JPH03293670A - Photopolymerizable composition - Google Patents

Abstract

PURPOSE:To enable photopolymerization by the visible light by incorporating a basic dye, an aliphatic tertiary amine and/or tertiary phosphine and tertiary thiophosphite in a photopolymerization initiator. CONSTITUTION:The photopolymerizable composition containing a polymerizable monomer having an ethylenically unsaturated double bond and the photopolymerization initiator comprising the basic dye, the aliphatic tertiary amine and/or the tertiary phosphine and the tertiary thiophosphite. Ten pts.wt. of the polymerizable monomer, 0.001 - 0.50 pts.wt. of the basic dye, 0.002 - 2.0 pts.wt. of the aliphatic tertiary amine, 0.002 - 2.0 pts.wt. of the tertiary phosphine, and 0.002 - 2.0 pts.wt. of the tertiary thophosphite are dispersed or dissolved at room temperature or when needed, with heating, to prepare the composition, thus permitting the obtained photopolymerizable composition to be enabled.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides a method for applying light in the ultraviolet or visible wavelength range to
The present invention relates to a composition for polymerization.

[Conventional technology]

Most conventional photopolymerizable compositions are polymerized by light with a wavelength in the ultraviolet region (hereinafter simply referred to as ultraviolet light).
Since these photopolymerizable compositions have low polymerization sensitivity, it is necessary to lengthen the irradiation time or increase the intensity of light energy.

As a result, the equipment for the ultraviolet generator becomes oversized, and there are problems such as the generation of ozone during use, which has an adverse effect on the body, and the ultraviolet rays, which have an adverse effect on the eyes, skin, and the like. In addition, when the intensity of light energy is increased, the photopolymerizable composition generates heat due to the heat rays emitted at the same time, deforming the polymerized composition, which significantly limits the range of applications of these photopolymerizable compositions. It had the disadvantage of being

Therefore, there is a need for a photopolymerizable composition that polymerizes with visible light of low energy intensity and has high polymerization sensitivity.
Publication No. 044, magazine [Surface Vol. 27 (19
89) Photopolymerizable compositions as described in J, pages 548 (35) to 559 (45) have been proposed.

C Problems to be Solved by the Present Invention] However, even with the photopolymerizable composition as described above, the polymerization sensitivity is still low, so only the surface portion of the photopolymerizable composition that is irradiated with visible light polymerizes immediately. However, the interior is difficult to polymerize and is not completely satisfactory. Furthermore, if a photopolymerization initiator is added to the photopolymerizable composition in advance, the viscosity of the photopolymerizable composition increases or it hardens, resulting in problems such as poor stability over time as a photopolymerizable composition. .

The present invention aims to improve the above-mentioned problems by polymerizing not only with ultraviolet rays but also with visible light that is safe for the human body and has low energy intensity such as from lighting sources, and in which a photopolymerization initiator is added to the photopolymerizable composition in advance. The object of the present invention is to obtain a photopolymerizable composition that has good stability over time even when it is blended.

[Means to solve the problem]

In order to achieve the above object, the present inventor conducted various studies in order to carry out photopolymerization using visible light.

As a result, (1) an aliphatic tertiary amine and/or a tertiary phosphine is added to a polymerizable monomer having an ethylenic double bond, or a tertiary thiophosphine is added to a polymerizable monomer having an ethylenic double bond; When phyto is added, it polymerizes under ultraviolet light, but not under visible light.

(2) When a basic dye is added as a sensitizer to each of the above formulations, they have the property of being polymerized by visible light, but the polymerization sensitivity is not satisfactory.

I found out.

The present inventor further investigated, and in order to obtain a photopolymerizable composition having high polymerization sensitivity with visible light, as a photopolymerization initiator,
A basic dye as a sensitizer, an aliphatic tertiary amine and/or a tertiary phosphine as a radical generator, and a tertiary
The present inventors have discovered that, when used in combination with grade thiophosphite, it is possible to obtain a photopolymerizable composition that has high curing sensitivity under visible light and good stability over time, which has not been possible in the past. It was completed.

That is, the present invention provides (1) a photopolymerizable composition containing a polymerizable monomer having an ethylenic double bond and a photopolymerization initiator, in which the photopolymerization initiator comprises a, a basic dye, and b. This is a photopolymerizable composition containing an aliphatic tertiary amine and/or a tertiary phosphine, Cl, and a tertiary thiophosphite.

(2) The polymerizable monomer having an ethylenic double bond is selected from prepolymers and oligomers such as heptadmers and trimers having at least one ethylenic double bond in the chemical structural formula. 2. The photopolymerizable composition according to claim 1, comprising one or more molecules.

(3) The photopolymerizable composition according to claim 1 or 2, wherein the basic dye consists of one or more selected from carbonium dyes, quinone imine dyes, and methine dyes.

Examples of the polymerizable monomer having an ethylenic double bond in the present invention include acrylic ester, isoamyl acrylate, lauryl acrylate, stearyl acrylate, butoxyethyl acrylate, phenoxyethyl acrylate, ethoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, Phenoxypolyethylene glycol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, β-acryloyloxyethyl hydrogen phthalate, β-acryloyloxyethyl hydrogen succinate, nonylphenoxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3- Phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl 2-hydroxyethylphthalate, 2-acryloyloxyethyl acid phosphate, triethylene gelicol diacrylate, polyethylene glycol #20
0 diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, EO-modified bisphenol A diacrylate, 2,2”-su[4-(acryloxyjethoxy)]phenylpropane Diacrylate, trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, neopentyl glycol acrylate benzoate, isooctyl acrylate, benzyl acrylate, 2-Hydroxybutyl acrylate, perfluorooctylethyl acrylate, hydrogenated dicyclopentagenyl diacrylate, urethane acrylates include phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane brevolimer, glycerin dimethacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol Examples of epoxy acrylates include triacrylate hexamethylene diisocyanate urethane prepolymer, and 2-hydroxy-3-phenoxypropyl acrylate.Other product names include Epolite 70P acrylic acid adduct, Epolite 1600 acrylic acid adduct, and Epolite. 80MF acrylic acid adduct, Evolite 3002 acrylic acid adduct, bisphenol A jepoxy acrylic acid adduct, Epolai) 200E acrylic acid adduct (manufactured by Kyoei Yuushi Kagaku Kogyo ■), as polyester acrylate, Viscoat #700, Viscoat # 2000, Viscoat #2100, Viscoat #3700 (manufactured by Osaka Organic Chemical Industry ■), and silicone conacrylates such as XE17-AO884 and XE17-AO46.
8. TFC7770°TFC7870 (manufactured by Toshiba Silicone ■) etc. are used alone or in combination.

The basic dye to be blended in the present invention can be any general basic dye, but carbonium dyes, quinone imine dyes, and methine dyes are preferably used.
c Yellow 2 (manufactured by Odugaya Chemical Co., Ltd.) ・Triphenylmethane-based AIZEN Victoria Blue BH (Ba
sic Blue 26 Hodogana” ([) Crystal Violet (Basic Violet 3) Malachite Green (Basic Green 4) A
IZEN Ac1d Violet 5B (Acid
Violet 49 Earth mining and pottery attack) AIZ
EN Ac1d Br+11rant Mjlljng
Green B (Acid Green 9 Dougaya ([)Naphthalene Green (
Acid Green 16) Fast Green
FCF Eating Green No. 3 Daiwai b 戊片帡体) ・Xanthine-based AIZEN Ac1d Rhodamine BH (A
cid Red 52 manufactured by Hodogaya Chemical ■) Rhodamine G (Basic Red 1) Rhodamine (Basic Violet 10) ・Acridine-based acridine yellow Acridine Orange (Basic Orange 14) As a quinone imine dye ・Azine-based neutral red CATHILON BRILLIANT FL AVIN
E l0GHF (Basic Yellow140Hodogasui X) Safranine O (Basic R
ed 2) AIZEN Ba5ic pure Blue
e 5GH (Basic Blue 3 manufactured by Odugaya Kagaku Co., Ltd.) - Thiazine-based lemon flavin 00 (Basic Yellow 1 manufactured by Kansai Dye ■) H3 C! - Thionine methylene blue (Basic Blue 9) ZURE ZtJRB ZURE Methylene green methine CATHILON Pink FGH (Basic R
ed 13 Hodogaya-fu Kengakushu) CATHILON B
r1ll Red 4GH (Basic Red 14
(manufactured by Hodogaya Chemical) Shih3 CATHILON Red 6GH (Basic Vi
OLat Maheshi Sink Handling Science [Yes] - Prefecture) H3 etc. can be used alone or in combination.

(Leaving space below) The aliphatic tertiary amine used in the present invention is represented by the following general formula, and has a two-pronged formula (R1-3=C+-z.alkyl group, C+-□.=alkanol group). , R2, R3 (bipedillin, morpholine derivatives)) For example, trimethylamine, triethylamine, tributylamine, trihexylamine, trioctylamine, trilaurylamine, dimethyloctylamine, dimethyllaurylamine, dimethylstearylamine, penta Methyldiethyltetramine, tetramethyldiaminohexazine, triethanolamine, methylgetanolamine, butylgetanolamine, dimethylamitubrobanol, dibutylamitutanol, dimethylbenzylamine, Sanol LS-765 (Sankyo ■ tertiary grade) amine), N-methyl-3-piperidinemethanol, dipiperidinomethane, MARK LA62, MARK L
A-63 (a tertiary amine manufactured by Adeka and Argus Chemical Co., Ltd.) and the like are used alone or in combination.

The tertiary phosphine used in the present invention can be represented by the following general formula, and includes a two-pronged formula (R represents an alkyl group or an aryl group), such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzyl Phosphine, tritolylphosphine, P-styryldiphenylphosphine, TPP-3 (Hokuko Chemical Industry ■
One or more selected from the following can be used:

The tertiary thiophosphite used in the present invention is Ch
elexSP-1 (manufactured by Sakai Chemical ■, tris(2-ethylhexyl-3-mercaptopropionate) phosphite), Che 1exLT-3 (manufactured by Sakai Chemical ■), JPS-
312 (manufactured by Johoku Kagaku Kogyo ■, trilauryltrithiophosphite), etc. are used alone or in combination.

Next, the photopolymerized crude product of the present invention contains 0.001 to 0.5 parts by weight of a basic dye, 0.001 to 0.5 parts by weight of an aliphatic grade amine 0.002-2 parts by weight, tertiary phosphine 0.002-2 parts by weight
It is prepared by dispersing or dissolving 2 parts by weight and 0.002 to 2 parts by weight of tertiary thiophosphite at room temperature or while heating if necessary. Furthermore, binder components, diluents, heat stabilizers,
Additional components such as colorants, extender pigments, antifoaming agents, and leveling agents may also be added as appropriate to the extent that they do not interfere with the effects of the present invention.

[Example] Although an example of the present invention will be described, the present invention is not limited to this example.

(Examples 1 to 28) 10 parts by weight of a polymerizable monomer having an ethylenic double bond (hereinafter simply referred to as a monomer) and 0.001 to 0.001 parts by weight of a basic dye (hereinafter referred to as a sensitizer) 0.5 parts by weight, and 0.5 parts by weight of aliphatic tertiary amine (hereinafter referred to as radical generator-1).
0.002 to 2 parts by weight, 0.002 to 2 parts by weight of tertiary phosphine (hereinafter referred to as radical generator-2), and tertiary phosphine (hereinafter referred to as radical generator-2).
class thiophosphite (hereinafter referred to as radical generator-3).

A photopolymerizable composition was obtained by dissolving or dispersing 0.002 to 2 parts by weight of additives and additives in the respective parts by weight of each composition in each Example shown in Table 1.

(Left below) (Comparative Example 1) Monomer trimethylolpropane triacrylate 10 parts by weight Radical generator-1 Sanol LS-765 1.0 parts by weight Radical generator-2 Triphenylphosphine o, 1 1 part by weight Radical generator -3 Che 1exSP-10,044 parts by weight The above components were mixed and dissolved to obtain a photopolymerizable composition.

(Comparative Example 2) Monomer trimethylolpropane triacrylate 10 parts by weight Sensitizer CAT) frLON PINK GH 0.01 parts by weight Radical generator-1 Sanol LS-765 1.0 parts by weight Radical generator-2 Triphenylphosphine 0, 1 weight part The above components were mixed and dissolved to obtain a photopolymerizable composition.

(Comparative Example 3) Monomer hydrogenated dicyclopentadienyl diacrylate 10 parts by weight Exacerbant Rhodamine BO, 01 parts by weight Radical generator-1 Methyljetanolamine 0.6 parts by weight The above components were mixed and dissolved, A photopolymerizable composition was obtained.

(Comparative Example 4) Monomer hydrogenated dicyclopentadienyl diacrylate 10 parts by weight Sensitizer Rhodamine BO 2 parts by weight Radical generator-1 Che 1exsP-10,044 parts by weight The above components were mixed and dissolved, A photopolymerizable composition was obtained.

The photopolymerizable compositions obtained in each Example and Comparative Example were then tested for visible light sensitivity and stability over time.

Visible Light Sensitivity: Exposure for 5 seconds through a xenon arc lamp (intensity 4 mwcm-'' 365 nm, ultraviolet cut filter (L-42)) in the middle of the day.

), and visually observed whether it hardened or not, and determined as follows.

The composition is cured... O The composition is partially cured... The composition is not cured at all... × Stability over time: In a light-shielding bottle After each composition was filled, sealed and left at 60°C for a day and night, the state of the composition was observed and judged as follows.

There is no change in the state of the composition... ○The viscosity of the composition has increased or the composition has hardened...
・・・・・・×The test results are shown in Table 2.

[Effects of the Invention] Since the photopolymerizable composition of the present invention has high polymerization sensitivity, it polymerizes not only with ultraviolet rays but also with visible light. When the composition is polymerized using an illumination lamp with low energy intensity as a visible light source, there is no fear that the polymer will undergo thermal deformation.

Furthermore, since visible light is used, it has become possible to obtain polymers with a thickness of several tens of microns to several tens of microns.

In addition, since it has good stability over time, a photopolymerizable composition containing a photopolymerization initiator in advance can be polymerized using visible light. There is no need to prepare the initiator and use it immediately.

Claims (3)

[Claims] (1) A photopolymerizable composition containing a polymerizable monomer having an ethylenic double bond and a photopolymerization initiator, wherein the photopolymerization initiator contains a) a basic dye and b) an aliphatic tertiary A photopolymerizable composition containing an amine and/or a tertiary phosphine, and c. a tertiary thiophosphite. (2) The polymerizable monomer having an ethylenic double bond is selected from monomers, prepolymers such as dimers, trimers, and oligomers having at least one ethylenic double bond in the chemical structural formula. 2. The photopolymerizable composition according to claim 1, comprising one or more molecules. (3) The photopolymerizable composition according to claim 1 or 2, wherein the basic dye consists of one or more selected from carbonium dyes, quinone imine dyes, and methine dyes.