JPH09272707A - Actinic-radiation-curing (meth)acrylate composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an actinic-radiation-curing (meth)acrylate composition which is rapidly curing and odorless and can give a cured product having a high refractive index when used as a coating material for optical materials by selecting a composition containing a (meth)acrylate having a specified structure. SOLUTION: This composition comprises a (meth)acrylate (A) represented by formula I or II (R is hydrogen or methyl), a compound (B) having a radical- polymerizable double bond in the molecule and being other than component A, and a photopolymerization initiator (C). The mixing ratio is such that 5-95wt.% component A and 95-5wt.% component B are present, and 0.1-10 pts.wt. component C is present per 100 pts.wt. total of components A and B. By adopting a composition in which the amount of component A is 20-90wt.%, and that of component B is 80-10wt.%, a composition having a refractive index of 1.55 or above can be obtained. The obtained composition is particularly suitable as a coating material for optical materials. It is desirable in this case that part or the whole of component B be constituted by a (meth)acrylate having an aromatic ring.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a (meth) acrylate composition curable by irradiation with an active energy ray such as visible light, ultraviolet ray or electron beam. Since the composition has a fast curing property, It can be used in various industrial fields such as coatings, paints, printing inks, adhesives, fillers and molding materials.
The obtained cured film has excellent transparency and high refractive index, and thus can be preferably used as a coating agent for optical materials such as lenses and prisms.
In the present specification, acrylate and / or methacrylate are represented by (meth) acrylate, acrylic acid and / or methacrylic acid are represented by (meth) acrylic acid, and acryloyl group and / or methacryloyl group are represented by (meth) acryloyl group. .

[0002]

2. Description of the Related Art An active energy ray-curable composition has a rapid curing property and is compared with a conventional solvent-drying resin composition.
In addition to drastically reducing the energy and time required for drying, the space used for drying is reduced, and the amount of solvent used is increasing year by year as a coating agent that is kind to the global environment and does not require the use of a small amount of solvent. in recent years,
There is a demand for a small amount of a variety of products and a composition capable of coping with an increase in line speed by utilizing the speed of curability.

[0003]

However, some active energy ray-curable compositions have skin irritation and odor, and if the line speed is further increased and curing becomes insufficient, Irritation and odor may be particularly problematic, and there is a demand for a composition that is more curable than ever. The active energy ray-curable composition, lenses, in the use of coating optical materials such as prisms, particularly fast curing is required, further the cured product is desired to have a composition having a high refractive index, The performance of currently known compositions was unsatisfactory.

[0004]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, a composition comprising a (meth) acrylate having a specific structure has a fast curing property. The inventors have found that the cured product obtained has no odor and has a high refractive index when used for coating optical materials such as lenses and prisms, and completed the present invention.

The first invention of the present invention comprises the following components A, B and C, and the ratio of the components A and B is 5 to 95% by weight for the A component and 95 to 5% by weight for the B component. Yes, A
The C component is 0.
1 to 10 parts by weight is an active energy ray-curable (meth) acrylate composition, wherein component A: (meth) acrylate represented by formula (1) or formula (2).

[0006]

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[0007]

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[In the formulas (1) and (2), R represents hydrogen or a methyl group. B component: a compound other than A component having a radically polymerizable unsaturated double bond in the molecule C component: photoinitiator In the second invention, the ratio of A component to B component is 20 to 20%.
90% by weight, B component is 80 to 10% by weight, and the active energy ray-curable (meth) acrylate composition of the first invention has a refractive index of 1.55 or more. The third invention is B
The active energy ray-curable (meth) acrylate composition of the second invention is characterized in that a part or all of the components are (meth) acrylates having an aromatic ring. Less than,
The present invention will be described in detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION

Component A The component A of the present invention is a compound represented by the above formula (1) or formula (2). Here, in the formulas (1) and (2), R represents a hydrogen atom or a methyl group.

As the compound represented by the formula (1) or (2), those obtained by various production methods can be used, but preferably, a condensate of o- or p-phenylphenol and epichlorohydrin is used. Which is obtained by the addition reaction of o- or p-phenylphenol glycidyl ether with (meth) acrylic acid.

As a preferred example of the condensation reaction, o- or p-phenylphenol glycidyl ether and (meth) acrylic acid are stirred with stirring in the presence of a catalyst.
The method of making it react at 0 degreeC-140 degreeC is mentioned. In this case, if the reaction temperature is lower than 70 ° C, the reaction may be slow, while if the reaction temperature exceeds 140 ° C,
The reaction system may become unstable, impurities may be generated, or gelation may occur. In this case, the catalyst includes tertiary amines such as N, N-dimethylbenzylamine, triethylamine and N, N-dimethylaniline; quaternary ammonium salts such as tetradiethylammonium chloride, tetrabutylammonium bromide and benzyltrimethylammonium chloride. Secondary amine hydrochlorides such as diethylammonium chloride; and phosphorus compounds such as triphenylphosphine. During the reaction,
Organic solvents may be used. Organic solvents used include aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, ketones such as methyl ethyl ketone and cyclohexanone, and acetic acid esters such as ethyl acetate and butyl acetate. Is mentioned. The solvent may be distilled off under reduced pressure after the reaction, or may be used as it is for adjusting the viscosity of the composition. Further, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or phenothiazine may be used for suppressing radical polymerization of the (meth) acryloyl group.

Component B The component B in the present invention is a compound having a radical-polymerizable unsaturated double bond other than the component A in the molecule, and preferred examples thereof include N-vinylpyrrolidone and (meth) acrylate. To be

As the (meth) acrylate, various compounds other than the component A can be used. Specifically, 2-hydroxyethyl (meth) acrylate,
Hydroxyalkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, (meth) acrylates of alkylene oxide adducts of phenol such as phenoxyethyl (meth) acrylate and halogen nucleus substitution products thereof, mono or di (of ethylene glycol). (Meth) acrylate, mono (meth) acrylate of methoxyethylene glycol, mono- or di (meth) acrylate of tetraethylene glycol, and mono- or di (meth) acrylate of glycol such as mono- or di (meth) acrylate of tripropylene glycol, Bisphenol A
Mono or di (meth) acrylate, bisphenol A
Mono- or di (meth) acrylates of alkylene oxide adducts such as ethylene oxide adducts or propylene oxide adducts, and trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate and pentaerythritol tetra (meth) acrylate , Polyols such as dipentaerythritol hexaacrylate, and (meth) acrylates of alkylene oxides thereof.

Examples of the oligomer include urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate and the like.

As the urethane (meth) acrylate,
Reaction products of alcohols, organic polyisocyanates and hydroxyl group-containing (meth) acrylates are mentioned. In this case, alcohols include lower alcohols such as ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol and 3-methyl-1,5-pentanediol, polyether polyols such as polyethylene glycol and polypropylene glycol, and the like. And a dibasic acid such as adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid or an anhydride thereof, and the like. Examples of the organic polyisocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate. Examples of the hydroxy group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

As the epoxy (meth) acrylate,
For example, a reaction product of a bisphenol A type epoxy resin or a halogen nucleus substitution product thereof, or a bisphenol F type epoxy resin or a halogen nucleus substitution product thereof, and (meth) acrylic acid can be mentioned.

Examples of the polyester acrylate include ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol, trimethylolpropane and alkylenes thereof. A polyester polyol obtained from an alcohol such as an oxide adduct and a dibasic acid such as adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid or an acid thereof such as an anhydride thereof; ) Examples include dehydration condensation products with acrylic acid. In the present invention, two or more compounds having these radically polymerizable unsaturated double bonds in the molecule may be used in combination.

Component C The component C photoinitiator is added to cure the composition by irradiation with active energy rays. Various types of photoinitiators can be used. Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and other benzoins and their alkyl ethers, acetophenone, 2,2-dimethoxy-
2-phenylacetophenone, 2,2-diethoxy-2
-Phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1-
[4- (methylthio) phenyl] -2-morpholino-
Acetophenones such as propan-1-one, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, anthraquinones such as 1-chloroanthraquinone and 2-amylanthraquinone, 2,4-dimethylthioxanthone, 2, 4-diethylthioxanthone, 2-chlorothioxanthone and 2,
Thioxanthones such as 4-diisopyrthioxanthone,
There are ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenones such as benzophenone, and xanthones. The photoinitiator may be used alone or in combination with a benzoic acid-based or amine-based photopolymerization initiation accelerator.

Production Method The composition of the present invention comprises the above-mentioned components A, B and C,
It can be obtained by stirring and mixing according to a conventional method. in this case,
The ratio of A component to B component is 5 to 95% by weight of A component, B
The content of the component is 95 to 5% by weight, and the component A is preferably 20.
To 90 parts by weight, and the component B is 80 to 10% by weight. If the component A is less than 5% by weight, the curability is poor,
On the other hand, if the component A exceeds 95% by weight, the cured product becomes brittle. The component C is 0.1 to 10 parts by weight per 100 parts by weight of the mixture of the components A and B. When the ratio of the C component is less than 0.1 parts by weight, the curability of the composition is not sufficient, while when it exceeds 10 parts by weight, the light resistance and thermal stability deteriorate.

In the second invention, the ratio of the A component and the B component is A
The active energy ray-curable (meth) acrylate composition of the first invention has a component content of 20 to 90% by weight, a B component content of 80 to 10% by weight, and a refractive index of 1.55 or more. By adopting such a composition, the composition is particularly suitable for coating an optical material. In the present invention, the refractive index is a value measured by an Abbe refractometer at 25 ° C. in a liquid before curing the composition. If the refractive index is less than 1.55, the film thickness cannot be reduced when coated with an optical material, which results in a heavy weight, poor moldability, and poor curability. Will end up.
There is no great difference in the refractive index between the composition and the cured product thereof.

The third invention is a composition containing (meth) acrylate having an aromatic ring as a part or all of the component B of the second invention. When the composition is used for coating an optical material, the cured product thereof has a higher refractive index and hardness. As the (meth) acrylate having an aromatic ring, as described above, a (meth) acrylate of an alkylene oxide adduct of phenol such as phenoxyethyl (meth) acrylate and a nuclear substitution product thereof with a halogen such as chlorine or bromine, bisphenol A. Of mono- or di (meth) acrylates, alkylene oxide adducts of bisphenol A such as ethylene oxide adducts or propylene oxide adducts, mono- or di (meth) acrylates, bisphenol A type epoxy resins or halogens such as chlorine or bromine Examples thereof include epoxy (meth) acrylates such as a reaction product of a substitution product, a bisphenol F type epoxy resin or a halogen nucleus substitution product thereof, and (meth) acrylic acid.

○ Method of Use The composition of the present invention is used for coatings, paints, printing inks,
Can be used for various applications such as adhesives, fillers and molding materials,
In particular, it can be preferably used as a coating agent for optical materials such as lenses and prisms. As a method of use, for example, a general method of applying to a substrate to be applied by a usual coating method and then curing by irradiating with active energy rays such as visible rays, ultraviolet rays and electron rays, is used. Can be adopted. As applicable substrates, various substrates such as wood, metals and plastics can be used, and the composition of the present invention is particularly useful for optical materials such as lenses and prisms. A general method can be adopted as a method for irradiating the active energy ray.

[0023]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below.

Production Example 1 226 g (1.0 mol) of o-phenylphenol glycidyl ether was placed in a flask equipped with a stirrer and a condenser.
72.1 g (1.0 mol) of acrylic acid, 3 g of tetrabutylammonium bromide and 0.15 g of hydroquinone monomethyl ether were charged and stirred at 90 ° C. for 8 hours. After cooling, 290 g containing the compound of formula (1) as the main component
Liquid A-1 was obtained. (Viscosity 6,600 cps / 25 ° C) The refractive index of A-1 alone was 1.577.

Examples 1 to 6 and Comparative Examples 1 to 5 Components A and B and C of the types and amounts shown in Tables 1 and 2
A composition was prepared by mixing the components according to a conventional method. The composition obtained was evaluated for curability, pencil hardness and odor according to the following methods. The results are shown in Tables 1 and 2.

However, the symbols in Tables 1 to 4 have the following meanings. 1) M-8060: Polyester acrylate, manufactured by Toagosei Co., Ltd. 2) M-1100: Urethane acrylate, manufactured by Toagosei Co., Ltd. 3) SP-1509: Bisphenol A type epoxy acrylate, manufactured by Showa High Polymer Co., Ltd. 4 ) M-220: tripropylene glycol diacrylate, manufactured by Toagosei Co., Ltd. 5) Irg651: benzyl dimethyl ketal (photoinitiator),
Ciba Geigy Co., Ltd. 6) M101: Phenol ethylene oxide 2 mol modified acrylate, Toagosei Co., Ltd. 7) V190: Ethyl carbitol acrylate, Osaka Organic Chemical Industry Co., Ltd. 8) TBBPA-DA: Tetrabromobisphenol A Diacrylate 9) M210: Bisphenol A ethylene oxide 4 mol modified diacrylate, manufactured by Toagosei Co., Ltd.

[0027]

[Table 1]

[0028]

[Table 2]

○ Evaluation / Curability Bonderite steel sheet as a base material (P made by Japan Test Panel Co., Ltd.
B-144), the composition is applied to a film thickness of 10 μ,
10m / m under 80W / cm condensing type high pressure mercury lamp (1 lamp)
It was passed at a conveyor speed of in. The coating film after passing was touched and evaluated by the number of passes until the surface tack disappeared.

[Pencil hardness] The pencil hardness was measured by hand according to the test method of JISK-5400.

Odor: The odor of the coating film immediately after curing was directly evaluated. In Table 1, ◯, Δ and × have the following meanings. ○: No odor △: Almost no X: Odor

Examples 7-9 and Comparative Examples 6-8 Components A and B and C of the types and amounts shown in Tables 3 and 4
The components were compounded in a conventional manner to produce a composition particularly useful for coating optical materials. The curability and odor of the obtained composition were evaluated in the same manner as in Example 1. The refractive index was measured as follows. The results are shown in Tables 3 and 4.

Refractive Index The refractive index at 25 ° C. was measured using an Abbe refractometer.

[0034]

[Table 3]

[0035]

[Table 4]

[0036]

EFFECTS OF THE INVENTION The composition of the present invention is extremely fast-curing and has no odor, and therefore it is useful in various industrial fields such as coatings, paints, printing inks, adhesives, fillers and molding materials. Yes, especially when used for coating optical materials such as lenses and prisms, it is fast-curing,
Further, since the cured product has a high refractive index, it can be applied to various optical materials.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area C08F 299/02 MRS C08F 299/02 MRS MRV MRV 299/04 MRT 299/04 MRT 299/06 MRX 299 / 06 MRX // (C08F 220/30 226: 10) (C08F 220/30 220: 26)

Claims (3)

[Claims] 1. A composition comprising the following components A, B and C:
The ratio of A component to B component is 5 to 95% by weight of A component, B
The component is 95 to 5% by weight, and the C component is 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the components A and B, the active energy ray-curable (meth) acrylate composition. . Component A: (meth) acrylate represented by formula (1) or formula (2) Embedded image [In the formulas (1) and (2), R represents hydrogen or a methyl group. Component B: compound other than component A having radically polymerizable unsaturated double bond in the molecule component C: photoinitiator 2. The ratio of A component to B component is 20 to A component.
The active energy ray-curable (meth) acrylate composition according to claim 1, wherein 90% by weight, the B component is 80 to 10% by weight, and the refractive index is 1.55 or more. 3. A part or all of the B component is a (meth) acrylate having an aromatic ring.
The active energy ray-curable (meth) acrylate composition described.