JPH06122705A - Polymerization initiator composition - Google Patents

Abstract

PURPOSE:To provide the subject composition with which not only thermal polymerization but also cationic and radical photopolymerizations are possible CONSTITUTION:This polymerization initiation composition comprises a thermally activable sulfonium salt initiator for cationic polymerization and a sensitizer. It enables a cationically polymerizable compound and/or a radical-polymerizable compound to cure in a short time upon irradiation with light and/or heating.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymerization initiator composition, and more specifically, it can cure a polymerizable compound such as a cationically polymerizable compound or a radically polymerizable compound in a short time by irradiation with light or heating. The present invention relates to a polymerization initiator composition. A cured product obtained by using the composition has excellent physical properties and is therefore suitably used as a material for paints, adhesives, inks and the like.

[0002]

2. Description of the Related Art Most of conventional sulfonium salt compounds functioning as a thermal latent cationic polymerization catalyst have low photoactivity (JP-A-2-178319, JP-A3-1).
7119, etc.). In addition, JP-A-2-178303
The sulfonium salts described in JP-A No. 2-196812 and the like are heat-latent cationic polymerization catalysts and also show activity by radiation such as X-rays and electron beams, and cure cationically polymerizable compounds in a short time. It is said that it is possible to do it. However, when applied to a commonly used photocuring system, the photoactivity is low. on the other hand,
A large number of initiators for curing radically polymerizable compounds such as acrylic compounds by light irradiation have been reported at present, and there are many commercially available products. Examples thereof include benzophenone and benzyl dimethyl ketal. However, these radical polymerization initiators have no cationic polymerization activity and cannot cure the cationically polymerizable compound. Therefore, a polymerization initiator and a polymerization initiator having both a curing activity for radically curing a radically polymerizable compound and a curing activity for cationically curing a cationically polymerizable compound by radiation in all regions such as heat, light, X-rays and electron beams. The composition has not yet been found.

[0003]

A compound obtained by cationically curing a cationically polymerizable compound such as an epoxy compound has a smaller curing shrinkage than that obtained by radically curing a radically polymerizable compound such as an acrylic compound. It has various characteristics such as not being affected by oxygen.

On the other hand, a radically polymerizable compound such as an acrylic compound has a faster curing rate than a cationically polymerizable compound and can be cured in a short time, and it is less susceptible to curing inhibition by a basic compound or an ionic compound. Since there are many types, it is easy to obtain various cured product characteristics. Therefore, it has a wide field of application as a material and has a long history, so it has a wide variety of fields of application.

In recent years, the field of materials has been advanced to have higher functionality and higher performance, and it has been required to improve the characteristics of each material. For this reason, individual cured products such as cation cured products and radical cured products have reached their limits as materials.
From these backgrounds, hybrids that can take advantage of their respective characteristics are drawing attention. However, the conventional polymerization initiators for cationic and radical curing are
In general, since it has a single function, both a cationic polymerization initiator and a radical polymerization initiator must be used in combination in order to carry out hybridization. Therefore, the proportion of the polymerization initiator in the resin component increases, which leads to deterioration of the properties of the cured product and an increase in cost.

[0006] Therefore, if the photoactivity of these sulfonium salt compounds can be increased, it will be possible to obtain a catalyst exhibiting high activity in all regions of radiation from heat to electron beams, which is industrially beneficial. . The present invention has been made in view of these circumstances, a polymerization initiator composition showing high activity in a wide range of radiation such as heat, light and electron beam for a cationically polymerizable compound or a radically polymerizable compound in a short time. It is intended to be provided.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and found that the use of a sulfonium salt compound in combination with a specific sensitizer makes it impossible to use a sulfonium salt compound alone. The present invention has been completed by finding that it is possible to cure a cationically polymerizable compound or a radically polymerizable compound which has been mentioned above, by radiation in a wide range of heat, light, electron beam and the like.

The present invention will be described in detail below. The sulfonium salt-based thermal latent cationic polymerization catalyst used in the present invention is not particularly limited as long as it is a sulfonium salt, and examples thereof include sulfonium salt compounds represented by the following general formulas 1 to 6. .

[0009]

[Chemical 1] [Wherein R ₁ and R ₂ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a nitro group, a cyano group, a vinyl group, a carbamoyl group or an alkanoyl group, and R 1
₃ represents a hydrogen atom, an alkyl group or an optionally substituted phenyl group, and R ₄ and R ₅ are the same or different linear or branched alkyl groups, an optionally substituted alkyl group or a benzyl group. And R ₄ and R ₅ may be bonded together, and X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ . ]

[0010]

[In the formula, R ₆ represents a hydrogen atom, an alkyl group, an alkylcarbonyl group, a benzyl group, a phenyl group, a benzylcarbonyl group or a benzoyl group, and R ₇ and R ₈ represent
Represents a hydrogen atom, a halogen atom or an alkyl group, R
₉ is an alkyl group containing an unsaturated bond even if substituted,
It represents an optionally substituted benzyl group or a phenacyl group, R ₁₀ represents an alkyl group or an optionally substituted benzyl group, and X represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ . ]

[0011]

[Wherein, R ₁₁ represents a hydrogen atom, an alkyl group or a cyano group, and R ₁₂ represents an alkyl group, an alkoxycarbonyl group, or an optionally substituted phenyl group,
R ₁₃ and R ₁₄ are the same or different linear or branched alkyl groups, optionally substituted alkyl groups or benzyl groups, and R ₁₃ and R ₁₄ may be bonded together, and X
Represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ . ]

[0012]

[Chemical 4] [In the formula, R ₁₅ and R ₁₆ represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, and R ₁₇ and R ₁₈ are the same or different linear or branched alkyl groups and may be substituted. It is an alkyl group or a benzyl group, R ₁₇ and R ₁₈ may be bonded together, and X is SbF ₆ AsF ₆ ,
Represents PF ₆ or BF ₄ . ]

[0013]

[Chemical 5] [Wherein R ₁₉ represents a hydrogen atom, an alkyl group, an alkylcarbonyl group, a benzyl group, a phenyl group, a benzylcarbonyl group or a benzoyl group, and R ₂₀ and R ₂₁ represent a hydrogen atom, a halogen atom or an alkyl group. , R ₂₂ , R
₂₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group, R ₂₄ represents an alkyl group or an optionally substituted benzyl group, X represents SbF ₆ , AsF ₆ ,
Represents PF ₆ or BF ₄ . ]

[0014]

[Chemical 6] [In the formula, R ₂₅ represents a hydrogen atom or an alkyl group which may be substituted, and R ₂₆ and R ₂₇ are the same or different linear or branched alkyl groups, an alkyl group which may be substituted or It is a benzyl group, and R ₂₆ and R ₂₇ may be bonded together, and X is SbF ₆ , AsF ₆ , PF ₆ or BF.
Represents ₄ . ]

The sulfonium salt compound of the present invention can be obtained, for example, by the following method. That is, benzyl bromide, α-substituted benzyl halides such as benzhydryl bromide, halides having unsaturated bonds such as cinnamyl bromide, crotyl bromide, propargyl bromide, or 1-bromomethylnaphthalene. A halogenated methylnaphthalene derivative or the like and a corresponding sulfide compound are equimolar at room temperature to reflux temperature for several hours to 30 in the presence of an inert solvent such as methyl alcohol, acetone, or acetonitrile, if necessary.
The resulting solid is reacted with water or water-
Dissolve in a water-organic solvent system such as methyl ethyl ketone,
It is obtained by adding a corresponding salt such as sodium hexafluoroantimonate and stirring vigorously, separating the precipitated liquid or solid product, and then drying.

The sensitizer used in the present invention is a compound that readily releases hydrogen radicals, and the compound itself after releasing the hydrogen radicals is an active radical, and has the ability to easily polymerize radically polymerizable compounds. Is said to have. For example, a thiol compound capable of curing a radically polymerizable compound by irradiation with a wide range of radiation when used in combination with a sulfonium salt compound and a compound represented by the following chemical formula 7 can be exemplified.

[0017]

[Chemical 7] [In the formula, R ₂₈ and R ₂₉ represent the same or different linear or branched alkyl groups, R ₂₈ and R ₂₉ may be bonded together, and R ₃₀ is a hydrogen atom, Represents a halogen atom or an alkyl group, R ₃₁ is a hydroxyl group, or an optionally substituted alkyl group, an alkoxy group, an optionally substituted phenyl group, an optionally substituted benzyl group, or an optionally substituted It represents a good phenoxy group or an optionally substituted benzyloxy group. ]

Examples of the compound represented by the above general formula [7] include isoamyl p-dimethylaminobenzoate, p-dimethylaminobenzoic acid, p-dimethylaminobenzaldehyde, ethyl p-dimethylaminobenzoate and p-dimethyl. Aminobenzoic acid (2-n-butoxyethyl), p-
Examples thereof include dimethylaminoacetophenone, p-diethylaminobenzoic acid, p-diethylaminobenzaldehyde and the like.

As the polymerizable compound used in the present invention, a cationically polymerizable compound and a radically polymerizable compound can be used. Examples of the cationically polymerizable compound include the following compounds. (A) As a compound having an epoxy group, 1,1,3-
Tetradecadiene dioxide, limonene dioxide, 4-vinylcyclohexene dioxide, (3,4
-Epoxycyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, di (3,4-epoxycyclohexyl) adipate, phenylglycidyl ether, bisphenol A type epoxy resin, halogenated bisphenol A type epoxy resin, o-, m-, Epoxy compounds such as p-cresol novolac type epoxy resin, phenol novolac type epoxy resin, polyglycidyl ether of polyhydric alcohol, etc.

(B) Styrene and α as vinyl compounds
-Styrenes such as methylstyrene and p-chloromethylstyrene; alkyl vinyl ethers such as n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and hydroxybutyl vinyl ether;
Alkenyl vinyl ethers such as allyl vinyl ether and 1-octahydronaphthyl vinyl ether; alkynyl vinyl ethers such as ethynyl vinyl ether and 1-methyl-2-propenyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; butanediol divinyl ether , Alkyldivinyl ethers such as triethylene glycol vinyl ether and cyclohexanediol divinyl ether; aralkyl dialkyl ethers such as 1,4-benzenedimethanol divinyl ether, N-m-chlorophenyldiethanolamine divinyl ether and m-phenylenebis (ethylene glycol) divinyl ether. Vinyl ethers; hydroquinone divinyl ether, resorcinol divinyl ether Aryl divinyl ethers such as ether; N- vinylcarbazole, N- vinylpyrrolidone and cationic polymerizable nitrogen-containing compounds such

As the (c) bicycloorthoester compound, 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2,2,2] octane, 1-ethyl-4-
Hydroxymethyl-2,6,7-trioxabicyclo [2,2,2] octane etc. (d) As the spiro orthocarbonate compound, 1,
5,7,11-Tetraoxaspiro [5,5] undecane, 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5,5] undecane and 1,4,6-trioxaspiro [4,4] nonane, 2-methyl-1,4
6-trioxaspiro [4,4] nonane, 1,4,6-
Examples thereof include spiro orthoester compounds such as trioxaspiro [4,5] decane. These may be used alone or in combination of two or more. Among (a) to (d), the compound having an epoxy group of (a) is preferably used.

As the radically polymerizable compound, for example,
Examples of the radically polymerizable oligomer include epoxy acrylate, epoxy methacrylate, polyester acrylate, polyester methacrylate, polyether acrylate, polyether methacrylate, polyurethane acrylate, polybutadiene acrylate, polybutadiene methacrylate and the like.

Examples of the radical-polymerizable reactive diluent include acrylic acid, acrylic acid ester monomers such as ethyl acrylate, methacrylic acid ester monomers such as methacrylic acid and ethyl methacrylate, and styrene.

In the present invention, the mixing ratio of the sulfonium salt compound and the cation polymerizable compound is 100 parts by weight of the cation polymerizable compound and 0.
It is blended at a ratio of 01 to 20 parts, preferably 0.1 to 10 parts. When the amount of this sulfonium salt compound is small, the heat and electron beam curability of the cationically polymerizable compound deteriorates, and when it is excessive, the properties of the cured product deteriorate.

On the other hand, the compounding ratio of the sensitizer and the cationically polymerizable compound is 0.01 to 20 parts, preferably 0.1 to 1 part of the sensitizer per 100 parts of the cationically polymerizable compound.
The ratio is 0. When the amount of these sensitizers is small, the photoreactivity of the sulfonium salt compound is lowered, and when the amount is excessive, depending on the type of the sensitizer, the cationic polymerization is inhibited and the photocurability of the cationically polymerizable compound is lowered. At the same time, the properties of the cured product deteriorate.

When the curable composition is heat-cured using the polymerization initiator of the present invention, it is 20 ° C. to 200 ° C., preferably
It is performed in the range of 50 ° C to 180 ° C. In the case of photo-curing, light having a wavelength of 400 nm or less, particularly ultraviolet light is preferably used, and therefore, as a light source, a low pressure mercury lamp, a medium pressure mercury lamp,
A high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a xenon lamp, a carbon arc lamp, etc. are used. Also, laser light can be used.

The curable composition of the present invention also contains α rays and β rays.
It can also be easily cured in a short time by ionizing radiation such as rays, γ rays, neutron rays, X rays, and accelerated electron rays. In the case of curing by ionizing radiation, usually 0.5 to 6
A dose range of 0 Mrad can be used, in particular 1-50 M
A range of rad is preferred. It is also possible to cure by using light, ionizing radiation and heat in combination.

[0028]

EXAMPLES The present invention will be described more specifically below with reference to examples and comparative examples. However, the present invention is not limited to these examples.

(Examples 1 to 73) ERL-4221 (U
CC alicyclic epoxy), UVR-6410 (UCC
Glycidyl type epoxy), BD-DIVE [1,4
-Butanediol-di- (2-vinyloxyethyl) ether], TMPT-A (trimethylolpropane triacrylate), 9G (polyethylene glycol 400)
Dimethacrylate) alone or in a mixture thereof, a sulfonium salt compound and a sensitizer are shown in Tables 1-1 to 1-1 below.
1 was blended at a predetermined ratio to prepare a curable composition. Further, CP-66 and CP77 are sulfonium salt-based cationic polymerization initiators manufactured by Asahi Denka Kogyo Co., Ltd. (Sensitizer) The sensitizers used in the examples are shown in Table 1-1 to Table 1-.
The following abbreviations in 11 were used. DMBI: isoamyl p-dimethylaminobenzoate P-DMAB: p-dimethylaminobenzoic acid P-DMABA: p-dimethylaminobenzaldehyde P-DMABE: ethyl p-dimethylaminobenzoate P-DMABBE: p-dimethylaminobenzoic acid ( 2-
n-butoxyethyl) P-DMAAP: p-dimethylaminoacetophenone P-DEAB: p-diethylaminobenzoic acid P-DEABA: p-diethylaminobenzaldehyde

[0030]

[Table 101]

[0031]

[Table 102]

[0032]

[Table 103]

[0033]

[Table 104]

[0034]

[Table 105]

[0035]

[Table 106]

[0036]

[Table 107]

[0037]

[Table 108]

[0038]

[Table 109]

[0039]

[Table 110]

[0040]

[Table 111]

(Comparative Examples 1 to 66) In each of the Examples, a curable composition corresponding to each Example was prepared in the same manner with the compounding composition excluding the sensitizer. The details of the composition at the time of preparation are summarized in Table 1-1 to Table 1-11.

<Preparation of Test Pieces for Test> The test pieces used in the tests of Examples and Comparative Examples were made of the above-mentioned curable composition and had a thickness of 10 μm on a tin plate with a doctor blade.
It was applied so as to have a thickness of m.

<Test method> (i) Photocurability test I 5 J / cm of a test piece under a nitrogen atmosphere and an ultra-high pressure mercury lamp.
² (25 ° C). At this time, if the coating film was cured,
Marks and thickened samples were evaluated as Δ, and those that were not cured were evaluated as x. The results of Examples are shown in Tables 2-1 and 2-2, and the results of Comparative Examples are shown in Table 3. Indicated.

[0044]

[Table 201]

[0045]

[Table 202]

[0046]

[Table 3]

(Ii) Photocurability test II The cured composition was subjected to UV-DSC measurement, and the time from UV irradiation to the top of the exothermic peak was determined. The results of Examples are shown in Tables 4-1 and 4-2, and the results of Comparative Examples are shown in Tables 5-1 and 5-2.

The UV-DSC measurement conditions are as follows. Measuring equipment of DSC: DSC220C (manufactured by Seiko Denshi Kogyo Co., Ltd.) UV irradiator: Ultra high pressure mercury lamp atmosphere: Nitrogen gas stream 30 ml / min Measurement temperature: 50 ° C Sample amount: 0.1-0.3 mg Membrane thickness: 2- 10 μm Illumination time: 10 minutes Illumination: 10 mW / cm ² (365 nm) (However, the measurement temperature for UV-DSC measurement in Example 13 and Comparative Example 9 is 20 ° C.)

[0049]

[Table 401]

[0050]

[Table 402]

[0051]

[Table 501]

[0052]

[Table 502]

[0053]

As described above, by using the polymerization initiator composition of the present invention, a cationically polymerizable compound or radically polymerizable compound can be produced in a short time by using a wide range of radiation such as heat, light and electron beam. Can be cured. That is, the sulfonium salt is originally a polymerization initiator by heat, but by using the sulfonium salt and a specific sensitizer together, not only cationic polymerization by heat but also cationic photopolymerization and radical photopolymerization are possible. Became.

[Chemical 2]

[Chemical 2]

Claims (1)

[Claims] 1. A polymerization initiator composition comprising a sulfonium salt-based thermally latent cationic polymerization initiator and a sensitizer.