrylate compound according to [1].

[3] A laminate having a substrate and a hard coat layer, wherein the hard coat layer is made of the cured product according to [2].

[4] The laminate according to [3], wherein the substrate is a thermoplastic resin substrate.

[5] The laminate according to [4], wherein the thermoplastic resin substrate is made of a cycloolefin polymer.

  According to the present invention, rapid hardening, high hardness, transparency, abrasion resistance, moisture permeation prevention, adhesion to non-polar materials, and all functions that were conventionally difficult to coexist can be provided. And a polyfunctional (meth) acrylate compound which can be suitably used as a curable resin material or the like.

  Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example of the embodiment of the present invention, and the present invention is limited to the following description unless departing from the gist thereof. is not. It should be noted that, when the expression “to” is used in this specification, it is used as an expression including numerical values or physical property values before and after that. Further, in the present invention, when the expression “(meth) acrylate” is used, it means one or both of “acrylate” and “methacrylate”. The same applies to “(meth) acryloyl”.

[Alicyclic polyfunctional (meth) acrylate compound]
The alicyclic polyfunctional (meth) acrylate compound of the present invention is a compound represented by the following general formula (I) and having two or more (meth) acryloyloxy groups via a carbon bond to an alicyclic skeleton. is there. As described above, by bonding the (meth) acryloyloxy group to the alicyclic skeleton via the carbon bond, it is possible to highly secure moisture permeation prevention and adhesion to a nonpolar material.

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydroxyl group or a monovalent organic group, and X represents an alicyclic hydrocarbon group having a 9 to 40-membered ring structure. However, when R ² is a monovalent organic group, two or more R ² may combine with each other to form a fused ring containing ring X. l represents an integer of 1 or 2, and m represents 2 to 2 Represents an integer of 10, and n represents an integer of 0 to 10. However, when the number of carbon atoms constituting the ring X is x, 2x ≧ m + n.)

In the general formula (I), m CH ₂ ＣＲCR ¹ COO— (CH ₂ ) ₁ — groups (hereinafter, may be referred to as “(meth) acryloyloxy (methyl / ethyl) group”). R ¹ may be the same or different. Also, _- (CH ₂₎ l - as, methylene group (l = 1) and an ethylene group (l = 2) may have been mixed, may have only one. Further, when n is 2 or more, for the n-number of R ^2, it may be the same or may be different.

In the above general formula (I), CH ₂ ＣＲCR ¹ COO— becomes an acryloyloxy group when R ¹ is a hydrogen atom, and becomes a methacryloyloxy group when R ¹ is a methyl group. Either one may be selected, and these groups may be mixed in one molecule.

In the general formula (I), R ² represents a hydroxyl group or a monovalent organic group, preferably a monovalent organic group, and R ² is a single bond directly to a carbon atom constituting the alicyclic hydrocarbon group of X. However, when R ² is a monovalent organic group, two or more R ² may combine with each other to form a condensed ring containing ring X. When prepared by a preferred production method described below, X preferably corresponds to a residue of a functional group in an alicyclic compound having a plurality of functional groups as a raw material or an intermediate.

As the monovalent organic group for R ^2, a monovalent organic group having 1 to 25 carbon atoms is preferable, for example, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an aroyloxy group, an alkoxycarbonyl group, And an aryloxycarbonyl group.
The carbon number of the alkoxy group and the alkyl group is preferably 1 to 24, more preferably 1 to 12. The carbon number of the acyloxy group and the alkoxycarbonyl group is preferably 2 to 25, more preferably 2 to 13. The number of carbon atoms of the aryl group and the aryloxy group is preferably 6 to 24, and more preferably 6 to 12. The carbon number of the aroyloxy group and the aryloxycarbonyl group is preferably from 7 to 25, more preferably from 7 to 13.
When R ² is a monovalent organic group and two or more R ² are bonded to each other to form a condensed ring containing ring X, the ring formed by two or more R ² includes It is preferable that the number of rings is equal to or less than that, and examples thereof include a 6- to 24-membered ring containing two or three adjacent carbon atoms on ring X.

  The monovalent organic group may have a substituent, and examples of the substituent include a fluorine atom, a chlorine atom, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group. When the monovalent organic group has a substituent, the monovalent organic group has a total carbon number of 1 to 25 including the substituent, and preferably has the above carbon number for each group. Is preferred.

  In the general formula (I), X represents an alicyclic hydrocarbon group having a 9 to 40 membered ring structure.

  The form of the alicyclic hydrocarbon group represented by X is any of 9 to 40-membered rings, preferably any of 9 to 20-membered rings, and more preferably any of 9 to 16-membered rings. Yes, more preferably any one of a 9- to 12-membered ring, particularly preferably any one of a 10- to 12-membered ring.

  The structure of the alicyclic hydrocarbon group for X may be a monocyclic structure or may have a plurality of rings, but is preferably a monocyclic structure. It is preferable that the alicyclic hydrocarbon group of X has a monocyclic structure in terms of compatibility when other components are blended.

  Examples of the monocyclic structure include, for example, cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cycloheptadecane, cyclooctadecane, cyclononadecane, cycloicosane, cyclohenicosane, cyclodokosan, Cyclotricosane, cyclotetracosane, cyclopentacosane, cyclohexacosane, cycloheptacosane, cyclooctacosane, cyclononacone, cyclotriacontan, cyclohentriacontane, cyclodotriacontane, cyclotritriacontane, cyclotetratria Contan, cyclopentatriacontane, cyclohexatriacontane, cyclotetracontane and the like can be mentioned.

  Among them, preferred are cyclononane, cyclodecane, cycloundecane, cyclododecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cyclooctadecane, and cycloicosane. More preferred are cyclononane, cyclodecane, cyclododecane, cyclotetradecane, cyclopentadecane, and cyclohexadecane. More preferred are cyclononane, cyclodecane and cyclododecane. Particularly preferred are cyclodecane and cyclododecane.

In the above general formula (I), m is an integer of 2 to 10, for example, when m = 2, the alicyclic polyfunctional (meth) acrylate compound of the present invention becomes di (meth) acrylate, and m = 3 Sometimes, the alicyclic polyfunctional (meth) acrylate compound of the present invention becomes tri (meth) acrylate.
m is preferably 2 to 8, more preferably 2 to 6, and still more preferably 3 to 6.

When the number of carbon atoms constituting the ring portion of X in the above general formula (I) is a (= 9 to 40), (meth) acryloyloxy (methyl / ethyl) is represented by the number of carbon atoms a of the alicyclic skeleton. The value m / a obtained by dividing the number m of the groups is preferably 1/4 or less, and from the viewpoint of being excellent in both curability and hydrophobicity (low hygroscopicity), preferably 1/12 to 1/4, It is more preferably 1/6 to 1/4, and still more preferably 1/4.
In addition, it is preferable that only one (meth) acryloyloxy (methyl / ethyl) group be bonded to one carbon atom constituting the ring portion of X.

In the above general formula (I), n is an integer of 0 to 10, preferably an integer of 0 to 8, more preferably 0 to 7, and still more preferably 0 to 3. n is a functional group in the alicyclic compound having a plurality of functional groups serving as a raw material or an intermediate, when prepared by a preferred production method described below, or a functional group, or an organic group obtained by converting the functional group by a reaction, or It is preferable to indicate the remaining number of organic groups derived from the raw materials. The type of R ² and the number n thereof may be appropriately set according to the performance required for the alicyclic polyfunctional (meth) acrylate compound of the present invention, the intended use, and the like.
For example, to increase the weather resistance, an alkyl group or an alkoxy group may be introduced as R ² , and to impart water repellency, a fluoroalkyl group or a fluoroalkoxy group may be introduced. When it is desired to increase the adhesiveness with another resin, a functional group having a high affinity with the resin may be introduced.

In the alicyclic polyfunctional (meth) acrylate compound of the present invention, when n = 0, m of the groups represented by CH ₂ ＣＲCR ¹ COO— are carbon atoms constituting an alicyclic hydrocarbon group of X And when n is 1 to 10, m (meth) acryloyloxy groups represented by CH ₂ ＣＲCR ¹ COO— each represent an alicyclic carbon represented by X A structure in which n atoms of R ² are each single-bonded to a carbon atom constituting the alicyclic hydrocarbon group of X while being bonded to a carbon atom constituting the hydrogen group via a methylene group or an ethylene group. Two or more (meth) acryloyloxy (methyl / ethyl) groups are preferably bonded to one carbon atom constituting the alicyclic hydrocarbon group of X, and there are a plurality of R ^2. In such a case, a plurality of R ² bonds to one or two carbon atoms constituting the alicyclic hydrocarbon group of X. Further, the (meth) acryloyloxy (methyl / ethyl) group and R ² may be bonded to the same carbon atom constituting the alicyclic hydrocarbon group of X, or may be bonded to another carbon atom. Is also good. In a preferred embodiment, one (meth) acryloyloxy (methyl / ethyl) group or one R ² is bonded to one carbon atom constituting the alicyclic hydrocarbon group of X. .

When the (meth) acryloyloxy (methyl / ethyl) group and the position of R ² in the alicyclic hydrocarbon group of X are bonded to each other, a plurality of starting materials or intermediates may be prepared when prepared by a preferable production method. It is preferably at the position of the functional group in the alicyclic compound having a functional group.

Specific examples of the alicyclic polyfunctional (meth) acrylate compound of the present invention preferably include, for example, the following compounds. In the following, a case where — (CH ₂ ) ₁ — in Formula (I) is a methylene group with l = 1 is illustrated, but the methylene group may be an ethylene group with l = 2.

  As a method for producing the alicyclic polyfunctional (meth) acrylate compound of the present invention, a (meth) acrylate is used for a part or all of a plurality of functional groups of an alicyclic compound having a plurality of functional groups as a raw material or an intermediate. Can be produced by reacting a compound that can be Specifically, it is preferable to employ any of the following manufacturing methods (1) to (4).

(1) A method of subjecting (meth) acrylic acid to an esterification reaction with an alicyclic compound having a plurality of methylol groups or ethylol groups.
(2) A method of subjecting (meth) acrylic esters to a transesterification reaction with an alicyclic compound having a plurality of methylol groups or ethylol groups.
(3) A method of reacting a halide of (meth) acrylic acid such as (meth) acrylic chloride with an alicyclic compound having a plurality of methylol groups or ethylol groups.
(4) A method of reacting (meth) acrylic anhydride with an alicyclic compound having a plurality of methylol groups or ethylol groups.

In the following, a methylol group or an ethylol group may be referred to as a "methylol / ethylol group", and an alicyclic compound having a plurality of methylol groups or an ethylol group may be referred to as a "methylol / ethylol group-containing alicyclic compound". .
In these production methods, the methylol / ethylol group-containing alicyclic compound is an alicyclic compound having a plurality of functional groups as a raw material or an intermediate, and includes (meth) acrylic acid, (meth) acrylic acid ester, A halide or anhydride of (meth) acrylic acid is a compound that can be (meth) acrylated.

In the above production method, a compound capable of being (meth) acrylated reacts with a part or all of a plurality of methylol / ethylol groups of the methylol / ethylol group-containing alicyclic compound, and a methylol / ethylol group-containing alicyclic compound is reacted. An alicyclic polyfunctional (meth) acrylate compound having a (meth) acryloyloxy group bonded thereto in place of the hydroxyl group of two or more methylol / ethylol groups of the compound may be formed.
Although the methylol / ethylol group-containing alicyclic compound is used as a starting material in the above-mentioned production method, in the production of the alicyclic polyfunctional (meth) acrylate compound of the present invention, the methylol / ethylol group-containing alicyclic compound is used. The cyclic compound may be used as a starting material or may be used as an intermediate.

For example, when cyclododecanetrimethanol is used as an alicyclic compound having a plurality of methylol / ethylol groups and cyclododecanetrimethyltriacrylate is produced as an alicyclic polyfunctional (meth) acrylate compound, the above (1) to (4) The reaction formula in the production method of (2) is as follows.
In the following formula, R ³ represents any one of a hydrogen atom, a methyl group, an ethyl group, a propyl group, and a butyl group.

  In the above production method, a monocyclic compound having a 9 to 40 membered ring is used as the methylol / ethylol group-containing alicyclic compound serving as a raw material or an intermediate, and the alicyclic polyfunctional compound of the present invention described above ( The methylol / ethylol group-containing alicyclic compound serving as a raw material or an intermediate may be appropriately selected depending on the preferred form of the (meth) acrylate compound.

The number of carbon atoms constituting the ring of the methylol / ethylol group-containing alicyclic compound is any of 9 to 40 membered rings, preferably any of 9 to 20 membered rings, and more preferably 9 to 16 membered rings. And more preferably any one of a 9- to 12-membered ring, and particularly preferably any one of a 10- to 12-membered ring.
Further, the methylol / ethylol group-containing alicyclic compound may be a single ring or may have a plurality of rings, but is preferably a single ring.

  As described above, when the number of carbon atoms constituting the ring portion of X in the general formula (I) is a (= 9 to 40), (meth) acryloyloxy (methyl / The value m / a obtained by dividing the number m of the ethyl) groups is preferably 1/4 or less, and from the viewpoint of excellent both curability and hydrophobicity (low moisture absorption), preferably 1/12 to 1/1. 4, more preferably 1/6 to 1/4, still more preferably 1/4. Therefore, in the above-mentioned production method, the number of a plurality of methylol / ethylol groups in the methylol / ethylol group-containing alicyclic compound is 1/4 or less, preferably 1/12 to 1/4, of the number of carbon atoms constituting the ring. , More preferably 1/6 to 1/4, further preferably 1/4.

  The compound capable of being (meth) acrylated may be added to a part of a plurality of methylol / ethylol groups of the alicyclic compound containing a methylol / ethylol group, and a part of the methylol / ethylol group may remain. Preferably, the compound capable of being (meth) acrylated reacts with all of a plurality of methylol / ethylol groups of the alicyclic compound containing a methylol / ethylol group.

When a part of the methylol / ethylol group remains, for example, in the general formula (I), R ² represents a methylol / ethylol group, and the residue of the methylol / ethylol group to which the compound capable of being (meth) acrylated was not added was added. The number becomes the number of n. At that time, the remaining methylol / ethylol group may be appropriately converted into a functional group suitable for the application by an organic synthetic technique.

  The reaction conditions and the like in each of the above production methods are as follows.

  As in the above production methods (1) and (2), the methylol / ethylol group-containing alicyclic compound is esterified and / or transesterified using (meth) acrylic acid and / or (meth) acrylate. When an alicyclic polyfunctional (meth) acrylate compound is produced, the reaction can be promoted by using a catalyst and continuously taking out the generated water or lower alcohol out of the system. The catalyst includes, for example, those known as esterification catalysts such as sulfuric acid, p-toluenesulfonic acid, boron trifluoride, and organotin compounds, and any of these catalysts can be arbitrarily selected and used. The amount of use is preferably from 10 to 100,000 ppm with respect to the total weight of the reaction substrate, from the viewpoint of reducing the load on the production apparatus and reducing the catalyst cost.

  Further, in order to prevent thermal polymerization of the (meth) acrylate, it is preferable to add a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, and 2,5-dihydroxy-. Examples include p-quinone, copper salt, phenothiazine, p-phenylenediamine, phenyl-β-naphthylamine and the like. The use amount thereof is preferably from 10 to 10,000 ppm with respect to the total weight of the reaction substrate, from the viewpoint of the influence on the catalytic activity and side reactions.

  The reaction temperature is preferably from −20 to 120 ° C., more preferably from 0 to 100 ° C., from the viewpoint of shortening the reaction time and preventing polymerization. The reaction time is preferably 1 to 20 hours.

Further, a solvent can be used for the reaction. The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitylene; pentane, hexane, heptane, octane, nonane, decane, cyclohexane, and cyclohexane. Aliphatic hydrocarbons such as octane; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, chlorobenzene, trifluoromethylbenzene; diethyl ether, diisopropyl ether, dibutyl ether, anisole, tetrahydrofuran, dioxane, etc. Ethers; ketones such as methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate and isopropyl acetate; nitriles such as acetonitrile; dimethylformamide; - acyclic or cyclic amides, such as methyl pyrrolidinone; dimethylsulfoxide acyclic or cyclic sulfoxide or sulfone, such as de; triethyl phosphate, phosphoric acid esters or phosphoric acid amides such as hexamethylphosphoric triamide and the like. These can be used alone or in combination of two or more.
The use amount of the solvent is preferably from 10 to 1,000 parts by mass with respect to 100 parts by mass of the alicyclic compound containing a methylol / ethylol group from the viewpoint of the reaction time.

  The total amount of (meth) acrylic acid and / or (meth) acrylic acid ester used for the methylol / ethylol group-containing alicyclic compound is preferably equal to or more than that for the methylol / ethylol group. For example, when cyclododecane trimethanol is used as the methylol / ethylol group-containing alicyclic compound, the total of (meth) acrylic acid and (meth) acrylate is 3.0 to 18 per equivalent of cyclododecane trimethanol. It is preferable to make it equivalent to 1.0 equivalent.

  When the alicyclic compound containing a methylol / ethylol group is esterified using a halide of (meth) acrylic acid to produce an alicyclic polyfunctional (meth) acrylate compound as in the above production method (3). The reaction is preferably performed in the presence of a basic compound, and the reaction can be promoted by using a catalyst.

  Examples of the basic compound include tertiary amines such as triethylamine and N-ethyldiisopropylamine; phosphates such as potassium phosphate and sodium phosphate; carbonates such as potassium carbonate and sodium carbonate; potassium hydroxide; Known basic compounds such as hydroxides of sodium and the like can be mentioned, and any of these can be arbitrarily selected and used. The amount of the basic compound to be used is 1.0 to 6.0 equivalents per equivalent of the halide of (meth) acrylic acid from the viewpoint of reducing the load on the production equipment and reducing the cost of raw materials. Is preferred.

  Examples of the catalyst include esterification of acid chlorides such as pyridines such as N, N-dimethyl-4-aminopyridine; imidazoles such as N-methylimidazole; and tertiary amines such as triethylenediamine. Known catalysts can be used, and any catalyst can be arbitrarily selected and used. The amount of use is preferably from 10 to 100,000 ppm with respect to the total weight of the reaction substrate, from the viewpoint of reducing the load on the production apparatus and reducing the catalyst cost.

  Further, a polymerization inhibitor may be added to prevent thermal polymerization of the halide of (meth) acrylic acid. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, and 2,5-dihydroxy-. Examples include p-quinone, copper salt, phenothiazine, p-phenylenediamine, phenyl-β-naphthylamine and the like. The use amount thereof is preferably from 10 to 10,000 ppm with respect to the total weight of the reaction substrate, from the viewpoint of the influence on the catalytic activity and side reactions.

  The reaction temperature is preferably from -20 to 120 ° C from the viewpoint of shortening the reaction time and preventing polymerization. More preferably, it is -10 to 90C. The reaction time is preferably from 0.1 to 10 hours.

  Further, a solvent can be used for the reaction. The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include the same solvents as those described above. The amount of the solvent to be used is preferably from 10 to 3000 parts by mass with respect to 100 parts by mass of the alicyclic compound containing a methylol / ethylol group from the viewpoint of the reaction time. The amount of the (meth) acrylic acid halide to be used in the methylol / ethylol group-containing alicyclic compound is preferably equal to or more than the methylol / ethylol group. For example, when cyclododecane trimethanol is used as a methylol / ethylol group-containing alicyclic compound and (meth) acrylic acid chloride is used as a halide of (meth) acrylic acid, the equivalent of (meth) ) It is preferable that the amount of acrylic acid chloride is 3.0 to 18.0 equivalents.

  When the alicyclic compound containing a methylol / ethylol group is esterified using (meth) acrylic anhydride to produce an alicyclic polyfunctional (meth) acrylate compound as in the above production method (4), The reaction is preferably performed in the presence of a basic compound, and the reaction can be promoted using a catalyst.

  Examples of the basic compound include tertiary amines such as triethylamine and N-ethyldiisopropylamine; phosphates such as potassium phosphate and sodium phosphate; carbonates such as potassium carbonate and sodium carbonate; potassium hydroxide; Known basic compounds such as hydroxides of sodium and the like can be mentioned, and any of these can be arbitrarily selected and used. From the viewpoint of reducing the load on the production equipment and reducing the cost of raw materials, the amount of the basic compound to be used is preferably 1.0 to 6.0 equivalents per equivalent of (meth) acrylic anhydride. preferable.

  Examples of the catalyst include pyridines such as N, N-dimethyl-4-aminopyridine; imidazoles such as N-methylimidazole; tertiary amines such as triethylenediamine; and acids such as p-toluenesulfonic acid. And known catalysts for the esterification reaction of acid anhydrides. Any of these catalysts can be used. The amount of use is preferably from 10 to 100,000 ppm with respect to the total weight of the reaction substrate, from the viewpoint of reducing the load on the production apparatus and reducing the catalyst cost.

  In order to prevent thermal polymerization of (meth) acrylic anhydride, a polymerization inhibitor may be added. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, 3-hydroxythiophenol, α-nitroso-β-naphthol, p-benzoquinone, and 2,5-dihydroxy-. Examples include p-quinone, copper salt, phenothiazine, p-phenylenediamine, phenyl-β-naphthylamine and the like. The use amount thereof is preferably from 10 to 10,000 ppm with respect to the total weight of the reaction substrate, from the viewpoint of the influence on the catalytic activity and side reactions.

  The reaction temperature is preferably 0 to 120 ° C. from the viewpoint of shortening the reaction time and preventing polymerization. More preferably, it is 10 to 100 ° C. The reaction time is preferably 0.1 to 20 hours.

  Further, a solvent can be used for the reaction. The solvent is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include the same solvents as those described above. The amount of the solvent to be used is preferably from 10 to 3000 parts by mass with respect to 100 parts by mass of the alicyclic compound containing a methylol / ethylol group from the viewpoint of the reaction time. The amount of (meth) acrylic anhydride to be used with respect to the methylol / ethylol group-containing alicyclic compound is preferably 0.5 equivalent or more with respect to the methylol / ethylol group. For example, when cyclododecane trimethanol is used as the methylol / ethylol group-containing alicyclic compound, it is preferable to make 1.5 to 9.0 equivalents of (meth) acrylic acid chloride per equivalent of cyclododecane trimethanol. .

Examples of the unsaturated alicyclic compound as a raw material in the above production method include compounds having two unsaturated bonds, such as cyclononadiene, cyclodecadiene, cycloundecadiene, cyclododecadiene, cyclotridecadiene, and cyclotetradecadiene. Decadiene, cyclopentadecadiene, cyclohexadecadiene, cycloheptadecadiene, cyclooctadecadiene, cyclononadecadiene, cycloicosadiene; as compounds having three unsaturated bonds, cyclododecatriene, cyclopentadeca Triene, cyclooctadecatriene, cyclohenicosantriene, cyclotetracosatriene; compounds having four unsaturated bonds include cyclohexadecatetraene, cycloicosatotetraene, cyclotetracosanetetraene, cyclooctatetraene; Santetraene, cyclodotriacontantetraene; compounds having five unsaturated bonds; cycloicosapentaene, cyclopentacosanpentaene, cyclotriacontanpentaene, cyclopentatriacontanpentaene; compounds having six unsaturated bonds Compounds having seven unsaturated bonds, such as cyclooctaicosaheptaene, cyclopentatriacontanheptaene; and eight unsaturated bonds; cyclotetraicosahexaene, cyclotriacontanhexaene, cyclohexatriacontanhexaene; Compounds having the following formulas: cyclodotriaconta octaene, cyclotetracontan octaene; compounds having 9 unsaturated bonds; cyclohexatriacontanonaene; compounds having 10 unsaturated bonds; Te, and a cycloalkyl tetraconta dec ene.
Among these, it is preferable to use cyclononadiene, cyclodecadiene, cyclododecadiene, cyclotetradecadiene, cyclohexadecadiene, cyclododecatriene, cyclopentadecatriene, and cyclooctadecatriene. Further, it is more preferable to use cyclodecadiene, cyclododecadiene, cyclododecatriene, and cyclohexadecatetraene.
In the above examples of the unsaturated alicyclic compound, the unsaturated bond may be present at any position as long as the number of unsaturated bonds is satisfied, as long as the position is capable of having the unsaturated bond.

  The method for producing the unsaturated alicyclic compound is not particularly limited, and may be appropriately selected from conventionally known methods. For example, (A) a method using a multimerization reaction of conjugated dienes (for example, JP-B-46-31216; JP-B-46-31849; JP-B-49-7153; JP-B-55-43874); U.S. Patent No. 2,964,574; G. Wilke, Angewandte Chemie International, Edition 2, 105-164 (1963), etc.), (B) a method using a ring expansion reaction of cycloalkenes or cycloalkadienes or cycloalkatrienes. (See, for example, Japanese Patent Publication No. 55-33689, etc.) and (C) a method using a ring-closing metathesis reaction of linear polyenes (see, for example, US Pat. No. 3,439,057). Preferably, the methods (A) and (B) are used.

Examples of the conjugated dienes include butadiene, isoprene, dimethylbutadiene, chloroprene, and dichlorobutadiene. Among these, butadiene, isoprene and dimethylbutadiene are preferably used from the viewpoint of the light resistance of the organic residue in the alicyclic polyfunctional (meth) acrylate compound.
Examples of the cycloalkenes include cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, and cyclododecene. Among these, it is preferable to use cyclopentene, cyclohexene, cycloheptene, and cyclooctene.
Examples of the cycloalkadienes include cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclononadiene, cyclodecadiene, cycloundecadiene, cyclododecadiene, cyclotridecadiene, cyclotetradecadiene, cyclopentadecadiene, and cyclohexadiene. Sadekadiene and the like. Among these, it is preferable to use cyclooctadiene, cyclodecadiene, cyclododecadiene, cyclotetradecadiene, and cyclohexadecadiene.
Examples of the cycloalkatrienes include cyclododecatriene, cyclopentadecatriene, cyclooctadecatriene, cyclohenicosatriene, cyclotetracosatriene and the like. Among these, it is preferable to use cyclododecatriene.

  Examples of the alicyclic compound containing a methylol / ethylol group as a raw material in the above-mentioned production method include compounds having two methylol / ethylol groups, such as cyclononane dimethanol, cyclodecane dimethanol, cycloundecane dimethanol, and cyclododecane dimethanol. Methanol, cyclotridecane dimethanol, cyclotetradecane dimethanol, cyclopentadecane dimethanol, cyclohexadecane dimethanol, cycloheptadecane dimethanol, cyclooctadecane dimethanol, cyclononadecane dimethanol, cycloicosandimethanol, cyclononanediethanol, cyclodecane Diethanol, cycloundecanediethanol, cyclododecanediethanol, cyclotridecanediethanol, cyclotetradecanediethanol Cyclopentadecanediethanol, cyclohexadecanediethanol, cycloheptadecanediethanol, cyclooctadecanediethanol, cyclononadecanediethanol, and cycloicosanediethanol; as compounds having three methylol / ethylol groups, cyclononane trimethanol, cyclodecane trimethanol, cyclo Undecane Trimethanol, Cyclododecane Trimethanol, Cyclotridecane Trimethanol, Cyclotetradecane Trimethanol, Cyclopentadecane Trimethanol, Cyclohexadecane Trimethanol, Cycloheptadecane Trimethanol, Cyclooctadecane Trimethanol, Cyclononadecane Trimethanol, Cycloicosane Trimethanol , Cyclohexicosan trimethanol, cyclod Santrimethanol, cyclotricosan trimethanol, cyclotetracosane trimethanol, cyclopentacosane trimmethanol, cyclohexacosan trimethanol, cycloheptacosane trimmethanol, cyclooctacosan trimmethanol, cyclononacosan trimmethanol, cyclotriacontan trimmethanol, cyclononane Triethanol, cyclodecane triethanol, cycloundecane triethanol, cyclododecane triethanol, cyclotridecane triethanol, cyclotetradecane triethanol, cyclopentadecane triethanol, cyclohexadecane triethanol, cycloheptadecane triethanol, cyclooctadecane triethanol, cyclooctane Clononadecane triethanol, cycloicosantrieetano , Cyclohexicosan triethanol, cyclodocosan triethanol, cyclotricosan triethanol, cyclotetracosane triethanol, cyclopentacosane triethanol, cyclohexacosane triethanol, cycloheptacosane triethanol, cyclooctacosane triethanol, cyclononaco Santriethanol, cyclotriacontantriethanol; compounds having four methylol / ethylol groups include cyclododecanetetramethanol, cyclotridecanetetramethanol, cyclotetradecanetetramethanol, cyclopentadecanetetramethanol, cyclohexadecanetetramethanol, and cycloheptadecanetetramethanol. Methanol, cyclooctadecanetetramethanol, cyclononadecanetetramethano , Cycloicosanetetramethanol, cyclohenicosanetetramethanol, cyclodocosanetetramethanol, cyclotricosanetetramethanol, cyclotetracosanetetramethanol, cyclopentacosanetetramethanol, cyclohexacosanetetramethanol, cycloheptacosanetetramethanol , Cyclooctacosan tetramethanol, cyclononacosan tetramethanol, cyclotriacontan tetramethanol, cyclohentriacontan tetramethanol, cyclodotriacontan tetramethanol, cyclotritriacontan tetramethanol, cyclotetratriacontan tetramethanol, cyclopentatria Contantetramethanol, cyclohexatriacontantetramethanol, cycloheptatria Ethanetetramethanol, cyclooctatriacontantetramethanol, cyclononatriacontantetramethanol, cyclotetracontantetramethanol, cyclododecanetetraethanol, cyclotridecanetetraethanol, cyclotetradecanetetraethanol, cyclopentadecanetetraethanol, cyclohexadecanetetraethanol, Cycloheptadecane tetraethanol, cyclooctadecane tetraethanol, cyclononadecane tetraethanol, cycloicosane tetraethanol, cyclohenicosane tetraethanol, cyclodocosane tetraethanol, cyclotricosane tetraethanol, cyclotetracosane tetraethanol, cyclopenta Kosan tetraethanol, cyclohexacosan tetraethanol , Cycloheptacosanetetraethanol, cyclooctacosanetetraethanol, cyclononacosantetraethanol, cyclotriacontantetraethanol, cyclohentriacontantetraethanol, cyclodotriacontantetraethanol, cyclotritriacontantetraethanol, cyclotetratria Examples thereof include contantetraethanol, cyclopentatriacontantetraethanol, cyclohexatriacontantetraethanol, cycloheptatriacontantetraethanol, cyclooctatriacontantetraethanol, cyclononatriacontantetraethanol, and cyclotetracontantetraethanol.

  Compounds having five methylol / ethylol groups include cyclopentadecane pentamethanol, cyclohexadecane pentamethanol, cycloheptadecane pentamethanol, cyclooctadecane pentamethanol, cyclononadecane pentamethanol, cycloicosane pentamethanol, cyclohenicosane pentamethanol , Cyclodocosane pentamethanol, cyclotricosan pentamethanol, cyclotetracosane pentamethanol, cyclopentacosane pentamethanol, cyclohexacosane pentamethanol, cycloheptacosane pentamethanol, cyclooctacosane pentamethanol, cyclononacosane pentamethanol, cyclonon Triacontanpentamethanol, cyclohentriacontanpentamethanol, cyclod Rear contan pentamethanol, cyclotritriacontan pentamethanol, cyclotetratriacontan pentamethanol, cyclopentatriacontan pentamethanol, cyclohexatriacontan pentamethanol, cycloheptatriacontan pentamethanol, cyclooctatriacontan pentamethanol, cyclononatria Contan pentamethanol, cyclotetracontan pentamethanol, cyclopentadecane pentaethanol, cyclohexadecane pentaethanol, cycloheptadecane pentaethanol, cyclooctadecane pentaethanol, cyclononadecane pentaethanol, cycloikosan pentaethanol, cyclohenicosan pentaethanol, Cyclodocosane pentaethanol, cyclotricosa Pentaethanol, cyclotetracosane pentaethanol, cyclopentacosane pentaethanol, cyclohexacosane pentaethanol, cycloheptacosane pentaethanol, cyclooctacosan pentaethanol, cyclononacosan pentaethanol, cyclotriacontan pentaethanol, cyclohentriacontan pentaethanol Ethanol, cyclodotriacontanpentaethanol, cyclotritriacontanpentaethanol, cyclotetratriacontanpentaethanol, cyclopentatriacontanpentaethanol, cyclohexatriacontanpentaethanol, cycloheptatriacontanpentaethanol, cyclooctatriacontanpentaethanol , Cyclononatriacontanpentaethanol, cyclotet Lacontan pentaethanol; compounds having six methylol / ethylol groups include cyclooctadecane hexamethanol, cyclononadecane hexamethanol, cycloicosane hexamethanol, cyclohenicosane hexamethanol, cyclodocosan hexamethanol, cyclotricosan hexamethanol Methanol, cyclotetracosane hexamethanol, cyclopentacosane hexamethanol, cyclohexacosane hexamethanol, cycloheptacosane hexamethanol, cyclooctacosane hexamethanol, cyclononacosan hexamethanol, cyclotriacontan hexamethanol, cyclohentriacontane hexamethanol , Cyclodotriacontan hexamethanol, cyclotritriacontan hexamethanol, cyclo Tratriacontan hexamethanol, cyclopentatriacontan hexamethanol, cyclohexatriacontan hexamethanol, cycloheptatriacontan hexamethanol, cyclooctatriacontan hexamethanol, cyclononatriacontan hexamethanol, cyclotetracontane hexamethanol, cyclooctadecane hexamethanol Ethanol, cyclononadecane hexaethanol, cycloicosane hexaethanol, cyclohexicosane hexaethanol, cyclodocosane hexaethanol, cyclotricosan hexaethanol, cyclotetracosane hexaethanol, cyclopentacosane hexaethanol, cyclohexacosane hexaethanol , Cycloheptacosan hexaethanol, cyclooctacosan hexa Tanol, cyclononacosan hexaethanol, cyclotriacontan hexaethanol, cyclohentriacontan hexaethanol, cyclodotriacontan hexaethanol, cyclotritriacontan hexaethanol, cyclotetratriacontan hexaethanol, cyclopentatriacontan hexaethanol, cyclohexa Satriacontanhexaethanol, cycloheptatriacontanhexaethanol, cyclooctatriacontanhexaethanol, cyclononatriacontanhexaethanol, cyclotetracontanehexaethanol; cyclohexicosanheptamethanol as a compound having seven methylol / ethylol groups , Cyclodocosane hepta-methanol, cyclotricosane hepta-methanol, cyclo Tetracosane heptamethanol, cyclopentacosane heptamethanol, cyclohexacosane heptamethanol, cycloheptacosane heptamethanol, cyclooctacosane heptamethanol, cyclononacosan heptamethanol, cyclotriacontan heptamethanol, cyclotriacontan heptamethanol, cyclohentriacontan heptamethanol, cyclod Triacontan heptamethanol, cyclotritriacontan heptamethanol, cyclotetratriacontan heptamethanol, cyclopentatriacontane heptamethanol, cyclohexatriacontan heptamethanol, cycloheptatriacontan heptamethanol, cyclooctatriacontan heptamethanol, cyclononatriatom Contan heptane methanol, cyclotetracontan heptane methanol , Cyclohexicosane heptaethanol, cyclodocosane heptaethanol, cyclotricosane heptaethanol, cyclotetracosane heptaethanol, cyclopentacosane heptaethanol, cyclohexacosane heptaethanol, cycloheptacosane heptaethanol, cycloheptacosane heptaethanol, cyclooctacosane heptaethanol, Cyclononacosan heptaethanol, cyclotriacontan heptaethanol, cyclohentriacontan heptaethanol, cyclodotriacontan heptaethanol, cyclotritriacontan heptaethanol, cyclotetratriacontan heptaethanol, cyclopentatriacontan heptaethanol, cyclopentatriacontan heptaethanol, cyclohexatria Contanheptaethanol, cycloheptatriacontanheptaethanol, cyclohexane Tatriacontanheptaethanol, cyclononatricontanheptaethanol, cyclotetracontanheptaethanol; as compounds having eight methylol / ethylol groups, cyclotetracosaneocta-methanol, cyclopentacosane-octa-methanol, cyclohexacosane-octa-methanol, cyclohexaoctane-methanol, cyclohepta Cosan octa-methanol, cyclononacosan octa-methanol, cyclooctacosane octa-methanol, cyclotriacontan octa-methanol, cyclohentria-contan octa-methanol, cyclodotriacontan octa-methanol, cyclotritriacontan octa-methanol, cyclotetratriacontan octa-methanol, Cyclopentatriacontanoctanemethanol, cyclohexatriacontanoctanemeta Nol, cycloheptatriacontan octa-methanol, cyclooctatriacontan octa-methanol, cyclononatriacontan octa-methanol, cyclotetracontan octa-methanol, cyclotetracosane octaethanol, cyclopentacosane octaethanol, cyclohexacosane octaethanol, cycloheptacosane Octaethanol, cyclooctacosan octaethanol, cyclononacosan octaethanol, cyclotriacontan octaethanol, cyclohentriacontan octaethanol, cyclodotriacontan octaethanol, cyclotritriacontan octaethanol, cyclotetratriacontan octaethanol, cyclo Pentatriacontanoctaethanol, cyclohexatriacontan Kuta ethanol, cycloheptanone triacontyl Tan oct ethanol, cyclooctadiene triacontyl Tan oct ethanol, cycloalkyl nona triacontyl Tan oct ethanol include cyclotetrasiloxane proximal oct ethanol.

  Among these, cyclononane dimethanol, cyclodecane dimethanol, cyclododecane dimethanol, cyclododecane trimethanol, cyclopentadecane trimethanol, cyclooctadecane trimethanol, and cycloicosane pentamethanol are preferred. Further, cyclononane dimethanol, cyclodecane dimethanol, cyclododecane dimethanol, cyclododecane trimethanol, and cyclohexadecanetetramethanol are more preferable.

  In the above-mentioned examples of the alicyclic compound containing a methylol / ethylol group, if the number of the methylol groups or the ethylol groups is satisfied, the position may be a methylol group or an ethylol group. May be present anywhere, but it is more preferable that one carbon atom on the alicyclic skeleton does not have two or more methylol groups or ethylol groups.

  The method for producing the methylol / ethylol group-containing alicyclic compound is not particularly limited, and may be appropriately selected from conventionally known methods. For example, (i) a method in which an unsaturated alicyclic compound is hydroformylated by reacting it with a mixed gas of carbon monoxide and hydrogen, and then hydrogenated by reacting with hydrogen (see, for example, JP-A-2004-359588) , (Ii) a method of reacting an unsaturated alicyclic compound with a mixed gas of carbon dioxide and hydrogen (for example, see Meher Ali, Aitor Gual, Gunter Ebeling, Jairton Dupont; Chem Cat Chem, 2014, 6, 2224-2228, etc.) ), (Iii) a method of reacting an unsaturated alicyclic compound with formic acid (for example, Manual G. Mura, Lidia De Luca, Giampaolo Giacomelli, Andrea Porcheddu; Adv. Synth. Catal., 2012, 354, 3180-3186, etc.) (Iv) a method of reacting an unsaturated alicyclic compound with an alcohol (see, for example, Stephen H. Brown, Robert H. Crabtree; J. Am. Chem. Soc., 1989, 111, 2946-2953). And the like. Preferably, the method (i) is used.

[Alicyclic polyfunctional (meth) acrylate compound-containing composition]
The alicyclic polyfunctional (meth) acrylate compound of the present invention is an alicyclic polyfunctional (meth) acrylate compound-containing composition containing the alicyclic polyfunctional (meth) acrylate compound (hereinafter referred to as “the present invention”). Alicyclic polyfunctional (meth) acrylate compound composition ").
The above-mentioned composition may be any one as long as the alicyclic polyfunctional (meth) acrylate compound is essential, and the alicyclic polyfunctional (meth) acrylate compound can be used as a curing component.
Further, a radical polymerizable compound other than the alicyclic polyfunctional (meth) acrylate compound may be contained as a curing component.

  Assuming that the total of the alicyclic polyfunctional (meth) acrylate compound and the radical polymerizable compound is 100% by mass, the mass ratio of the alicyclic polyfunctional (meth) acrylate compound exceeds 10% by mass. Is preferred. The mass ratio of the alicyclic polyfunctional (meth) acrylate compound is more preferably more than 20% by mass, still more preferably 40% by mass or more, and particularly preferably 60% by mass or more. The upper limit is not particularly limited, but is usually 100% by mass.

  The radical polymerizable compound other than the alicyclic polyfunctional (meth) acrylate compound is not particularly limited. For example, monofunctional (meth) acrylate, difunctional (meth) acrylate, trifunctional or higher ( (Meth) acrylate, monofunctional (meth) acrylamide, bifunctional (meth) acrylamide, trifunctional or higher (meth) acrylamide, styrene, (meth) acrylonitrile, maleic anhydride (maleic acid or maleic anhydride), and the like. Can be These may be used alone or in combination of two or more.

  Specifically, as the monofunctional (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, n-stearyl (meth) acrylate Phenoxyethyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide Modified (n = 2) (meth) acrylate, nonylphenol propylene oxide modified (n = 2.5) (meth) acrylate, 2- (meth) acryloyloxyethyl acid phosphate, furfuryl ( (T) acrylate, carbitol (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and the like.

Examples of the bifunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and propylene glycol di (meth) acrylate. Acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide-modified bisphenol A type di (meth) acrylate, propylene oxide Modified bisphenol A type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) acrylate, Antaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, hydroxypivalic acid-modified neopentyl glycol di (meth) ) Acrylate, 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate and the like.
Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipenta Erythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, tris (2-acryloyloxyethyl) isocyanurate, and the like.

In the alicyclic polyfunctional (meth) acrylate compound-containing composition of the present invention, one or more kinds of the alicyclic polyfunctional (meth) acrylate compound of the present invention are essential, and one of the above radical polymerizable compounds is used. It may contain species or two or more species.
Further, it may contain a monomer component other than the alicyclic polyfunctional (meth) acrylate compound and the radically polymerizable compound of the present invention, for example, a (meth) acrylate compound, a (meth) acrylamide compound, and a (meth) acrylic compound. It may contain one or more (meth) acrylic monomers such as acids and other monomers.

  The alicyclic polyfunctional (meth) acrylate compound composition of the present invention may contain a radical generator in addition to the alicyclic polyfunctional (meth) acrylate compound of the present invention. Any of a photoradical generator and a thermal radical generator used for curing a monomer can be used. These may be appropriately selected from radical polymerization initiators and the like generally used in curable resins.

Examples of the photo radical generator include benzyldimethyl ketal, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and 2-methyl-1- (4- Alkylphenone photopolymerization initiators such as methylthiophenyl) -2-morpholinopropan-1-one; acylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide; benzophenone And the like.
Examples of the thermal radical generator include an azo radical initiator such as azobisisobutyronitrile; a peroxide radical initiator such as benzoyl peroxide.
These may be used alone or in combination of two or more.

  The amount of the radical generator is not particularly limited, but is preferably from 0.1 to 15 parts by mass based on 100 parts by mass of the alicyclic polyfunctional (meth) acrylate compound of the present invention from the viewpoint of avoiding the effect on resin performance. It is preferable that it is a mass part, and it is more preferable that it is 0.2-5 mass parts.

  In addition, the alicyclic polyfunctional (meth) acrylate compound composition of the present invention may be, for example, a solvent, a pigment, an antioxidant, a leveling agent, an ultraviolet absorber, Various additives such as a flame retardant and inorganic particles can also be contained.

  Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and mesitin; aliphatic hydrocarbons such as pentane, hexane, heptane, octane, nonane, decane, cyclohexane, and cyclooctane; diethyl ether, diisopropyl Ethers such as ether, dibutyl ether, anisole and tetrahydrofuran; ketones such as methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; esters such as ethyl acetate and isopropyl acetate. These may be used alone or in combination of two or more.

  When a solvent is used, the solid concentration is preferably 5 to 95% by mass. The solid content concentration of 5% by mass or more is also preferable in order to prevent an unintended curing reaction (eg, gelation) of the alicyclic polyfunctional (meth) acrylate compound-containing composition. Further, it is preferable that the solid content concentration is 95% by mass or less from the viewpoint of coatability and storage stability. From these viewpoints, the solid content concentration is more preferably 10% by mass or more, further preferably 15% by mass or more, and more preferably 90% by mass or less, and further preferably 85% by mass or less. And particularly preferably 80% by mass or less. In the present invention, “solid content” means a component excluding a solvent, and includes not only a solid component but also a semi-solid or viscous liquid material.

  Examples of the inorganic particles include silica (including organosilica sol), alumina, titania, zeolite, mica, synthetic mica, calcium oxide, zirconium oxide, zinc oxide, magnesium fluoride, smectite, synthetic smectite, vermiculite, and ITO (indium oxide). / Tin oxide), ATO (antimony oxide / tin oxide), tin oxide, indium oxide, antimony oxide, and the like. Of these, silica is preferable. Further, the above-mentioned inorganic particles may be used alone or in combination of two or more.

  The amounts of the various additives and inorganic particles are not particularly limited, and may be appropriately selected as desired.

[Cured product]
The cured product of the present invention contains a structural unit derived from the alicyclic polyfunctional (meth) acrylate compound of the present invention, and usually contains the above-described alicyclic polyfunctional (meth) acrylate compound-containing composition of the present invention. It is obtained by curing an object.

  In the preparation of the cured product of the present invention, the curing conditions may be light curing or heat curing. In any case, the effect of quick-setting can be obtained.

  The photo-curing method is not particularly limited, but after applying the alicyclic polyfunctional (meth) acrylate compound-containing composition of the present invention onto a substrate, or after pouring into a mold, ultraviolet light (UV) The method of irradiating in an irradiation device is preferable. The amount of UV irradiation may be appropriately adjusted depending on the intensity of the light source, the type and concentration of the curing component to be mixed, and the like.

In the case of photo-curing, the irradiation amount of ultraviolet rays (unit: mJ / cm ² ) is usually from 10 to 10,000 mJ / cm ² , and the curability of the alicyclic polyfunctional (meth) acrylate compound composition of the present invention, from the viewpoint of flexibility, etc. of the cured product (cured film) is 100~5,000mJ / cm ^2, more preferably 200~3,000mJ / cm ^2.

  The thermosetting method is not particularly limited, but the alicyclic polyfunctional (meth) acrylate compound-containing composition of the present invention is applied on a substrate or poured into a mold, and then in an oven or A method of heating on a hot plate is preferred. The curing temperature and the rate of temperature rise may be appropriately adjusted depending on the type and concentration of the curing component, and are usually about 15 to 160 ° C.

  In the case of a conventional polyfunctional (meth) acrylate compound, for example, when used for optical applications, etc., the properties such as the light transmittance required of such a curable resin are sufficiently obtained, and then the fast curing property and the high The alicyclic polyfunctional (meth) acrylate compound of the present invention could not have all of the properties such as hardness, scratch resistance, light transmittance, moisture permeability prevention, and adhesion to non-polar materials. Then, all of these characteristics can be provided.

  As described above, the alicyclic polyfunctional (meth) acrylate compound of the present invention, the composition containing the same, and the cured product thereof are, as described above, fast-setting, high-hardness, abrasion-resistant, light-transmitting, and light-transmitting. Since all of the functions that have been difficult to coexist conventionally, such as anti-moisture properties and adhesion to non-polar materials, can be provided, they can be suitably used for various applications. That is, it is suitable for use in photocurable resins and thermosetting resins, particularly for acrylic resins.For example, it is suitable as an acrylic hard coat agent, paint, ink, diluent, adhesive, adhesive, and the like. Things.

[Laminate]
The laminate of the present invention has a substrate and a layer composed of the above-described cured product of the present invention as a hard coat layer on the substrate, and the alicyclic polyfunctional (meth) acrylate compound of the present invention. By using, it has characteristics such as fast curing, high hardness, scratch resistance, light transmittance, moisture permeability prevention, and adhesion to non-polar materials.

  The hard coat layer formed on the substrate is formed by, for example, applying (coating) the alicyclic polyfunctional (meth) acrylate compound composition of the present invention on the substrate and irradiating the substrate with an active energy ray. Can be formed. As a method of applying (coating) the alicyclic polyfunctional (meth) acrylate compound composition of the present invention on a substrate, for example, a reverse coating method, a gravure coating method, a rod coating method, a bar coating method, a Meyer bar A coating method, a die coating method, a spray coating method and the like can be mentioned. Although the form of the cured product of the present invention is not particularly limited, usually, a cured product obtained by irradiating an active energy ray on a substrate to cure the cured product is a cured film (cured) on at least a part of one surface of the substrate. Film).

  As the substrate, various thermoplastic resin substrates such as a thermoplastic resin film and a thermoplastic resin plate can be used. The thermoplastic resin substrate is not particularly limited as long as it is a resin that exhibits plasticity when heated. Examples of the thermoplastic resin film include a triacetyl cellulose (TAC) film, a polyethylene terephthalate (PET) film, a diacetylene cellulose film, an acetate butyrate cellulose film, a polyether sulfone film, a poly (meth) acrylic resin film, and a polyurethane resin film. Resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth) acrylonitrile film, cycloolefin polymer (COP) film and the like can be used. Further, as a thermoplastic resin plate, for example, acrylic plate, triacetyl cellulose plate, polyethylene terephthalate plate, diacetylene cellulose plate, acetate butyrate cellulose plate, polyether sulfone plate, polyurethane plate, polyester plate, polycarbonate plate, polysulfone plate, poly Examples include an ether plate, a polymethylpentene plate, a polyetherketone plate, and a (meth) acrylonitrile plate. Further, glass or the like can be used as needed. All of these base materials have excellent transparency and are preferable for application to a display device described later. Of these, the cured product of the present invention has excellent adhesion to non-polar materials, and thus it is preferable to use a non-polar material such as a cycloolefin polymer, polypropylene, or polyethylene, particularly a substrate made of a cycloolefin polymer. In addition, the thickness of the base material can be appropriately selected according to the application, but generally, a thickness of about 1 to 5000 μm is used.

  The thickness of the hard coat layer formed of the cured product of the present invention formed on such a substrate is not particularly limited, and is usually 0.01 to 100 μm, and preferably various thicknesses in the range of 0.1 to 50 μm. It can be appropriately set in consideration of the factors.

Note that the laminate of the present invention may have a base material and the above-described hard coat layer, and may have another functional layer such as a primer layer between the base material and the hard coat layer. Good.
Further, the hard coat layer may be formed in multiple layers, or another functional layer such as an optical adjustment layer may be provided on the hard coat layer.

  Such a laminate of the present invention can be applied to a display device using the laminate together with a light source. In this case, the substrate on which the hard coat layer is formed is preferably a light-transmitting substrate. Further, the light source is preferably disposed on the back surface of the base material, that is, on the surface of the base material opposite to the surface on which the hard coat layer is formed, and emits light toward the base material therefrom.

  A display device using the laminate of the present invention includes a liquid crystal display device (liquid crystal display), an LED (light emitting diode display), an ELD (electroluminescence display), a VFD (fluorescent display), a PDP (plasma display panel), and the like. It can be applied to flat panel displays.

  In addition, as an application of the display device using the laminate of the present invention outdoors or semi-outdoor, a touch panel is given, which has a mechanism for operating a device by pressing a display on a screen, for example, Guidance display devices installed in facilities such as bank ATMs, vending machines, personal digital assistants (PDAs), copiers, facsimile machines, game machines, museums and department stores, car navigation systems, multimedia stations (multiple facilities installed in convenience stores) The present invention is useful in functional terminals, mobile phones, monitoring devices for railway vehicles, and the like.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist of the present invention.
In the following, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise specified.

[Example 1]
<Synthesis of cyclododecane trimethanol>
1800 g of 1,5,9-cyclododecatriene (manufactured by Aldrich) is dissolved in 3200 ml of toluene, and 1.95 g of dicarbonylacetylacetonatotrodium and tris (2,4-di-t-butylphenyl) phosphite are dissolved. 49.63 g were added. The liquid was charged into a stainless steel induction stirring type autoclave having an internal volume of 10 L, and a reaction was carried out at 50 ° C. and 5 MPa while flowing a mixed gas of H ₂ / CO = 1/1 (mol / mol). The reaction was finally performed at 80 ° C. and 7 MPa while gradually increasing the temperature and pressure, and the reaction was completed for a total of 15 hours.
Thereafter, the autoclave was cooled to room temperature, and after purging with an H ₂ / CO mixed gas, the inside of the system was replaced with nitrogen. The autoclave was opened, 630 g of the nickel / silica catalyst was put in a metal basket, set in the autoclave, and reacted at 110 ° C. and 12 MPa while flowing H ₂ gas. The pressure was gradually increased, and the reaction was finally performed at 14 MPa, thus completing the reaction for a total of 68 hours. 370 g of the reaction solution from which toluene was removed was collected, and 130 g of cyclododecane trimethanol was obtained by distillation and purification.

<Synthesis of cyclododecane trimethyl triacrylate (CDTMTA)>
8 g of the obtained cyclododecane trimethanol, 19 g of triethylamine and 0.5 g of N, N-dimethyl-4-aminopyridine were dissolved in 100 ml of dichloromethane. While cooling with ice in a nitrogen atmosphere, 16 g of acrylic acid chloride was added dropwise, and the mixture was stirred at room temperature for 1 hour. 100 ml of diisopropyl ether was added to the reaction solution, dichloromethane was distilled off, and the solvent was exchanged. It was washed twice with 100 ml of pure water, twice with 100 ml of a 0.2% aqueous sodium hydroxide solution, and twice with 3.5% hydrochloric acid. After performing the filtration treatment, the solvent was distilled off, and 6 g of cyclododecane trimethyl triacrylate (CDTMTA) was obtained.

When the ¹ H NMR spectrum of CDTMTA was measured using a nuclear magnetic resonance apparatus (“AVANCE 400” manufactured by Bruker) using CDCl ₃ as a solvent, the following results were obtained.
δ 1.09-2.00, bm, 21H (alicyclic skeleton)
_{δ 3.93-4.14, bm, 6H (OCH} 2)
δ 5.78-5.87, d, 3H (acryloyl)
δ 6.07-6.19, m, 3H (acryloyl)
δ 6.35-6.44, d, 3H (acryloyl)

<Preparation of alicyclic polyfunctional (meth) acrylate compound-containing composition>
To 100 parts of cyclododecane trimethyl triacrylate obtained by the above steps, 60 parts of methyl ethyl ketone and 3 parts of a photopolymerization initiator (Irgacure 184, manufactured by BASF) are added and dissolved, and an alicyclic polyfunctional (meth) acrylate compound is dissolved. A containing composition was obtained. Next, using a bar coater, coating films of the above composition were prepared on various substrates, and various evaluations (excluding viscosity) described later were performed.

[Comparative Examples 1 to 6]
Using the following commercially available polyfunctional acrylate, a composition and a coating film were prepared in the same manner as in Example 1 above, and various evaluations (excluding viscosity) described later were performed.
Comparative Example 1: DPHA (dipentaerythritol hexaacrylate)
Comparative Example 2: TCDDA (tricyclodecane dimethanol diacrylate)
Comparative Example 3: TMPTA (trimethylolpropane triacrylate)
Comparative Example 4: NDDA (1,9-nonanediol diacrylate)
Comparative Example 5: NPDA (neopentyl glycol diacrylate)
Comparative Example 6: DDDA (1,10-decanediol diacrylate)

  In the above Examples and Comparative Examples, the viscosity, UV curability, COP adhesion, pencil hardness, transparency, scratch resistance, and moisture permeability prevention (moisture permeability) were measured by the following procedures. Table 1 shows the results.

<Viscosity>
The viscosities of the compositions obtained in the above Examples and Comparative Examples were measured using an E-type rotational viscometer (“VISCOMMETER TVE-20L” manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and 20 rpm. This viscosity is preferably from 200 to 1,000,000 mPas.

<UV curability>
The coating films prepared in the above Examples and Comparative Examples were irradiated with a UV lamp at 100 mW / cm ² , the surface was lightly touched by hand, and the irradiation amount (mJ) until the coating film was tack-free was measured. Curable (mJ / cm ² ). The thickness of the coating film was about 20 μm (the thickness after evaporating the solvent), and 1 mm thick PMMA (polymethyl methacrylate) was used as the substrate. The smaller the numerical value, the better the UV curability (mJ / cm ² ). In addition, in the evaluation according to the present example, a material having a UV curability of 500 mJ / cm ² or less is useful as a hard coat agent.

<COP adhesion>
The coating films prepared in the above Examples and Comparative Examples were irradiated with a UV lamp under the condition of an irradiation amount of 1000 mJ / cm ² (300 mW / cm ² ) to be UV-cured, and then the cured film was cross-cut into 100 squares. did. Next, a scotch tape was stuck to the cross cut portion, and the number of squares remaining on the substrate after peeling was measured. The thickness of the coating film was about 3 μm (the thickness after evaporating the solvent), and a COP (cycloolefin polymer) having a thickness of 100 μm was used as the substrate. The upper limit of the COP adhesion is 100, which indicates that the smaller the COP adhesion, the lower the adhesion to non-polar materials. In the evaluation according to the present example, a COP adhesive having a COP of 90 or more is useful as a hard coat agent for a COP substrate.

<Pencil hardness>
The coating films prepared in the above Examples and Comparative Examples were irradiated with a UV lamp at a dose of 500 mJ / cm ² (300 mW / cm ² ) and UV-cured. Were rubbed with a load of 750 g using a pencil having a low hardness in order to check for scratches. The test was performed five times, and the maximum hardness at which no damage was found three or more times was measured. The thickness of the coating film was about 125 μm (the thickness after evaporating the solvent), and PET (polyethylene terephthalate) having a thickness of 125 μm was used as the substrate. The pencil hardness is expressed as 4B, 3B, 2B, B, F, H, 2H, 3H, 4H, and becomes higher in the order of writing. In the evaluation according to the present example, a material having a hardness of H or more is useful as a hard coat agent.

<Transparency>
The coating films prepared in the above Examples and Comparative Examples were irradiated with a UV lamp under a condition of an irradiation amount of 500 mJ / cm ² (300 mW / cm ² ) (however, NDDA only was irradiated at 2000 mJ / cm ² (300 mW / cm ² ) to perform UV irradiation. After curing, the total light transmittance (%) and haze (%) were measured using a haze meter (“Haze Meter HM-65W” manufactured by Murakami Color Research Laboratory). A PMMA (polymethyl methacrylate) having a thickness of 1 mm was used as a substrate, and the larger the value of the total light transmittance (%), the better the transparency. The smaller the numerical value of the haze (%), the better the transparency.In the evaluation according to the present example, if the total light transmittance is 90% or more and the haze is 1% or less, the hard coat It is useful as an agent.

<Scratch resistance>
Steel wool # 0 was applied to the surface of the coating film used in the above-described transparency evaluation, and the coating film was reciprocated 10 times under a load of 500 g. Thereafter, the haze (%) was measured again using a haze meter (“Haze Meter HM-65W” manufactured by Murakami Color Research Laboratory), the degree of change in the value (ΔHz (%)) was calculated, and the scratch resistance (ΔHz) was measured. (%)). The thickness was about 12 to 36 μm (the thickness after evaporating the solvent), and PMMA (polymethyl methacrylate) having a thickness of 1 mm was used as the base material. The smaller the value of the scratch resistance (ΔHz (%)), the better. In the evaluation according to the present example, a scratch resistance of 5% or less is useful as a hard coat agent.

<Moisture permeability prevention (moisture permeability)>
To coating films prepared in Examples and Comparative Examples, was irradiated under the conditions of irradiation dose 1000 mJ ^/ cm 2 UV-lamp (300mW / cm ²⁾ (where NDDA only ^{2000mJ / cm 2 (300mW / cm} 2)) After UV curing, the moisture permeability (g / m ² · day) was measured by a method according to JIS Z0208. The thickness of the coating film was about 7 to 11 μm (the thickness after evaporating the solvent), and TAC (triacetyl cellulose) having a thickness of 40 μm was used as the base material. The smaller the value of the moisture permeability (g / m ² · day), the better the moisture permeability. In the evaluation according to the present example, a material having a moisture permeability of 200 (g / m ² · day) or less is useful as a hard coat agent.

(* 1) In the COP adhesion evaluations of Comparative Examples 1 and 3, the composition repelled the COP substrate, and a coating film could not be formed. For this reason, it was impossible to evaluate the adhesion itself.
(* 2) In the evaluation of the COP adhesion in Comparative Example 2, although 86 masses adhered, peeling occurred around the test portion.
(* 3) In all of Comparative Examples 4 to 6, the UV curability was insufficient, so that a cured film was not obtained, and the COP adhesion and the pencil hardness were not evaluated.
(* 4) In Comparative Example 6, the viscosity could not be measured because it was a solid at 25 ° C.
(* 5) In Comparative Example 6, a uniform coating film could not be obtained on the TAC base material, so that it was impossible to evaluate the moisture permeability prevention property.

  Both the alicyclic polyfunctional (meth) acrylate compound of the present invention and the comparative polyfunctional (meth) acrylate compound have characteristics such as light transmittance. With regard to properties such as transparency, moisture permeability prevention, abrasion resistance, and adhesion to non-polar materials, conventional polyfunctional (meth) acrylate compounds cannot all exhibit high performance. However, the alicyclic polyfunctional (meth) acrylate compound of the present invention can exhibit a high level of performance in all of these properties required for the curable resin. In particular, the alicyclic polyfunctional (meth) acrylate compound of the present invention has excellent adhesion to non-polar materials, which is not present in conventional polyfunctional (meth) acrylate compounds. Also, with respect to the moisture permeation prevention property, it is the best among the polyfunctional (meth) acrylate compounds compared, and has a higher viscosity.

  In the above example, cyclododecanetrimethyltriacrylate having a structure in which X is a 12-membered alicyclic hydrocarbon group and has three acryloyloxymethyl groups in the general formula (I) is used. In the alicyclic polyfunctional (meth) acrylate compound of the present invention, since the (meth) acryloyloxy group is bonded to the ring structure via a methylene group or an ethylene group, the concentration of the polar group is higher than that of the conventional polyfunctional (meth) acrylate compound. The mechanism of action in which all the above-mentioned properties are exhibited by being lower than that of the functional (meth) acrylate compound and being non-aromatic is the same for any alicyclic polyfunctional (meth) acrylate compound. it is conceivable that.

Claims (5)

An alicyclic polyfunctional (meth) acrylate compound represented by the following general formula (I).

(Wherein, R ¹ represents a hydrogen atom or a methyl group, R ² represents a hydroxyl group or a monovalent organic group, and X represents an alicyclic hydrocarbon group having a monocyclic structure of a 9 to 40-membered ring. However, when R ² is a monovalent organic group, two or more R ² may combine with each other to form a condensed ring containing ring X. l represents an integer of 1 or 2; Represents an integer of 2 to 10, and n represents an integer of 0 to 10. However, when the number of carbon atoms constituting the ring X is x, 2x ≧ m + n.) A cured product comprising a curable resin containing a structural unit derived from the alicyclic polyfunctional (meth) acrylate compound according to claim 1.   A laminate comprising a substrate and a hard coat layer, wherein the hard coat layer comprises the cured product according to claim 2.   The laminate according to claim 3, wherein the substrate is a thermoplastic resin substrate.   The laminate according to claim 4, wherein the thermoplastic resin substrate is made of a cycloolefin polymer.