WO2017177796A1 - Applications of novel free radical photocuring system and composition thereof - Google Patents

Abstract

A free radical photocuring composition comprises: an anthraquinone sensitizer, selected from a compound having a structure represented by formula (I) and/or a macromolecular compound using the compound represented by formula (I) as a main structure; a free radical reaction compound; and a free radical initiator. The composition has low costs, has excellent response to light sources having a wavelength ranging from 200 nm to 500 nm, a high curing speed, a good development property and good pattern integrity, allows a cured film to have a high hardness and has a strong adhesive force on a substrate, and can be used in paints, coatings, ink, molding materials and other aspects.

Description

Application of a novel free radical photocuring system and its composition Technical field

The invention belongs to the technical field of organic light curing, and in particular relates to a novel free radical photocurable composition and its application in the field of photocuring.

Background technique

Free radical photocuring has the advantages of fast curing rate and low price, and is widely used in the field of photocuring. Like other photocuring systems, the existing free radical photocuring system is based on high-pressure mercury lamps (wavelength range is usually 200-360nm), which has high energy consumption, large environmental pollution, and is used more and more. limits. LED light sources (typically in the range of 320-500 nm) have low damage, high energy and low consumption, and are considered to be a good alternative to mercury lamps as a conventional light source in photocuring systems. However, most of the existing free radical photocuring systems have poor absorption capacity for LED light sources, and are often difficult to cure or have poor curing effects. The active intermediates in the combined free radical photocuring system have a short life span and basically have no post-cure characteristics. This largely limits the application of LED light sources in the field of free radical light curing. In view of this, in line with current technological development trends and practical application requirements, it is particularly necessary to develop a free radical photocuring system with excellent photocuring properties in the wavelength range of 200-500 nm (including mercury lamps and LED light sources).

Summary of the invention

It is an object of the present invention to provide a novel free radical photocurable composition. The composition has excellent response to a light source in the wavelength range of 200-500 nm, low cost, fast curing speed, good developability and pattern integrity, high hardness of the cured film, and strong adhesion on the substrate.

Specifically, the radical photocurable composition of the present invention comprises the following components:

(A) an oxime ester sensitizer selected from the group consisting of a compound having the structure of the formula (I) and/or a macromolecular compound having a compound of the formula (I) as a main structure:

R ₁ and R ₂ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C ₄₀ linear or branched alkyl, C ₁ -C ₄₀ alkoxy, or -O-CO-R group, and R ₁ and R ₂ at least one -O-CO-R group, R Representative C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ alkylcycloalkyl or cycloalkyl group An alkyl group, a C ₂ -C ₄₀ ester-containing group, a C ₂ -C ₄₀ -containing epoxy group, a halogen, or a C ₃ -C ₂₀ halogen-substituted alkyl group;

R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C ₄₀ linear or branched alkyl a C ₃ -C ₄₀ cycloalkyl group, a C ₄ -C ₄₀ alkylcycloalkyl group or a cycloalkylalkyl group, a C ₂ -C ₄₀ alkenyl group, or a C ₆ -C ₄₀ aryl group, and The acyclic -CH ₂ - in these groups may be optionally substituted by -O-, -CO-, -NH-, -S- or 1,4-phenylene;

(B) a radical reactive compound;

(C) A radical photoinitiator.

The radical photocurable composition of the present invention has a good response to light in the wavelength range of 200-500 nm, and the applicable light source includes, but is not limited to, a mercury lamp, a halogen lamp, an electrodeless lamp, an LED lamp, a laser, and the like.

In view of its excellent performance, the photocurable composition of the present invention can be applied to paints, coatings, inks and molding materials, and can be specifically applied to: in plastics, metals, glass, ceramics, wood, walls, optical fibers, and the like. Coating materials for coating; protective coating materials such as hard coating agent, antifouling film, antireflection film, impact buffer film; photocurable adhesive, adhesive, photodegradable coating, coating film, molding; holographic image Optical recording medium for materials, etc.; optical molding resin, for example, 3D printing ink (resin), photoresist for electronic circuit and semiconductor manufacturing, photoresist for electronic materials such as color filter, black matrix, dry film, etc. Etching; interlayer insulating film, light extraction film, brightness enhancement film, sealing material; printing ink for screen printing, offset printing, gravure printing, photocuring ink for inkjet printing; lens, lens array, optical waveguide, guide Optical components such as light plates, light diffusing plates, and diffractive elements; optical spacers, rib walls, materials for nanoimprinting, and the like.

The components of the radical photocurable composition of the present invention mainly comprise components (A), (B) and (C), all of which belong to the class of compounds known in the prior art. Through the combination of these three components, the radical photocurable composition has excellent response to light sources (such as mercury lamps and LED lamps) in the wavelength range of 200-500 nm, fast curing speed, excellent developability and pattern integrity. The cured film has high hardness, strong adhesion on the substrate, low cost, and superior application effect.

The photocurable composition of the present invention mainly comprises components (A) to (C), and the components will be described in more detail below.

<Component (A) oxime ester sensitizer>

As the oxime ester sensitizer of the component (A), it is selected from a compound having a structure represented by the formula (I) and/or a macromolecular compound having a main structure of the compound of the formula (I):

R ₁ and R ₂ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C ₄₀ linear or branched alkyl, C ₁ -C ₄₀ alkoxy, or -O-CO-R a group, and at least one of R ₁ and R ₂ is a -O-CO-R group, R represents a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ alkylcycloalkyl group or a cycloalkyl group An alkyl group, a C ₂ -C ₄₀ ester-containing group, a C ₂ -C ₄₀ -containing epoxy group, a halogen, or a C ₃ -C ₂₀ halogen-substituted alkyl group;

R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C ₄₀ linear or branched alkyl a C ₃ -C ₄₀ cycloalkyl group, a C ₄ -C ₄₀ alkylcycloalkyl group or a cycloalkylalkyl group, a C ₂ -C ₄₀ alkenyl group, or a C ₆ -C ₄₀ aryl group, and The acyclic -CH ₂ - in these groups may be optionally substituted by -O-, -CO-, -NH-, -S- or 1,4-phenylene.

Herein, the non-cyclic -CH ₂ - means that no cyclic structure in -CH ₂ -, i.e. exclude cyclic structure -CH ₂ -. For example, the above R "acyclic ₂ -CH -" ₃ -R ₁₀ in ₂ includes straight chain or branched chain alkyl -CH - alkyl structure, alkylcycloalkyl and cycloalkylalkyl in -CH ₂ -, alkenyl and -CH ₂ - in aryl.

Preferably, in the structure of the formula (I), R ₁ and R ₂ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C ₂₀ linear or branched alkyl, C ₁ -C Alkoxy group of ₂₀ , or -O-CO-R group, and at least one of R ₁ and R ₂ is a -O-CO-R group, and R represents a C ₃ -C ₁₀ cycloalkyl group, C ₄ -C ₁₄ alkylcycloalkyl or cycloalkylalkyl, C ₃ -C ₂₀ ester-containing group, C ₃ -C ₂₀ epoxy group-containing group, halogen, or C ₃ -C ₂₀ An alkyl group substituted by a halogen.

In the optional group of R, the ester group-containing group means that the group contains at least one -CO-O- or -O-CO-, and for example, may be a group containing a (meth) acrylate group. Preferably, in addition to the ester group, other structural moieties containing an ester group are of an alkyl structure and/or an alkenyl structure. The epoxy group-containing group means that the group contains at least one epoxy group; preferably, in addition to the epoxy group, the other structural moiety containing the epoxy group belongs to the alkyl structure.

Further preferably, in the structure represented by the formula (I), R ₁ and R ₂ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C ₁₀ linear or branched alkyl, C ₁ -C ₁₀ alkoxy, or -O-CO-R group, and at least one of R ₁ and R ₂ is a -O-CO-R group, and R is selected from one of the following groups:

Wherein h = 0-3, i = 1-4, and when h = 0, hydrogens on the cycloalkyl can be optionally substituted with C ₁ -C ₄ alkyl;

-(CH ₂ ) _j -CO-OC _k H _2k+1 or -(CH ₂ ) _j -O-CO-C _k H _2k+1 , wherein j=1-4, k=1-6;

-(CH ₂ ) _r -O-CO-CH=CH ₂ , wherein r=1-5;

Where m=1-3, n=0-5;

Wherein x = 1-3, y = 1-2, z = 0-3;

Where p=1-5, q=0-5;

Cl, F, Br, -(CH ₂ ) _s (CH ₂ ) _t CCl, -(CH ₂ ) _s (CH ₂ ) _t CF, -(CH ₂ ) _s (CH ₂ ) _t CBr, where s=1- 6, t = 1-6;

And the hydrogen in the structure in which h, j, r, m, x, y, p, s, t is present may be optionally substituted by a C ₁ -C ₄ alkyl group. Among these groups, C _k H _2k+1 , C _n H _2n+1 , C _z H _2z+1 and C _q H _2q+1 represent a linear or branched alkyl group having a corresponding number of carbon atoms; The value includes an integer value between the end value and the end value, for example h=0-3 indicating that h can be 0, 1, 2 or 3; these are very clear and obvious to those skilled in the art.

Preferably, in the structure represented by the formula (I), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C straight or branched ₂₀ alkyl group, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ alkylcycloalkyl or cycloalkylalkyl, C ₂ -C ₁₀ alkenyl is Or a C ₆ -C ₂₀ aryl group, and the acyclic -CH ₂ - of these groups may be optionally substituted by -O-, -CO- or 1,4-phenylene.

Further preferably, R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ each independently represent a straight chain of hydrogen, nitro, cyano, halogen, C ₁ -C ₁₂ or Branched alkyl, C ₃ -C ₁₀ cycloalkyl, C ₄ -C ₁₀ alkylcycloalkyl or cycloalkylalkyl, C ₂ -C ₆ alkenyl, or C ₆ -C ₁₀ An aryl group, and the acyclic -CH ₂ - in these groups may be optionally substituted by -O- or -CO-.

In the present invention, a compound having a structure represented by the formula (I) can be obtained commercially or conveniently obtained by a conventionally known method. For example, the preparations can be referred to the methods described in CN104991418A, CN105001081A, CN105037587A, and JP2013107848A, which are hereby incorporated by reference in entirety.

As an optional oxime ester sensitizer, the macromolecular compound having the main structure of the compound of the formula (I) may be a compound of the formula (I) by polymerization (including homopolymerization and copolymerization), esterification or transesterification. And the formation of macromolecular compounds. The corresponding synthetic methods can be found in the Chinese Patent Application Publication No. WO104991418A, the disclosure of which is incorporated herein by reference.

Illustratively, the oxime ester sensitizer as the component (A) may be one or a combination of two or more of the compounds shown by the following structures:

In the radical photocurable composition of the present invention, the oxime ester sensitizer as the component (A) may be one or a combination of two or more compounds selected from the structures represented by the formula (I). a compound and/or a macromolecular compound having a main structure of the compound of the formula (I). The content of the component (A) oxime ester sensitizer in the composition is from 0.001 to 10%, preferably from 0.01 to 5%, more preferably from 0.1 to 2% by mass.

<Component (B) radical reactive compound>

In the photocurable composition of the present invention, the component (B) radical reactive compound is a (meth) acrylate compound and/or an alkenyl ether compound, and the compound may be a monomer, a prepolymer, or an oligomer. Chemical forms such as substances and polymers.

The (meth) acrylate compound may be selected from the group consisting of alkyl (meth) acrylate, hydroxy (meth) acrylate, (meth) acrylate of (poly)alkylene glycol, and ternary or higher polyhydric alcohol. (Meth) acrylate or its dicarboxylic acid modification, epoxy acrylate, urethane (meth) acrylate, polyester acrylate, (meth) acrylate of terminal hydroxylated polymer, urethane resin, (meth) acrylate of an oligomeric resin such as a silicone resin or a spiro resin.

The (meth) acrylate compound is preferably an alkyl (meth) acrylate or a (poly)alkylene glycol from the viewpoints of compatibility effects such as curing efficiency, developability, film hardness, and substrate adhesion. One or a combination of two or more of (meth) acrylate, a (meth) acrylate of a trihydric or higher polyhydric alcohol, an epoxy acrylate, and a urethane (meth) acrylate.

The (meth) acrylate type compound may be selected from one or a combination of two or more of the following compounds: methyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylate. Isobutyl ester, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, Bisphenol A epoxy acrylate resin, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, tripropylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trishydroxymethyl Alkane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, Dipentaerythritol hexa(meth) acrylate or the like.

The above alkenyl ether compound may be a vinyl ether, a 1-propenyl ether, a 1-butenyl ether, and/or a 1-pentenyl ether compound, and is preferably a vinyl ether compound. More preferably, the vinyl ether compound may be selected from the group consisting of triethylene glycol divinyl ether, 1,4-cyclohexyl dimethanol divinyl ether, 4-hydroxybutyl vinyl ether, glycerin carbonate vinyl ether, ten One or a combination of two or more of dialkyl vinyl ethers and the like.

In the radical photocurable composition of the present invention, the content of the component (B) radical-reactive compound is from 10 to 90% by mass, preferably from 40 to 90% by mass.

<Component (C) radical type photoinitiator>

Common free-radical photoinitiators are dialkoxyacetophenones, α-hydroxyalkylphenones, α-aminoalkylphenones, acylphosphine oxides, benzophenones, benzoin Classes, benzil, heterocyclic aryl ketones, oxime ester photoinitiators, and the like.

The radical type photoinitiator as the component (C) is preferably a benzophenone, an α-hydroxyalkyl phenone, and a combination of effects such as a cost and a synergistic effect such as photoinitiation efficiency and curing speed. / or α-aminoalkyl phenones, benzil compounds.

Illustratively, the radical type photoinitiator as component (C) is one or a combination of two or more of the compounds shown in the following structures:

In the radical photocurable composition of the present invention, when two or more kinds of radical photoinitiators are selected, a combination of two or more kinds of the same type of compounds may be used, or a combination of different types of compounds may be used. The component (C) radical type photoinitiator is contained in the composition in an amount of from 0.001 to 20%, preferably from 0.1 to 10% by mass.

<Component (D) Other Components>

In addition to the above components (A), (B) and (C), the photocurable composition of the present invention may optionally be added with organic and/or inorganic auxiliaries commonly used in the art, including but It is not limited to pigments, leveling agents, dispersants, curing agents, surfactants, solvents, etc., as will be apparent to those skilled in the art. In addition, other sensitizers and/or photoinitiators may be added to the composition for compounding without adversely affecting the application of the composition.

According to the application requirements of the product, one or more macromolecules or polymer compounds may be selectively added to the composition to improve the application performance of the composition during use. The macromolecular or high molecular compound may be a polyol. Or polyester An alcohol; a polymer not containing a reactive functional group, which is usually a resin containing an acidic functional group such as a phenolic hydroxyl group or a carboxyl group, may also be selectively added.

<Preparation of Photocurable Composition>

The photocurable composition of the present invention can be obtained by weighing each component by weight and uniformly mixing.

At present, the marketed products in the field of free radical light curing, especially the middle and high-end products, are still mainly imported. Most of these products have patented technology and the prices of products are high, while domestic enterprises lack core technology and independent intellectual property rights, under strict technical barriers. Corporate development and even R&D layout have been greatly limited. The invention is optimized by components, especially the addition of a specific oxime sensitizer, so that the photocurable composition has a large wavelength range of light and good light curing effect, and can be applied in various fields such as paints, coatings, inks, molding materials and the like. , with strong technology and market competitiveness.

detailed description

It should be noted that the embodiments in the present application and the features in the embodiments may be combined with each other without conflict. The invention will be described in detail below with reference to the embodiments.

The present application is further described in detail below with reference to the specific embodiments, which are not to be construed as limiting the scope of the claims.

Unless otherwise stated, the parts described below are by weight. And the meanings of the abbreviations are as follows:

MMA: Methyl methacrylate (CM205)

TEDE: Triethylene glycol divinyl ether (DVE-3)

HDDA: 1,6-hexanediol diacrylate (SR238)

TPGDA: Tripropylene glycol diacrylate (SR306)

TMPTA: Trimethylolpropane triacrylate (SR351)

Solvent: acetone.

1. Preparation of photocurable composition

The photocurable composition was formulated according to the formulation shown in Table 1 below.

Table 1

2, performance test

(1) Film formation test under high pressure mercury lamp

The photocurable composition was stirred under a yellow light, and a film was formed by roll-coating on a PET template, and dried at 90 ° C for 5 minutes to remove a solvent to form a coating film having a film thickness of about 2 μm. The substrate on which the coating film was formed was cooled to room temperature, a mask was attached, and the coating film was exposed to light with a high pressure mercury lamp (exposure model RW-UV70201, light intensity: 50 mW/cm ² ) for an exposure time of 30 s. Visual observation was performed to evaluate the film formation of the exposed area.

Subsequently, it was immersed in a 1% aqueous NaOH solution at 25 ° C for 30 s, washed with ultrapure water, and air-dried; then baked in an oven at 240 ° C for 30 min to obtain a mask transfer pattern. The pattern on the substrate was observed with a scanning electron microscope (SEM) to evaluate developability and pattern integrity.

The evaluation criteria for film formation are as follows:

○: the surface of the film is smooth;

◎: There is flaw on the surface of the film;

●: Film formation is not possible.

The developability evaluation criteria are as follows:

○: no residue was observed in the unexposed portion;

◎: a small amount of residue was observed in the unexposed portion, but the residual amount was acceptable;

●: Obvious residue was observed in the unexposed portion.

The pattern integrity evaluation criteria are as follows:

○: no pattern defects were observed;

◎: A small defect was observed in a small part of the pattern;

●: Many pattern defects were clearly observed.

The evaluation results are shown in Table 2.

Table 2

Note: "-" is because it cannot be filmed, which makes it impossible to evaluate.

(2) Film formation test under LED light source

The photocurable composition was stirred under a yellow light, and a film was formed by roll-coating on a PET template, and dried at 90 ° C for 5 minutes to remove a solvent to form a coating film having a film thickness of about 2 μm. The substrate on which the coating film was formed was cooled to room temperature, and a mask was attached thereto. The LED light source having a wavelength of 395 nm and a light intensity of 2300 mW/cm ² was used to maintain the distance between the substrate on which the coating film was formed and the tube at 10 cm, and exposed and detected. Its initial curing time.

The initial curing time refers to the time when the surface hardness of the material reaches the trace without using the 1H Zhonghua advanced drawing pencil under the illumination of the LED light source. The preliminary curing time can be used to measure the initiation efficiency of the photoinitiator.

After the preliminary curing, the same development and post-baking steps as in the above (1) were carried out, and the developability and pattern integrity were evaluated by the same criteria.

The test results are shown in Table 3 below.

table 3

(3) substrate adhesion test

Taking the photocurable composition of Example 1 as a representative, refer to the "Scratch Test of Paint and Paint Film of GBT9286-1998", using the QFH knife-cutting method, using the QFH paint film scribing method, the photocurable composition is Adhesion on different substrates was tested.

The specific method is as follows:

The photocurable composition is uniformly applied to different substrates and cured under a high pressure mercury lamp and an LED lamp source respectively (the application conditions and the curing conditions are as described in the above (1) and (2), without using a mask, high pressure Exposure to mercury lamp for 30s, exposure to LED light source for 3s), aging at room temperature for 24h after curing, then use a 100-blade knife to cut 100 squares in the horizontal and vertical directions to form 100 small squares, then use the brush diagonal direction Each brush was applied five times, and the tape was attached to the slit with 3M600 tape, and the condition of the lattice area was observed with a magnifying glass. The degree of adhesion of the coating film to the substrate was evaluated by evaluating the integrity of the coating film in the square. The more complete the coating in the square, the stronger the adhesion.

The evaluation criteria are as follows:

A: the edge of the slit is completely smooth, and the edge of the lattice is not peeled off;

B: There is a small piece of peeling at the intersection of the incisions, and the actual damage in the cross-cut area is ≤ 5%;

C: flaking at the edge and/or intersection of the slit, the area of which is 5%-30% (excluding 5%);

D: There is partial peeling along the edge of the slit or a large piece of peeling or peeling off, or a part of the lattice is peeled off. The area of flaking is more than 30%.

The evaluation results are shown in Table 4 below.

Table 4

It can be seen from the test results of Table 2-4 that the radical photocurable composition of the present invention has good photocuring effect under both mercury lamp and LED light source, high sensitivity, fast curing speed, developability and pattern completeness. It has good properties and high hardness of the coating film, showing strong adhesion on different substrates.

From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the present invention enables the photo-curing composition to have a large photosensitive wavelength range by component optimization, particularly the addition of a specific oxime ester sensitizer. It has good light curing effect and can be applied in many aspects such as paint, paint, ink and molding materials, and has strong technical and market competitiveness.

The above description is only the preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes can be made to the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims (18)

1. A radical photocurable composition comprising the following components:

   (A) an oxime ester sensitizer selected from the group consisting of a compound having the structure of the formula (I) and/or a macromolecular compound having a compound of the formula (I) as a main structure:

   

   R ₁ and R ₂ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C ₄₀ linear or branched alkyl, C ₁ -C ₄₀ alkoxy, or -O-CO-R a group, and at least one of R ₁ and R ₂ is a -O-CO-R group, R represents a C ₃ -C ₂₀ cycloalkyl group, a C ₄ -C ₂₀ alkylcycloalkyl group or a cycloalkyl group An alkyl group, a C ₂ -C ₄₀ ester-containing group, a C ₂ -C ₄₀ -containing epoxy group, a halogen, or a C ₃ -C ₂₀ halogen-substituted alkyl group;

   R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C ₄₀ linear or branched alkyl a C ₃ -C ₄₀ cycloalkyl group, a C ₄ -C ₄₀ alkylcycloalkyl group or a cycloalkylalkyl group, a C ₂ -C ₄₀ alkenyl group, or a C ₆ -C ₄₀ aryl group, and The acyclic -CH ₂ - in these groups may be optionally substituted by -O-, -CO-, -NH-, -S- or 1,4-phenylene;

   (B) a radical reactive compound;

   (C) A radical photoinitiator.
2. The radical photocurable composition according to Claim 1, wherein in the structure of the formula (I), R ₁ and R ₂ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C a straight-chain or branched-chain alkyl group of _20, C ₁ -C ₂₀ alkoxy or -O-CO-R group, and R ₁ and R ₂ at least one -O-CO-R group, R represents a C ₃ -C ₁₀ cycloalkyl group, a C ₄ -C ₁₄ alkylcycloalkyl group or a cycloalkylalkyl group, a C ₃ -C ₂₀ ester group-containing group, and a C ₃ -C ₂₀ ring-containing ring. An oxy group, a halogen, or a C ₃ -C ₂₀ alkyl group substituted by a halogen.
3. The radical photocurable composition according to claim 1 or 2, wherein in the optional group of R, the ester group-containing group means that the group contains at least one -CO-O- Or -O-CO-, and in addition to the ester group, the other structural moiety of the ester group-containing group belongs to an alkyl structure and/or an alkenyl structure.
4. The radical photocurable composition according to claim 1 or 2, wherein in the optional group of R, the epoxy group-containing group means that the group contains at least one epoxy group. And, in addition to the epoxy group, the other structural moiety containing the epoxy group belongs to the alkyl structure.
5. According to claim 1 or 2 radicals or photo-curable composition as claimed in claim, wherein: formula (I) shown in the structure, R ₁ and R ₂ each independently represent hydrogen, nitro, cyano, halogen, C ₁ -C straight or branched chain alkyl of _10, C ₁ -C ₁₀ alkoxy or -O-CO-R group, and R ₁ and R ₂ is at least a group -O-CO-R Group, R is selected from one of the following groups:

   

   Wherein h = 0-3, i = 1-4, and when h = 0, hydrogens on the cycloalkyl can be optionally substituted with C ₁ -C ₄ alkyl;

   -(CH ₂ ) _j -CO-OC _k H _2k+1 or -(CH ₂ ) _j -O-CO-C _k H _2k+1 , wherein j=1-4, k=1-6;

   -(CH ₂ ) _r -O-CO-CH=CH ₂ , wherein r=1-5;

   

   Where m=1-3, n=0-5;

   

   Wherein x = 1-3, y = 1-2, z = 0-3;

   

   Where p=1-5, q=0-5;

   Cl, F, Br, -(CH ₂ ) _s (CH ₂ ) _t CCl, -(CH ₂ ) _s (CH ₂ ) _t CF, or -(CH ₂ ) _s (CH ₂ ) _t CBr, where s=1 -6, t=1-6;

   And the hydrogen in the structure in which h, j, r, m, x, y, p, s, t is present may be optionally substituted by a C ₁ -C ₄ alkyl group.
6. The radical photocurable composition according to Claim 1, wherein R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R _{10 are} represented by the formula (I). Each independently represents hydrogen, nitro, cyano, halogen, C ₁ -C ₂₀ linear or branched alkyl, C ₃ -C ₂₀ cycloalkyl, C ₄ -C ₂₀ alkylcycloalkyl or a cycloalkylalkyl group, a C ₂ -C ₁₀ alkenyl group, a C ₆ -C ₂₀ aryl group, and the acyclic -CH ₂ - of these groups may be optionally -O-, -CO- or Substituted by 1,4-phenylene.
7. The radical photocurable composition according to claim 1 or 6, wherein R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R _{9 are} in the structure represented by the formula (I). R ₁₀ each independently represents hydrogen, nitro, cyano, halogen, C ₁ -C ₁₂ linear or branched alkyl, C ₃ -C ₁₀ cycloalkyl, C ₄ -C ₁₀ alkylcycloalkane Or a cycloalkylalkyl group, a C ₂ -C ₆ alkenyl group, a C ₆ -C ₁₀ aryl group, and the acyclic -CH ₂ - of these groups may be optionally -O- or -CO - replaced by.
8. The radical photocurable composition according to claim 1, wherein the component (B) radical reactive compound is a (meth) acrylate compound and/or an alkenyl ether compound.
9. The radical photocurable composition according to claim 8, wherein the (meth) acrylate compound is selected from the group consisting of alkyl (meth) acrylate, hydroxy (meth) acrylate, (poly) (Meth) acrylate of alkylene glycol, (meth) acrylate of ternary or higher polyol or modified product thereof, epoxy acrylate, polyamine A (meth) acrylate of an oligomeric resin such as an ester (meth) acrylate, a polyester acrylate, a terminal hydroxylated polymer (meth) acrylate, a urethane resin, a siloxane resin, or a spiro resin.
10. The radical photocurable composition according to claim 8 or 9, wherein the (meth) acrylate compound is an alkyl (meth) acrylate or a (poly)alkylene glycol (A) One of a (meth) acrylate, an epoxy acrylate, and a urethane (meth) acrylate of a acrylate or a trihydric or higher polyhydric alcohol, or a combination of two or more.
11. The radical photocurable composition according to claim 8, wherein the alkenyl ether compound is selected from the group consisting of vinyl ethers, 1-propenyl ethers, 1-butenyl ethers, and 1- A pentenyl ether compound is preferably a vinyl ether compound.
12. The radical photocurable composition according to claim 11, wherein the vinyl ether compound is selected from the group consisting of triethylene glycol divinyl ether, 1,4-cyclohexyl dimethanol divinyl ether, and 4-hydroxybutyl group. One or a combination of two or more of vinyl ether, glycerin carbonate vinyl ether, and dodecyl vinyl ether.
13. The radical photocurable composition according to Claim 1, wherein the component (C) radical photoinitiator is selected from the group consisting of benzophenones, α-hydroxyalkylphenones and/or α- Amine alkyl phenones, benzil compounds.
14. The radical photocurable composition according to claim 8, wherein the (meth) acrylate compound is selected from the group consisting of alkyl (meth) acrylate, hydroxy (meth) acrylate, (poly) (Meth) acrylate of alkylene glycol, (meth) acrylate of ternary or higher polyol or modified product thereof, epoxy acrylate, urethane (meth) acrylate, polyester acrylate One or more of an ester, a (meth) acrylate of a terminal hydroxylated polymer, and a (meth) acrylate of an oligomeric resin; preferably, the (meth) acrylate of the oligomeric resin is selected One or more of a urethane resin, a silicone resin, and a spiro resin.
15. The radical photocurable composition according to claim 8, wherein the alkenyl ether compound is selected from the group consisting of vinyl ethers, 1-propenyl ethers, 1-butenyl ethers, and One or more of the pentenyl ether compounds are preferably vinyl ether compounds.
16. The radical photocurable composition according to Claim 1, wherein the component (C) radical photoinitiator is selected from the group consisting of benzophenones, α-hydroxyalkylphenones and/or α- One or more of an amine alkyl phenone, and a benzil compound.
17. Use of the radical photocurable composition of any of claims 1-16 in the field of photocuring.
18. The use according to claim 17, wherein the field of photocuring comprises paints, coatings, inks and molding materials.