JP3326775B2 - Polymerization initiator composition - Google Patents

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. The cured product obtained 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 Many of the conventional sulfonium salt compounds functioning as heat latent cationic polymerization catalysts have low photoactivity (JP-A-2-178319, JP-A-3-3-1).
No. 7119). In addition, Japanese Patent Application Laid-Open No. 2-178303
And sulfonium salts described in JP-A-2-196812 are heat-latent cationic polymerization catalysts, exhibit activity even by radiation such as X-rays and electron beams, and cure cationically polymerizable compounds in a short time. Is said to be possible. However, when applied to a commonly used photocuring system, the photoactivity is low. on the other hand,
Many initiators for curing a radical polymerizable compound such as an acrylic compound by light irradiation have been reported at present, and there are many commercial products. For example, benzophenone, benzyldimethyl ketal and the like can be mentioned. However, these radical polymerization initiators do not have cationic polymerization activity and cannot cure cationically polymerizable compounds. Accordingly, a polymerization initiator and a polymerization initiator having both curing activity for radically curing a radical polymerizable compound and curing activity for cationically curing a cationically polymerizable compound by radiation of all regions such as heat, light, X-rays, and electron beams. No composition has yet been found.

[0003]

A compound obtained by cationically curing a cationically polymerizable compound such as an epoxy compound has smaller curing shrinkage and a lower curing time than a compound obtained by radically curing a radically polymerizable compound such as an acrylic compound. It has various features such as being unaffected by oxygen.

On the other hand, radically polymerizable compounds such as acrylic compounds have a higher curing speed than that of cationically polymerizable compounds and can be cured in a short time, and are hardly hindered by a basic compound or an ionic compound. Since there are many types, it is easy to obtain various cured product characteristics. Therefore, the field of application as a material is wide and the history is old, so the field of application is also diverse.

[0005] In recent years, in the field of materials, higher functionality and higher performance have been advanced, and there is a demand for improvement in characteristics of each material. For this reason, a single cured product such as a cationically cured product or a radically cured product has a limit as a material.
From these backgrounds, hybrids that can make use of each characteristic are receiving attention. However, conventional polymerization initiators for cationic curing and radical curing are:
In general, since it is a single function, in order to perform hybrid, both a cationic polymerization initiator and a radical polymerization initiator must be used in combination. For this reason, the ratio of the polymerization initiator in the resin component increases, and this leads to a decrease in the properties of the cured product and an increase in cost.

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

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above-mentioned object, and have found that using a sulfonium salt compound and a specific sensitizer in combination makes it impossible to use the sulfonium salt compound alone. It has been found that the cationically polymerizable compound or the radically polymerizable compound can be cured by a wide range of radiation such as heat, light, and electron beam, and the present invention has been completed.

Hereinafter, the present invention will be described in detail. The sulfonium salt-based heat 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]

Embedded image 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;
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]

Wherein 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 are
Represents a hydrogen atom, a halogen atom or an alkyl group;
₉ is a substituted or unsubstituted alkyl group containing an unsaturated bond,
R ₁₀ represents an alkyl group or a benzyl group which may be substituted; 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; 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;
Represents SbF ₆ , AsF ₆ , PF ₆ or BF ₄ . ]

[0012]

Embedded image [Wherein, 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 An alkyl group or a benzyl group, R ₁₇ and R ₁₈ may be bonded together, and X is SbF ₆ AsF ₆ ,
It represents a PF ₆ or BF _4. ]

[0013]

Embedded image [In the formula, 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 a benzyl group which may be substituted, X represents SbF ₆ , AsF ₆ ,
It represents a PF ₆ or BF _4. ]

[0014]

Embedded image [In the formula, R ₂₅ represents a hydrogen atom or an alkyl group which may be substituted, and R ₂₆ and R ₂₇ may be the same or different linear or branched alkyl groups, an alkyl group which may be substituted or A benzyl group, 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 halide such as benzhydryl bromide, cinnamyl bromide, crotyl bromide, halide having an unsaturated bond such as propargyl bromide, or 1-bromomethyl naphthalene such as Halogenated methylnaphthalene derivatives and the like and corresponding sulfide compounds are equimolarly added, if necessary, in the presence of an inert solvent such as methyl alcohol, acetone, or acetonitrile.
Days, and then the resulting solid is treated with water or water-
Dissolve in water-organic solvent system such as methyl ethyl ketone,
It is obtained by adding the corresponding salt such as sodium hexafluoroantimonate, stirring vigorously, separating the precipitated liquid or solid product, and then drying.

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

[0017]

Embedded image [Wherein, 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 represents a hydroxyl group, an optionally substituted alkyl group, an alkoxy group, an optionally substituted phenyl group, an optionally substituted benzyl group, an optionally substituted It represents a good phenoxy group or a benzyloxy group which may be substituted. ]

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

As the polymerizable compound used in the present invention, a cationic polymerizable compound and a radical polymerizable compound can be used. Examples of the cationic polymerizable compound include the following compounds. (A) As the compound having an epoxy group, 1,1,3-
Tetradecadiene dioxide, limonenedioxide, 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 novolak type epoxy resin, phenol novolak type epoxy resin and polyglycidyl ether of polyhydric alcohol

(B) Styrene, α as the vinyl compound
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 Divinyl ethers such as triethylene glycol vinyl ether and cyclohexanediol divinyl ether; aralkyl divinyl ethers such as 1,4-benzene dimethanol divinyl ether, Nm-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

(C) As the bicyclo orthoester 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 and the like (d) Spiro orthocarbonate compounds include
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-1,4,4
6-trioxaspiro [4,4] nonane, 1,4,6-
And spiroorthoester 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 particularly preferably used.

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

Examples of the radical polymerizable reactive diluent include acrylic acid ester monomers such as acrylic acid and 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 cationically polymerizable compound is 100 parts by weight of the cationically polymerizable compound, and the sulfonium salt compound is added in an amount of 0.1 part by weight.
It is blended in an amount of from 0.1 to 20 parts, preferably from 0.1 to 10 parts. If the amount of the sulfonium salt compound is small, the heat and electron beam curability of the cationically polymerizable compound will decrease, and if it is excessive, the properties of the cured product will decrease.

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

When the curable composition is heat-cured by using the polymerization initiator of the present invention, it is preferably at 20 ° C. to 200 ° C.,
It is performed in a 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. 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 and the like are used. Alternatively, laser light can be used.

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

[0028]

EXAMPLES The present invention will be described more specifically 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 company alicyclic epoxy), UVR-6410 (UCC
Glycidyl epoxy), BD-DEV [1, 4
-Butanediol-di- (2-vinyloxyethyl) ether], TMPT-A (trimethylolpropane triacrylate), 9G (polyethylene glycol 400
Dimethacrylate) alone or in a mixture thereof, and a sulfonium salt compound and a sensitizer in the following Table 1-1 to Table 1-1.
The curable composition was prepared by mixing at a predetermined ratio shown in No. 1. CP-66 and CP77 are sulfonium salt-based cationic polymerization initiators manufactured by Asahi Denka Kogyo. (Sensitizer) The sensitizers used in the examples are shown in Table 1-1 to Table 1
The following abbreviations were used in 11: 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 Example, a curable composition corresponding to each Example was prepared in the same manner except that the sensitizer was omitted. The details of the composition at the time of preparation are summarized in Tables 1-1 to 1-11.

<Preparation of Test Piece for Test> The test piece used in the tests of Examples and Comparative Examples was prepared by using the above-mentioned curable composition and applying a thickness of 10 μm to a tin plate with a doctor blade.
m.

<Test Method> (i) Photocurability Test I A test piece was placed in a nitrogen atmosphere under an ultra-high pressure mercury lamp at 5 J / cm.
² (25 ° C) irradiation. At this time, the cured film is
A mark, a thickened one was evaluated with a triangle, and a hardened one was evaluated with a cross, 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 to determine the time from UV irradiation to the top of the exothermic peak. The results of the examples are shown in Tables 4-1 and 4-2, and the results of the comparative examples are shown in Tables 5-1 and 5-2.

The UV-DSC measurement conditions are as follows. DSC measurement equipment: DSC220C (manufactured by Seiko Instruments Inc.) UV irradiator: ultra-high pressure mercury lamp Atmosphere: 30 ml / min in nitrogen gas flow Measurement temperature: 50 ° C. Sample amount: 0.1 to 0.3 mg Film thickness: 2 to 2 10 μm Irradiation time: 10 minutes Illumination: 10 mW / cm ² (365 nm) (However, the measurement temperature of the UV-DSC measurement of 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 a radically polymerizable compound can be converted in a short time by using a wide range of radiations such as heat, light and electron beams. Can be cured. That is, sulfonium salts are inherently polymerization initiators by heat, but by using a sulfonium salt and a specific sensitizer in combination, not only cationic polymerization by heat, but also photocationic polymerization and photoradical polymerization are possible. It became.

Embedded image

Embedded image

Claims (1)

(57) [Claims] (1)Sulfo represented by the general formulas [1] to [6]
At least one of the sodium salt compoundsAnd sensitizers
A polymerization initiator composition comprising: Embedded image [Wherein, R ₁ , R _Two Represents a hydrogen atom, a halogen atom,
Group, alkoxy group, nitro group, cyano group, vinyl group,
A carbamoyl group or an alkanoyl group, _Three Is the water
A hydrogen atom, an alkyl group or an optionally substituted phenyl
R represents a group _Four , R _Five Are the same or different linear or branched
Alkyl group, optionally substituted alkyl group or ben
A zyl group, R _Four And R _Five May be joined together
And X is SbF ₆ , AsF ₆ , PF ₆ Or BF _Four The table
You. ] Embedded image [Wherein, R ₆ Represents a hydrogen atom, an alkyl group,
Bonyl group, benzyl group, phenyl group, benzyl carbonyl
A benzoyl group or a benzoyl group; ₇ , R ₈ Is a hydrogen atom,
Represents a halogen atom or an alkyl group; ₉ Is replaced
An alkyl group containing an unsaturated bond, which may be substituted
A benzyl group or a phenacyl group,
_Ten Is an alkyl group or an optionally substituted benzyl group
X represents SbF ₆ , AsF ₆ , PF6 or BF _Four The table
You. R ₁₁ Represents a hydrogen atom, an alkyl group or a cyano group.
Then R ₁₂ Is an alkyl group, Alkoxycarbonyl group, or
Represents an optionally substituted phenyl group; ₁₃ , R ₁₄
Are the same or different linear or branched alkyl groups,
An optionally substituted alkyl or benzyl group, ₁₃
And R ₁₄ May be combined together, and X is Sb
F ₆ , AsF ₆ , PF ₆ Or BF _Four Represents ] Embedded image [Wherein, R _Fifteen , R ₁₆ Represents a hydrogen atom, a halogen atom,
A kill group or an alkoxy group; ₁₇ , R ₁₈ Are the same or
Is a different linear or branched alkyl group, even if it is substituted
A good alkyl or benzyl group; ₁₇ And R ₁₈ Haichi
X may be SbF ₆ , AsF ₆ ,
PF ₆ Or BF _Four Represents ] Embedded image [Wherein, R ₁₉ Represents a hydrogen atom, an alkyl group,
Bonyl group, benzyl group, phenyl group, benzyl carbonyl
A benzoyl group or a benzoyl group; ₂₀ , R _{twenty one} Is a hydrogen source
R, a halogen atom or an alkyl group; _{twenty two} , R
_{twenty three} Is a hydrogen atom, halogen atom, alkyl group or alcohol
Represents a xy group; _{twenty four} Is an alkyl group or a substituted
X represents SbF ₆ , AsF ₆ , P
F ₆ Or BF _Four Represents ] Embedded image [Wherein, R _{twenty five} Is a hydrogen atom, an optionally substituted
Represents a kill group; ₂₆ , R ₂₇ Are the same or different linear or
A branched alkyl group, an optionally substituted alkyl group or
Is a benzyl group, and R ₂₆ And R ₂₇ Are united and joined
X may be SbF ₆ , AsF ₆ , PF ₆ Or BF _Four To
Represent. ]