JPH11286531A - Noncrystalline urethane (meth)acrylate and its composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject compound capable of readily carrying out handling, or the like and forming a coating film excellent in flexibility, or the like by reacting a specific diol with a polyisocyanate and a specific (meth) acrylate. SOLUTION: This compound is obtained by reacting (A) (i) a poly-ε- caprolactone-based diol of the formula H-[O(CH2 )5 CO]m -ORO-[CO(CH2 )5 O-]n -H [(m) and (n) are each a positive integer and (m+n) is 3-10; ORO is a residue of diol R(OH)2 used as a polymerization initiator for the component (i)] having 3-8 average value of caprolactone chain and 1.0-1.5 Mw/Mn distribution of molecular weight or (ii) a mixture of the component (i) with a low molecular weight polyol having <=300 molecular weight in an amount of 1-20 mol based on 1 mol component (i), (B) a polyisocyanate and (C) a hydroxy group-containing (meth)acrylate at a ratio of 1-15 mol component A and 2-16 mol component B to 2 mol component C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a non-crystalline urethane (meth) acrylate and an active energy ray-curable urethane (meth) acrylate composition containing the non-crystalline urethane (meth) acrylate as a curing component. Things.

[0002]

2. Description of the Related Art In recent years, non-solvent active energy ray-curable paints, which are cured by active energy rays, have been widely used in place of organic solvent-based paints due to environmental pollution problems and energy saving. This contains a resin and a monomer which can be cured by an active energy ray, and has an advantage that the solvent does not volatilize during the formation of a coating film since the monomer also functions as a solvent. Examples of the resin and monomer that can be cured by the active energy ray include oligomers having a (meth) acryloyl group at a molecular terminal, such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate, and (meth) acryl-based resins. And the like are used.

[0003] Among them, urethane (meth) acrylate resin has a good balance of physical properties, and a coating composition using the resin can be used for decorative paper coating and paper varnish (OP).
V), widely used for woodworking paints, hard coatings for plastics, adhesives, inks for resists, etc. In the use of such a coating agent, performances such as flexibility (elongation), adhesion, scratch resistance, and stain resistance of a coating film to be formed are required. Various improvements in performance have been studied. In order to satisfy these performances, a high molecular weight caprolactone diol is generally used for the polyol component. However, urethane (meth) acrylate using the above-mentioned high molecular weight caprolactone diol as the polyol component has difficulty in handling and workability due to its crystallinity. Therefore, since the composition using this urethane (meth) acrylate also has crystallinity, handling and workability are difficult.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to form a coating film which is easy to handle and work, and has excellent flexibility (elongation), adhesion, abrasion resistance and stain resistance. It is to provide a non-crystalline urethane (meth) acrylate and a composition thereof.

[0005]

The present inventor has made intensive studies to solve the above-mentioned problems, and as a result, has found that a specific poly-ε
-The urethane (meth) acrylate obtained by reacting a caprolactone-based diol with a polyisocyanate and a hydroxy group-containing (meth) acrylate has non-crystallinity, and a compound using the urethane (meth) acrylate is non-crystalline. Crystalline and flexible (elongation),
The present inventors have found that a coating film excellent in adhesion, abrasion resistance and stain resistance is formed, and have reached the present invention.

That is, a first aspect of the present invention is the following general formula (1)
Wherein the average value of the caprolactone chain is in the range of 3 to 8 and the molecular weight distribution Mw / Mn is in the range of 1.0 to 1.5, the poly-ε-caprolactone diol (A)
And a non-crystalline urethane (meth) acrylate obtained by reacting a polyisocyanate (B) with a hydroxy group-containing (meth) acrylate (C). _{H- [O (CH 2) 5} CO] m-ORO- [CO (CH 2) 5 O-] n-H (1) ( here, m and n represent a positive integer, m + n is 3 to 1
0 and -ORO- represents a residue of diol R (OH) ₂ used as a polymerization initiator of poly-ε-caprolactone diol (A). A second aspect of the present invention is that the poly-ε-caprolactone diol (A) is 1 to 15 mol and the polyisocyanate (B) is 2 to 16 mol based on 2 mol of the hydroxy group-containing (meth) acrylate (C). A non-crystalline urethane (meth) acrylate according to the first aspect of the present invention, which is obtained by increasing the molecular weight using a mole. A third aspect of the present invention is the method according to the first or second aspect, wherein a low-molecular-weight polyol (D) having a molecular weight of 300 or less is further added to the poly-ε-caprolactone-based diol (A). An amorphous urethane (meth) acrylate is provided. A fourth aspect of the present invention is that the mixing ratio of the poly-ε-caprolactone diol (A) and the low molecular weight polyol (D) is such that the mixing ratio of the low molecular weight polyol (D) is 1 mol per 1 mol of the poly-ε-caprolactone diol (A). ), Wherein the amorphous urethane (meth) acrylate is used in an amount of 1 to 20 mol. A fifth aspect of the present invention is an active energy comprising the non-crystalline urethane (meth) acrylate and the (meth) acryloyl group-containing monomer (E) according to the first, second, third or fourth aspect of the present invention. Provided is a line-curable urethane (meth) acrylate composition.

[0007]

DETAILED DESCRIPTION OF THE INVENTION (A) Poly-ε-caprolactone diol will be described. Poly-ε used in the present invention
-Caprolactone diol (A) is a polymerization initiator R
It is synthesized by reacting (OH) ₂ with ε-caprolactone at a reaction temperature of 130 ° C. or lower in the presence of a tin-based catalyst. The ratio of ε-caprolactone was 3 per mole of the polymerization initiator.
10 to 10 mol is preferred. If the amount is less than 3 mol, physical properties such as flexibility when urethane (meth) acrylated are insufficient, which is not preferable. On the other hand, if it exceeds 10 mol, it becomes undesirably crystalline.

[0008] The polymerization initiator has 2 to 12 carbon atoms.
And at least one diol selected from the group consisting of straight-chain glycols, diols having side chains, and alicyclic diols. Examples of the linear glycols include ethylene glycol oligomers such as ethylene glycol, diethylene glycol and triethylene glycol, propylene glycol oligomers such as propylene glycol, dipropylene glycol and tripropylene glycol, 1,3-propanediol, butanediol, and pentanediol. Hexanediol and the like can be mentioned, and diols having a side chain include neopentyl glycol and the like, and alicyclic diols include cyclohexanediol and cyclohexanedimethanol.

Examples of the above-mentioned tin catalyst include monobutyltin oxide, monobutyltin tris (2-ethylhexanoate), dibutyltin oxide, diisobutyltin oxide and the like. The addition amount of the tin-based catalyst is 10 to 100 ppm based on the whole reaction raw materials.
Is appropriate.

The poly-polysaccharide of the present invention synthesized as described above
The ε-caprolactone diol has an average caprolactone chain in the range of 3 to 10, and Mw / Mn showing the molecular weight distribution in the range of 1.0 to 1.5. The poly-ε-caprolactone diol of the present invention differs from those synthesized by the conventional production method in that the number of caprolactone chains and the molecular weight distribution thereof are precisely controlled.
-Urethane (meth) using caprolactone diol
Acrylates are non-crystalline.

The poly-ε-caprolactone diol (A) may be used alone or a mixture of the poly-ε-caprolactone diol and the low molecular weight polyol (D). The mixing ratio is such that the low molecular weight polyol is 1 to 2 with respect to 1 mol of the poly-ε-caprolactone diol.
0 mol, preferably 3 to 10 mol. If the low molecular weight polyol is less than 1 mol, the elongation becomes insufficient when converted to urethane (meth) acrylate, and if it exceeds 20 mol, the viscosity increases when converted to urethane (meth) acrylate, making handling difficult. Low molecular weight polyol (D)
Are those having a molecular weight of 300 or less, specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2- or 1,3-propylene glycol, 1,3- or 1,4-butanediol, Examples thereof include 1,5-pentanediol, 1,6-hexanediol, and neopentyl glycol.

The (B) polyisocyanate will be described below. Polyisocyanate (B) used in the present invention
Known polyisocyanates such as aromatic, aliphatic, cycloaliphatic or alicyclic polyisocyanates or mixtures, adducts, modified products and polymers thereof can be used. Among them, tolylene diisocyanate (TDI),
Diphenylmethane diisocyanate (MDI), hydrogenated diphenylmethane diisocyanate (H ₁₂ MDI), polyphenylmethane polyisocyanate (Crude MD)
I), modified diphenylmethane diisocyanate (modified M
DI), xylylene diisocyanate (XDI), hydrogenated xylylene diisocyanate (H-XDI), hexamethylene diisocyanate (HMDI), trimethylhexamethylene diisocyanate (TMXDI), polyisocyanate such as isophorone diisocyanate (IPDI), or these isocyanates And a trimer compound.

The (C) hydroxy group-containing (meth) acrylate will be described below. Examples of the hydroxy group-containing (meth) acrylate (C) used in the present invention include 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, tripropylene glycol (meth) acrylate, glycerol mono (meth) acrylate Glycerol di (meth) acrylate, glycerol methacrylate acrylate, and the like.

As a method for producing the urethane (meth) acrylate of the present invention, the above-mentioned poly-ε-caprolactone diol (A), polyisocyanate (B), and hydroxy group-containing (meth) acrylate (C) are reacted. The method is not particularly limited as long as it is a method, and it can be produced by a known method. For example, a method in which (A), (B), and (C) are mixed together and reacted, and a urethane isocyanate prepolymer containing one or more isocyanate groups per molecule by reacting (A) and (B). And then reacting the prepolymer with (C) or reacting (B) and (C) to form a urethane isocyanate prepolymer containing one or more isocyanate groups per molecule. And a method of reacting the preformer with (A). In the above reaction method, instead of the poly-ε-caprolactone diol (A),
The same applies when a mixture of (A) and low molecular weight polyol (D) is used.

The reaction rate of the poly-ε-caprolactone diol (A) (or a mixture of (A) and (D)), the polyisocyanate (B), and the hydroxy group-containing (meth) acrylate (C) are as follows: 1) to 15 moles of (A) (or a mixture of (A) and (D)) per 2 moles
Mol, preferably 2 to 10 mol, and (B) is 2 to 1 mol.
6 mol, preferably 3 to 11 mol. If (A) (or a mixture of (A) and (D)) is less than 1 mol, the elongation becomes insufficient when urethane (meth) acrylate is formed, and if (B) is less than 2 mol, urethane (meth) acrylate Can not be converted.

The active energy ray-curable urethane (meth) acrylate composition of the present invention comprises the above urethane (meth)
It contains acrylate as a curable component.
When the composition is cured by irradiation with an electron beam, a photopolymerization initiator is not used, but when the composition is cured by irradiation with ultraviolet rays, a photopolymerization initiator is blended. As the photopolymerization initiator,
1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-
1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoyl Acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenylsulfide, 3,3′-dimethyl-4-methoxybenzophenone, thio Sanson, 2 black Lucio hexane Son, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 2,4
-Dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, methylphenylglyoxylate, benzyl, camphorquinone and the like. The amount of the photopolymerization initiator is preferably 1 to 10% by weight based on the whole composition.

The urethane (meth) acrylate composition of the present invention comprises the above urethane (meth) acrylate and (meth)
It is preferable to mix the acryloyl group-containing monomer (E). The (meth) acryloyl group-containing monomer (E) is not particularly limited, and a known monomer having a (meth) acryloyl group can be used. Examples of the (meth) acryloyl group-containing monomer (E) include, for example, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, 1,6-hexanediol (meth) acrylate , Tripropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxy tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and the like. The amount of the (meth) acryloyl group-containing monomer (E) is preferably from 0 to 50% by weight based on the whole composition. If it exceeds 50% by weight, elongation becomes insufficient, which is not preferable.

In the present invention, an organic solvent or the like can be added as needed for adjusting the viscosity. Examples of such organic solvents include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate and methoxyethyl acetate; ether solvents such as diethyl ether, ethylene glycol methyl ether and dioxane. Solvents: aromatic solvents such as toluene and xylene; aliphatic solvents such as pentane and hexane; halogen solvents such as methylene chloride, chlorobenzene and chloroform; alcohol solvents such as isopropanol and butanol. The amount of the organic solvent is preferably from 0 to 30% by weight based on the whole composition.

The urethane (meth) acrylate composition may further contain various other additives. Examples of such additives include fillers, dyes and pigments, leveling agents, ultraviolet absorbers, light stabilizers, defoamers, dispersants, and thixotropic agents. After the urethane (meth) acrylate composition is applied to an object, the composition is cured by irradiating ultraviolet rays or electron beams.

As a light source for performing ultraviolet irradiation, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a xenon lamp, a metal halide lamp, and the like are used. The irradiation time is
Although it depends on the type of light source, the distance between the light source and the application surface, and other conditions, the time is at most several tens of seconds, usually several seconds. After the ultraviolet irradiation, if necessary, heating can be performed to complete the curing. In the case of electron beam irradiation, 50 ~
It is preferable to use an electron beam having an energy in the range of 1,000 KeV and to set the irradiation amount to 2 to 5 Mrad.

The objects to be coated include plastics such as polyethylene terephthalate (PET), polymethacrylate, polycarbonate, and vinyl chloride resin, wood,
Examples include a metal plate and paper. Urethane (meta) of the present invention
The plastics, wood, metal, paper and the like coated with the acrylate resin composition are useful for various building materials, furniture, printing paper, can products, and household electric appliances. Since the urethane (meth) acrylate composition of the present invention uses non-crystalline urethane (meth) acrylate as a component, the urethane (meth) acrylate composition is non-crystalline, and the formed coating film has flexibility, adhesion, and resistance. Excellent scratch resistance.

[0022]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. The molecular weight distribution was determined by gel permeation chromatography (GPC) under the following conditions. Apparatus: LC-3A manufactured by Shimadzu Corporation Solvent: tetrahydrofuran Temperature: 50 ° C Carrier flow rate: 1 ml / min Column: Shodex KF801 x 1; KF8025 x 1; KF804 x 1 Detector: Shimadzu RID-6A

(Synthesis Example 1) Synthesis of poly-ε-caprolactone diol (1) 1,4-butanediol 1 was added to a flask as a polymerization initiator.
84 g (2 mol), 1860 g of ε-caprolactone (1
6.3 mol) (m + n = 8.15 in general formula (1))
Was heated to 120 ° C., and 50 ppm of monobutyltin oxide was added as a catalyst, followed by aging. In addition,
All reactions are carried out under a nitrogen stream until the residual caprolactone monomer becomes 1% or less by gas chromatography. (1) having a molecular weight distribution of 1.24 was obtained.

(Synthesis Example 2) Synthesis of poly-ε-caprolactone diol (2) Except that the charged amount of ε-caprolactone was changed to 1140 g (10.0 mol) (m + n = 5.0 in the general formula (1)). Performed in the same manner as in Synthesis Example 1. (2) having a molecular weight distribution of 1.20 was obtained.

(Synthesis Example 3) Synthesis of poly-ε-caprolactone diol (3) As polymerization initiator, cyclohexanedimethanol 288 was used.
g (2 mol) (m + n = 8.1 in the general formula (1))
Except having changed to 5), it carried out similarly to the synthesis example 1, and obtained (3) of molecular weight distribution 1.18.

(Synthesis Example 4) Synthesis of poly-ε-caprolactone diol (4) Ethylene glycol 126 was added to a flask as a polymerization initiator.
g (2.0 mol) and 1860 g (16.3 mol) of ε-prolactone (m + n = 8.15 in the general formula (1)) were heated to 170 ° C., and aging was performed by adding 10 ppm of tetrabutyl titanate as a catalyst. . All the reactions were carried out under a nitrogen gas flow until the residual caprolactone monomer became 1% or less by gas chromatography, whereby (4) having a molecular weight distribution of 1.87 was obtained.

Example 1 Synthesis of Urethane Acrylate (A) A flask was charged with 444 g (2 mol) of isophorone diisocyanate, heated to an internal temperature of 70 ° C., and 1025 g (1 mol) of poly-ε-caprolactone diol (1). At the time when the residual isocyanate groups became 5.7%, 232 g of 2-hydroxyethyl acrylate (2
Mol) and 0.35 g of dibutyltin laurylate were added, and the reaction was carried out until the residual isocyanate groups became 0.1% or less.

[Example 2] Synthesis of urethane acrylate (B) The charged components and charged amounts are shown below. The reaction conditions are the same as in Example 1. Isophorone diisocyanate: 444 g (2 mol) Poly-ε-caprolactone diol (2): 610 g
(1 mol) 2-hydroxyethyl acrylate: 232 g (2 mol) dibutyltin laurylate: 0.25 g

Example 3 Synthesis of Urethane Acrylate (C) Charged components and charged amounts are shown below. The reaction conditions are the same as in Example 1. Isophorone diisocyanate: 444 g (2 mol) Poly-ε-caprolactone diol (3): 1020
g (1 mol) 2-hydroxyethyl acrylate: 232 g (2 mol) Dibutyltin laurate: 0.35 g

Example 4 Synthesis of Urethane Acrylate (D) The charged components and charged amounts are shown below. The reaction conditions are the same as in Example 1. Isophorone diisocyanate: 888 g (4 mol) Poly-ε-caprolactone diol (1): 1025
g (1 mol) Diethylene glycol: 318 g (3 mol) 2-hydroxyethyl acrylate: 232 g (2 mol) Dibutyltin laurylate: 0.5 g

Example 5 Synthesis of Urethane Acrylate (E) The charged components and charged amounts are shown below. The reaction conditions are the same as in Example 1. Isophorone diisocyanate: 888 g (4 mol) Poly-ε-caprolactone diol (1): 3075
g (3 mol) 2-hydroxyethyl acrylate: 232 g (2 mol) Dibutyltin laurylate: 0.8 g

Example 6 Synthesis of Urethane Acrylate (F) The charged components and charged amounts are shown below. The reaction conditions are the same as in Example 1. Isophorone diisocyanate: 2220 g (10 mol) Poly-ε-caprolactone diol (1): 3075
g (3 mol) Diethylene glycol: 636 g (6 mol) 2-hydroxyethyl acrylate: 232 g (2 mol) Dibutyltin laurylate: 0.9 g

[Comparative Example 1] Synthesis of urethane acrylate (G) Charged components and charged amounts are shown below. The reaction conditions are the same as in Example 1. Isophorone diisocyanate: 444 g (2 mol) Poly-ε-caprolactone diol (4): 1025
g (1 mol) 2-hydroxyethyl acrylate: 232 g (2 mol) Dibutyltin laurate: 0.35 g

[Comparative Example 2] Synthesis of urethane acrylate (H) Charged components and charged amounts are shown below. The reaction conditions are the same as in Example 1. Isophorone diisocyanate: 888 g (4 mol) Poly-ε-caprolactone diol (4): 1025
g (1 mol) Diethylene glycol: 306 g (3 mol) 2-hydroxyethyl acrylate: 232 g (2 mol) Dibutyltin laurylate: 0.5 g

With respect to the urethane acrylates A to H obtained in the above Examples 1 to 6 and Comparative Examples 1 and 2, the presence or absence of crystallinity was determined in the following manner.
The H coating film was examined for scratch resistance and flexibility.

[Example 7] Urethane acrylate composition The urethane acrylate (A) 8 obtained in the above Example 1
About a urethane acrylate composition in which 20 parts by weight of tripropylene glycol diacrylate is added as a curable (meth) acryloyl group-containing monomer to 0 parts by weight,
The presence or absence of crystallinity, scratch resistance and flexibility were examined in the same manner as described above.

(Presence or absence of crystallinity)
After storing at 10 ° C. for one week, the crystalline state was visually observed. The evaluation criteria are as follows. 〇: not crystallized at all, but in a liquid state △: slightly crystallized, ×: crystallized and in a waxy or solid state

(Scratch resistance) The resin composition was applied to a glass plate using an applicator so that the thickness became 10 μm, and then applied under a high-pressure mercury lamp of 80 W / cm at a line speed of 5 m / min at a line speed of 5 m / min. The film was passed twice to form a coating film. Next, the surface of the coating film was scratched with a nail, and the presence or absence of a nail mark generated on the surface was examined. The evaluation criteria are as follows. 〇: No nail mark is observed at all △: Slight but slight nail mark is observed ×: Nail mark is clearly observed (Flexibility) The resin composition is applied to a vinyl chloride film with a thickness of 10 μm using an applicator. And then apply 80 W / cm at a line speed of 5 m / min.
Was passed twice under a high-pressure mercury lamp to form a coating film. Next, the vinyl chloride film was bent at 180 ° and the presence or absence of cracks generated in the folds was examined. Evaluation criteria are
It is as follows. 〇: No cracks are observed at all △: Slight, but cracks are observed ×: Cracks are clearly observed

Table 1 shows the results of the above Examples and Comparative Examples.

[0040]

[Table 1]

[0041]

The urethane acrylate and its composition of the present invention synthesized using a specific poly-ε-caprolactone diol are non-crystalline, and the coating film formed therefrom has scratch resistance, flexibility, Excellent adhesion.

Claims (5)

[Claims] An average value of the caprolactone chain represented by the following general formula (1) is in the range of 3 to 8, and the molecular weight distribution Mw is
/ Mn in the range of 1.0 to 1.5, poly-ε-caprolactone diol (A) and polyisocyanate (B)
And a hydroxy group-containing (meth) acrylate (C) to obtain a non-crystalline urethane (meth) acrylate. _{H- [O (CH 2) 5} CO] m-ORO- [CO (CH 2) 5 O-] n-H (1) ( here, m and n represent a positive integer, m + n is 3 to 1
0 and -ORO- represents a residue of diol R (OH) ₂ used as a polymerization initiator of poly-ε-caprolactone diol (A). ) 2. Use of 1 to 15 mol of poly-ε-caprolactone diol (A) and 2 to 16 mol of polyisocyanate (B) to 2 mol of hydroxy group-containing (meth) acrylate (C). The non-crystalline urethane (meth) acrylate according to claim 1, which is obtained by increasing the molecular weight. 3. The non-crystalline urethane according to claim 1, wherein a low molecular weight polyol (D) having a molecular weight of 300 or less is further added to the poly-ε-caprolactone diol (A). (Meth) acrylate. 4. The mixing ratio of the poly-ε-caprolactone-based diol (A) and the low-molecular-weight polyol (D) is such that the low-molecular-weight polyol (D) is mixed with 1 mole of the poly-ε-caprolactone-based diol (A). The amorphous urethane (meth) acrylate according to claim 3, wherein 1 to 20 mol is used. 5. An active energy ray-curable urethane comprising the non-crystalline urethane (meth) acrylate and the (meth) acryloyl group-containing monomer (E) according to claim 1, 2, 3 or 4. (Meth) acrylate compositions.