JPH111507A - Photopolymerizable composition, its adhesive and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of polymerizing in high sensitivity by using a light from visible region to near infrared region by compounding a monomer having a functional group with ethylenic unsaturated bond with an organic ionic dye compound and a specific photopolymerization initiator. SOLUTION: This photopolymerizable composition comprises (A) 100 pts.wt. monomer having one or more polymerizable functional groups having ethylenic unsaturated bond (e.g. methylacrylate or ethylacrylate) and/or its oligomer, (B) 0.1-3 pts.wt. organic ionic dye compound having absorption in visible or near-infrared region (e.g. polymethine-based dye compound, diphenylmethane- based dye compound, triphenylmethane-based dye or azo-based dye compound and (C) 0. 2-5 pts.wt. organoazobis compound of photopolymerization initiator (e.g. 2-cyano-2-propylazoforamide).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition, and more particularly, to a monomer and / or oligomer having at least one polymerizable functional group having an ethylenically unsaturated bond. A novel photopolymerizable composition that contains an organic ionic dye compound having absorption in the near infrared region and an organic azobis compound as a photopolymerization initiator, and can be polymerized with high sensitivity to light in the visible to near infrared region. Adhesives, fillers, sealants (sealants, molding agents),
The present invention relates to a photopolymerizable composition that can be used for a resin paint, a coating agent, an ink, a photoresist, a printing plate, and the like.

[0002]

2. Description of the Related Art It is well known that monomers and / or oligomers having one or more polymerizable functional groups having an ethylenically unsaturated bond are photopolymerized in the presence of a photopolymerization initiator. Adhesives, paints,
It is used for ink, photoresist, and printing plate materials. Commercially available photopolymerization initiators used for these include:
2,4-diethylthioxanthone, benzophenone, benzyldimethylketal (all manufactured by Nippon Kayaku), 2-
Methyl-1- [1- (methylthio) phenyl] -2-morpholinopropane-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenol) -butanone-
1,2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexylphenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, − (4-
Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-
Propane-1-one (all manufactured by Nippon Ciba Geigy),
Examples include 2-ethylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone (all manufactured by Mitsui Toatsu) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (manufactured by BASF).

However, these photopolymerization initiators have high sensitivity to light in the ultraviolet region, but have low sensitivity to light in a longer wavelength region (light of 450 nm or more). Use of these photopolymerization initiators is not possible because polymerization of compositions containing additives such as coloring pigments and ultraviolet absorbers that affect the transmittance of ultraviolet light, or compositions containing fillers, etc., are irregularly reflected by ultraviolet light. Was not suitable. In particular, when plastics are bonded, ultraviolet rays hardly pass through plastics, so that these polymerization initiators cannot be used as plastic adhesives. In addition, these are large, such as ultra-high pressure mercury lamps,
It has the disadvantage that it requires expensive irradiating equipment which is expensive and requires a large amount of running cost due to the risk of handling.
Further, regarding the photopolymerizable composition, a system of an organic peroxide and a dye (JP-A-59-140203, JP-A-59-18934)
However, organic peroxides are more difficult to handle than organic azobis compounds, and the photosensitivity is low unless the dye and the organic peroxide are added at a ratio of 1: 1. Had.

[0004]

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to be able to sufficiently polymerize using light in the visible to near-infrared region and to use resin coatings, inks, photoresists, and fillers. An object of the present invention is to provide a photopolymerizable composition that can be used as an agent, a sealant, and the like, an adhesive using the composition, and a bonded laminate.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a monomer and / or an oligomer having at least one polymerizable functional group having an ethylenically unsaturated bond can be combined with an organic ionic dye compound in a specific manner. The present inventors have found that the above problems can be solved by blending a photopolymerization initiator, and have reached the present invention. That is, the present invention includes the following items. (1) It is composed of a monomer and / or oligomer having one or more polymerizable functional groups having an ethylenically unsaturated bond, an organic ionic dye compound having absorption in a visible or near infrared region, and an organic azobis compound. Photopolymerizable composition. (2) The above-mentioned (1), wherein the organic ionic dye compound having absorption in the visible or near infrared region is a polymethine dye compound, a diphenylmethane dye compound, a triphenylmethane dye compound, or an azo dye compound. Photopolymerizable composition. (3) A resin composition containing the photopolymerizable composition according to (1) or (2). (4) An adhesive comprising the composition described in (1) to (3). (5) The adhesive according to (4), wherein at least one of the materials to be bonded is plastic. (6) A laminate in which materials are adhered using the adhesive according to (4). (7) The laminate according to (6), wherein at least one of the materials is plastic.

[0006]

DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention comprises a monomer and / or an oligomer having at least one polymerizable functional group having an ethylenically unsaturated bond and an absorption in the visible or near infrared region. An organic ionic dye compound having
An organic azobis compound as a photopolymerization initiator is contained as a component. Since the composition of the present invention is polymerized by light in the visible or near-infrared region, it may be a plastic molded member containing an ultraviolet absorber, or a translucent plastic molded member colored by adding a pigment. However, there is an advantage that adhesion, coating, and printing can be performed easily and effectively without being hindered by these ultraviolet absorbers and pigments. In addition, even if the composition itself contains an ultraviolet absorber and a pigment, polymerization can be performed without being affected by these.

Hereinafter, the components constituting the composition of the present invention will be described in detail. Organic ionic dye compounds having absorption in the visible or near infrared region that can be used in the composition of the present invention include organic cationic dye compounds and organic anionic dye compounds. Representative of the former are polymethine dye compounds, diphenylmethane dye compounds,
It is a triphenylmethane dye compound, the latter being an azo dye compound. In the composition of the present invention, those appropriately selected from these groups, alone or
A combination of more than one type can also be used. Examples of the aforementioned organic ionic dye compounds that can be used for the purpose of the present invention are described in, for example, "Dye Handbook" edited by Okawara, Kodansha, 1
47 to 233, 345 to 417, and the like. Examples of organic ionic dyes particularly suitable for the purposes of the present invention are listed in Table 1 together with their maximum absorption wavelength (λmax).
However, it goes without saying that the present invention is not limited to these dyes.

[0008]

[Table 1]

[0009] The photopolymerization initiator that can be used in the present invention is an organic azobis compound. Examples of the organic azobis compound that can be preferably used in the present invention include 2-cyano-2-propylazoformamide, 1,1′-azobis (cyclohexane-1-carbonitrile),
2'-azobis (2-methylbutyronitrile), 2,
2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 4,4 ′ -Azobis (4-cyanovaleric acid), 2,
Dimethyl 2'-azobisisobutyrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane],
2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propanamide}, 2,2′-azobis (2,4,4-trimethylpentane), 2,2'-azobis [2-methyl-N
-(2-hydroxyethyl) propionamide, 2,
2′-azobis [2- (hydroxyethyl) propionitrile] and the like.

The monomer having at least one polymerizable functional group having an ethylenically unsaturated bond which can be used in the present invention can be basically any compound as long as it is a compound capable of radical polymerization. And a compound having at least one acryloyl group or methacryloyl group. Examples of the compound having at least one acryloyl group or methacryloyl group in a molecule that can be suitably used in the present invention include methyl acrylate,
Ethyl acrylate, isopropyl acrylate, n-
Butyl acrylate, 2-ethylhexyl acrylate, isoamyl acrylate, isooctyl acrylate, lauryl acrylate, stearyl acrylate,
Tetrahydrofurfuryl acrylate, isobornyl acrylate, 2-hydroxyethyl acrylate, 2-
Hydroxypropyl acrylate, 2-hydroxy-3
-Phenoxypropyl acrylate, 3-chloro-2-
Hydroxypropyl acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, acryloyl morpholine, N, N-dimethylacrylamide, N, N-diethylacrylamide, N, N-
Dimethylaminopropylacrylamide, N, N-dimethylaminoethyl acrylate, phenoxyethyl acrylate, butoxyethyl acrylate, nonylphenoxyethyl acrylate, tetraethylene glycol-
4-nonylphenyl ether acrylate, decaethylene glycol-4-nonylphenyl ether acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclo [5.2.
1.0 ^2.6 ] decanyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, isoamyl methacrylate, isooctyl methacrylate, isodecyl methacrylate, lauryl methacrylate, stearyl methacrylate, tetrahydrofurfuryl methacrylate, Isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2
-Hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminomethyl methacrylate , N, N-diethylaminoethyl methacrylate, phenoxyethyl methacrylate, nonylphenoxyethyl methacrylate, tetraethylene glycol-4-nonylphenyl ether methacrylate, decaethylene glycol-4-nonylphenyl ether methacrylate, tricyclo [5.2.1.0
^2.6 ] decanyl methacrylate, glycidyl methacrylate, 2-methacryloylethyl isocyanate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, dimethylol tricyclodecane diacrylate, Tripropylene glycol diacrylate, hexapropylene glycol diacrylate, 2-hydroxy-1-
Acryloxy-3-methacryloxypropane, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butane Diol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6
-Hexanediol dimethacrylate, trimethylolpropane trimethacrylate and the like.

As oligomers, epoxy oligomers (trade names: UE8200 (manufactured by Dainippon Ink and Chemicals, Inc.), SP-1529X, SP-1509X (manufactured by Showa Polymer), YPB-40AM40 (manufactured by Toto Kasei)
K ester A-BPE-4, NK ester BPE-20
0, NK ester BPE-500, NK ester BPE
-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), epoxy ester 30
02M, epoxy ester 3000A (manufactured by Kyoeisha Yushi Kagaku KK) and the like. As urethane oligomers, U-4HA, U-6HA, U-324A, U
-200AX, U-340AX, UA-311 (manufactured by Shin-Nakamura Chemical Co., Ltd.), UN-9000PEP, UN-5200,
UN-9200A (manufactured by Negami Industry Co., Ltd.) and the like.

In the photopolymerizable composition of the present invention, the above-mentioned organic ionic dye compound having absorption in the visible or near infrared region, an organic azobis compound, and a polymerizable functional group having an ethylenically unsaturated bond 1 The mixing ratio with the monomer and / or oligomer having at least one monomer and / or oligomer is not particularly limited, but 100 parts by weight of a monomer and / or oligomer having at least one polymerizable functional group having an ethylenically unsaturated bond is included. Then, the organic ionic dye compound having absorption in the visible or near infrared region is 0.05 to
Within the range of 5 parts by weight, more preferably within the range of 0.1 to 3 parts by weight, and the organic azobis compound within the range of 0.1 to 10 parts by weight, more preferably within the range of 0.2 to 5 parts by weight. is there. If the amount of the organic ionic compound and the organic azobis compound is less than the above range, the photoactivity becomes insufficient and the curing becomes insufficient or the curing time becomes long, which is disadvantageous. Also,
Even if it is blended beyond the above range, the adhesive strength, the coating film strength and the printing stability are not so much improved, which causes a cost increase.

The composition of the present invention can be applied to each of the above-mentioned applications such as an adhesive as it is in the composition described above. Further, the photopolymerizable composition of the present invention may further comprise a chlorinated polyolefin resin or a chlorinated polyester resin if necessary. , Elastomers, tackifiers, dyes, pigments, fillers (talc, silica gel, alumina, calcium carbonate, etc.), metal salts (magnesium oxide, zinc oxide, etc.), ultraviolet absorbers, antioxidants, dye fillers, thickeners, Thixotropic agents, suspending agents, matting agents, solvents and the like can be added.

In the composition of the present invention, the monomer and / or oligomer having at least one polymerizable functional group having an ethylenically unsaturated bond adjusts the viscosity at the time of application of the composition and increases the adhesive strength after curing. It is used to improve. The amount used should be appropriately adjusted according to the viscosity required for the present composition and the adhesive strength after curing. However, excessive use reduces the adhesion. Therefore, it is preferable that the monomer and / or oligomer having one or more functional groups is contained in the composition in an amount of 3% by weight or more. The composition of the present invention can be used for bonding of various materials, etc., but it is difficult to bond the conventional photopolymerizable composition between plastic materials, or when one is plastic and the other is another material. It is suitable for. This gives a firmly bonded laminate.

Examples of the plastic molded product to which the composition of the present invention is applied include films, sheets, tapes, cloths, and the like.
In addition, it may be a molded product of various shapes, these may be reinforced by glass fiber, metal fiber, carbon fiber, or the like, and the composition application surface is a plastic, which is composited with another material. It may be a composite molded product. Further, as long as the object of the present invention is not impaired, additives such as an ultraviolet absorber may be contained as described later. Particularly, polycarbonate and polypropylene are blended with an ultraviolet absorber to prevent deterioration by ultraviolet rays. In many cases, the composition of the present invention is cured by using visible light or infrared light. Therefore, even if an ultraviolet absorbent is incorporated, the curing is not inhibited.

The photopolymerizable composition of the present invention can be obtained by mixing and stirring each of the above-mentioned components, and the storage thereof may be performed in a state where light is blocked. This composition can be used for applications such as screen printing, lithographic printing, letterpress printing, metal surface treatment, ink, paint, adhesive, and filler. The photopolymerizable composition of the present invention is cured with high sensitivity when irradiated with light in the visible or near infrared region.As the light source, as an incandescent bulb, a halogen bulb, a xenon bulb, a krypton bulb, a fluorescent lamp,
Any of LED, sunlight, and the like can be used. The light intensity and the irradiation time are experimentally determined in consideration of the light transmittance, light sensitivity, thickness, and the like of the composition application portion. Since the composition of the present invention does not use ultraviolet rays, which are often used for photopolymerization, during curing, it has the advantage that man-hours, equipment, and security measures are small.

[0017]

Next, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited by these examples. The names and contents of the components used in the following examples are shown below. Organic cationic dye compound (for structural formula, see Table 1): Crystal Violet (Basic Violet 3); for structural formula, see D14 [X = N (CH ₃ ) ₂ ] of Table 1. Rhodamine B (Basic Violet 10); For structural formula, see D9 in Table 1. Astrazone Orange G (Basic Violet 1
0); for structural formula, see D4 in Table 1 Congo Red (Direct Red 28); for structural formula, see D17 in Table 1 1,1,5,5-tetrakis- (4-diethylaminophenyl) pentadienylium para Toluene sulfonic acid;
For structural formula, see D11 in Table 1. Plastic molded product: Polycarbonate resin (manufactured by Teijin Chemicals Ltd., Teijin Panlite PC111, hereinafter referred to as “PC111”) Acrylic resin (Sumitomo Chemical Co., Ltd., SUMIPEC 000, hereinafter referred to as “SUMIPEC”) ) Light source: Halogen lamp (100V500WH, wavelength 37)
0 to 900 nm)

Evaluation of Composition The above-mentioned materials were adhered, and the adhesion was evaluated. The adhesive strength was determined according to the bending adhesive strength JIS K6856. Table 2 shows the results of the bending adhesive strength of the examples and the comparative examples.

Example 1 Ingredients Compounding amount (parts by weight) isobornyl acrylate 100 acryloylmorpholine 16 2,2′-azobis (2,4-dimethylvaleronitrile) 1 1,1,5,5-tetrakis- (4-Diethylamino 0.1 phenyl) pentadienylium p-toluenesulfonic acid Using the above composition, the bending adhesive strength of PC111 and Sumipec was measured. The adhesive sample was a test piece (length 1
(2.5 cm, width 2.5 cm, thickness 2 mm), 0.02 g of the above composition was applied to an area of 2.5 × 1.0 cm at the end of the test piece, and another test piece was stacked thereon and pressed. I sandwiched it. This was irradiated with light from a distance of 10 cm for 2.5 minutes. The following examples were similarly performed.

Example 2 Ingredients Compounding amount (parts by weight) isobornyl acrylate 100 acryloylmorpholine 16 2,2′-azobisisobutyronitrile 1 1,1,5,5-tetrakis- (4-diethylamino) 0.1 Phenyl) pentadienylium p-toluenesulfonic acid

Example 3 Ingredients Compounding amount (parts by weight) dicyclopentenyl acrylate 100 isobornyl acrylate 4 2,2′-azobis (2,4-dimethylvaleronitrile) 1 1,1,5,5- Tetrakis- (4-diethylamino 0.1 phenyl) pentadienylium paratoluenesulfonic acid

Example 4 Ingredients Compounding amount (parts by weight) phenoxyethyl acrylate 100 acryloylmorpholine 16 2,2′-azobisisobutyronitrile 1 Congo red 0.1

Example 5 Ingredients Compounding amount (parts by weight) isobornyl acrylate 100 2,2′-azobis (2,4-dimethylvaleronitrile) 1 rhodamine B 0.1

(Example 6) Ingredients Compounding amount (parts by weight) UN-9200A 12 Isobornyl acrylate 88 Acryloylmorpholine 19 2,2′-azobis (2,4-dimethylvaleronitrile) 1 Crystal violet 0.1

(Example 7) Ingredients Compounding amount (parts by weight) UN-9200A 12 Isobornyl acrylate 88 Acryloylmorpholine 19 2,2′-azobis (2,4-dimethylvaleronitrile) 1 1,1,5 5-tetrakis- (4-diethylamino 0.1 phenyl) pentadienylium paratoluenesulfonic acid

(Example 8) Ingredients Compounding amount (parts by weight) UN-9200A 12 Isobornyl acrylate 88 Acryloylmorpholine 19 2,2'-azobis (2,4-dimethylvaleronitrile) 1 Astrazone orange G 0. 1

(Comparative Example 1) Ingredient Compounding amount (parts by weight) UN-9200A 12 Isobornyl acrylate 88 Acryloylmorpholine 19 2,2′-azobis (2,4-dimethylvaleronitrile) 1

(Comparative Example 2) Component Compounding amount (parts by weight) isobornyl acrylate 100 2,2′-azobis (2,4-dimethylvaleronitrile) 1

(Comparative Example 3) Ingredients Compounding amount (parts by weight) UN-9200A 12 Isobornyl acrylate 88 Acryloylmorpholine 19 2,2′-azobisisobutyronitrile 1

[0030]

[Table 2]

The term "material failure" refers to a state in which when a test piece is loaded to a depth of 2 cm, the adhesive surface does not break and the material breaks first. Examples 1 to 8 show a monomer and / or oligomer having one or more polymerizable functional groups having an ethylenically unsaturated bond, an organic ionic dye compound having absorption in a visible or near infrared region, and a photopolymerization initiator. Are photopolymerizable compositions comprising an organic azobis compound, and Comparative Examples 1 and 2 are compositions containing no organic cationic dye compound having absorption in the visible or near infrared region. The results in Table 2 show that all of these examples have strong adhesion to plastic molded parts. In particular, in Examples 6, 7, and 8, the polycarbonate resin and the acrylic resin can be strongly bonded, but in Comparative Example 3 in which the organic cationic dye was not added, 2.5
It was in a gel state by light irradiation for minutes. This indicates that the organic ionic dye interacts with the organic azobis compound. Further, although the polycarbonate resin contains an ultraviolet absorbent, it is shown that any of the examples can strongly adhere without being affected by the ultraviolet absorbent.

[0032]

The photopolymerizable composition of the present invention comprises a monomer and / or an oligomer having at least one polymerizable functional group having an ethylenically unsaturated bond, and an organic ion having an absorption in the visible or near infrared region. It is a novel photopolymerizable composition that contains an organic azobis compound as a light-sensitive dye compound and a photopolymerization initiator and can be polymerized with high sensitivity with light in the visible to near-infrared region. Can be bonded by light irradiation. Further, since the photopolymerizable composition of the present invention does not use ultraviolet rays even if it is photopolymerizable, it can be applied to materials which cannot be subjected to ultraviolet polymerization even if the plastic molded member contains an ultraviolet absorber.

[Table 1]

[Table 1]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09J 157/00 C09J 157/00

Claims (7)

[Claims] 1. A method comprising: a monomer and / or an oligomer having at least one polymerizable functional group having an ethylenically unsaturated bond; an organic ionic dye compound having absorption in a visible or near infrared region; and an organic azobis compound. A photopolymerizable composition comprising: 2. The organic ionic dye compound having absorption in the visible or near infrared region is a polymethine dye compound, a diphenylmethane dye compound, a triphenylmethane dye compound, or an azo dye compound. A photopolymerizable composition. 3. A resin composition comprising the photopolymerizable composition according to claim 1. 4. An adhesive comprising the composition according to claim 1. 5. The adhesive according to claim 4, wherein at least one of the materials to be bonded is plastic. 6. A laminate obtained by bonding materials using the adhesive according to claim 4. 7. The laminate according to claim 6, wherein at least one of the materials is a plastic.