JPH06157626A - Cationically polymerizable and curable composition - Google Patents

Abstract

PURPOSE:To obtain a polymerizable and curable compsn. having improved adhesiveness, abrasion resistance. insulating properties, etc., by compounding a cationically polymerizable compd. with a specific sulfur compd. CONSTITUTION:A sulfonimide is reacted with N-bromosuccinimide or chlorine gas in a molar ratio of the former to the latter of (10:1) to (1:10) at -30 to 10 deg.C for 5min to 5hr to give a chlorine adduct, which is reacted with a sec. amine in a molar ratio of the adduct to the amine of (10:1) to (1:50) at -20 to 50 deg.C for 1-40hr to give a sulfur compd. of the formula [wherein R<1>, R<2>, and R<3> are each 1-30C (halogenated)alkyl, (halogenated)aryl, arylsulfonyl, aralkyl, alkenyl, cyclo(alkyl)alkyl, arylcycloalkyl, alkylene, arylene, or (oxa)aralkylene; X is 0 or S; and (m), (n), and (p) are each 0 or 1]. The objective compsn. is obtd. by compounding 100 pts.wt. cationically polymerizable compd. with 0.001-50 pts.wt. the sulfur compd.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel cationically polymerizable curable composition, more specifically, a cationically polymerizable compound capable of being polymerized or cured at a relatively low temperature by irradiation with energy rays within a practical period of time. And a specific sulfur-containing compound as an active ingredient.

[0002]

2. Description of the Related Art In recent years, photo- or thermal-polymerization of a cationically polymerizable compound such as an epoxy resin has attracted attention because of its excellent physical properties. In particular, photopolymerizable polymer materials have attracted attention especially in the field of coating materials from the viewpoints of energy saving, space saving, and pollution-free, but it is generally difficult to photopolymerize an epoxy resin. However, recently, as a catalyst for cationic polymerization,
There have been reports on aromatic diazonium salts of Lewis acids (British Patent No. 1321263, U.S. Pat. No. 3,205,157), which were reported to be useful as photopolymerization initiators for epoxy resins. However, since this aromatic diazonium salt releases nitrogen gas in addition to the Lewis acid by photolysis, it has a defect that the coating film foams when formed into a coating film.
It has also been reported that aromatic iodonium salts of Lewis acids and Group VIA onium salts are similarly useful as cationic polymerization catalysts for epoxy resins (Japanese Patent Publication No. 52-142).
77, Japanese Patent Publication No. 52-14278, and Japanese Patent Laid-Open No. 5
5-65219, British Patent No. 1526923, British Patent No. 1516511, British Patent No. 1518141, US Patent No. 4069054). However, in photopolymerization of an epoxy resin or the like using these known onium salts by ultraviolet irradiation, it is generally difficult to cure to a deep portion, and therefore the development of an initiator having higher curability is strongly desired. Is the actual situation.

[0003]

Under the circumstances described above, the present invention is capable of irradiating an energy ray within a practical period of time and / or polymerizing and curing at a relatively low temperature to cure a coating film. The purpose of the present invention is to provide a cationically polymerizable curable composition that does not generate bubbles and gives a cured coating film of good quality.

[0004]

Means for Solving the Problems As a result of intensive studies on the initiator of a cationically polymerizable compound, the present inventors have found that
It was found that a specific sulfur-containing compound polymerizes a cationically polymerizable compound under irradiation of energy rays and / or at a relatively low temperature to give a cured coating film of good quality, and based on this finding, the present invention was completed. I arrived. That is, the present invention provides (A) a cationically polymerizable compound, and (B) a general formula

[0005]

[Chemical 2]

(In the formula, R ¹ , R ² and R ³ are each an alkyl group having 1 to 30 carbon atoms, a halogenated alkyl group, an aryl group, a halogenated aryl group, an arylsulfonyl group, an aralkyl group, an alkenyl group, Cycloalkyl group,
A cycloalkylalkyl group, an arylcycloalkyl group, an alkylene group, an arylene group, an aralkylene group or an oxaalkylene group, which may be the same or different from each other, and X is an oxygen atom or a nitrogen atom. , M, n and p are each 0 or 1), and a cationic polymerization curable composition comprising a sulfur-containing compound represented by the formula (1) as an active ingredient.

The present invention will be described in detail below. The cationically polymerizable compound used as the component (A) in the composition of the present invention is a cationically polymerizable monomer or a cationically polymerizable polymer having a functional group capable of undergoing cationic polymerization in the molecule. Examples thereof include glycidyl ether and epoxy novolac resin obtained by reacting bisphenol A [2,2-bis (4-hydroxyphenyl) propane] or its alkylene oxide adduct with epichlorohydrin; Cyclohexene oxide or cyclopentene oxide obtained by epoxidizing a polyglycidyl ether of a polyhydric alcohol having an alicyclic functional group, cyclohexene or a cyclopentene ring-containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid Alicyclic epoxy resins such as compounds; glycidyl ether obtained by reaction of hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin; glycidyl ether of 1,6-hexenediol, triglyceride of glycerin Ethers, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, aliphatic polyhydric alcohol to one or two or more alkylene oxides such as glycerin (e.g. ethylene oxide, propylene oxide)
An epoxy compound such as a polyglycidyl ether of a polyether polyol obtained by adding a vinyl ether group; an acrylic resin derivative containing a vinyl ether group in which a vinyl ether group is introduced into a side chain of a polymer through an ester bond; a cyclic group such as an epoxide and an episulfide Ethers and cyclic thioethers; cyclic ketones; lactones; oxetanes; styrenes; acrolein; vinylarenes such as 4-vinylbiphenyl; alicyclic vinyl compounds such as vinylcyclohexene;
Isobutylene; dienes such as butadiene and isoprene; phenolic resins such as phenol / formaldehyde resins; aminoplast resins such as urea / formaldehyde resins and melamine / formaldehyde resins; methylol compounds; polyacrylic acid amides or polymethacrylic acid amide derivatives Methylol ethers of carboxylic acid amides; alkyd resins having urethane groups and N
-Cationically polymerizable monomers or polymers such as resins containing carbonic acid ester of methylolamide. Among these, vinyl ethers and epoxy resins are preferably used. Further, it is also possible to use acid-polymerizable or acid-curable ethylenically unsaturated compounds such as vinylcarbazole, vinyl ether and diketene, and further include a crosslinkable binder-containing resinous compound which can be cured by an acid. To be done. These cationically polymerizable compounds may be used alone, but it is preferable to use a combination of two or more kinds as appropriate according to the desired performance. In the composition of the present invention, as the component (B), a compound represented by the general formula

[0008]

[Chemical 3]

A sulfur-containing compound represented by the formula (wherein R ¹ , R ² , R ³ , X, m, n and p have the same meanings as described above) is used. Specific examples of R ¹ , R ² and R ³ in the general formula [1] include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, isobutyl group, t-butyl group and phenyl group. , Benzyl group, p-tolyl group, p-tosyl group, p-chlorophenyl group, p-bromophenyl group and the like can be preferably mentioned. Also - as the ² groups (X) _n -R, it may also be mentioned preferably cyclic amino group such as a morpholino group or a piperidinyl group.
The sulfur-containing compound represented by the general formula [1], for example, sulfilimine, is obtained by mixing sulfide and chloramine T in methanol, and then pouring the mixture into a dilute aqueous sodium hydroxide solution at a temperature of about 50 ° C. for 1-5. It can be produced by leaving it for a while, or it can be produced by mixing sulfide and chloramine T in methanol, adding acetic acid thereto, and then pouring it into an aqueous solution of sodium hydroxide and letting it stand. You can This reaction formula is shown below.

[0010]

[Chemical 4]

The sulfonimide amide can be produced by a method in which sulfinamide is reacted with N-bromosuccinimide (NBS) or chlorine gas and then with a secondary amine. This reaction formula is shown below.

[0012]

[Chemical 5]

A sulfur-containing compound represented by the general formula [1],
For example, in the case of producing sulfonimide amide, the reaction temperature of the sulfinamide and N-bromosuccinimide (NBS) or chlorine gas is preferably in the range of -30 ° C to 10 ° C, and the reaction temperature is about 5 minutes to 5 hours. is there. The molar ratio of sulfinamide and NBS or chlorine gas charged is preferably in the range of 1: 0.1 to 1:10. Next, when the obtained chlorine adduct is reacted with the secondary amine, the charged molar ratio is preferably in the range of 1: 0.1 to 1:50, and the reaction temperature and reaction time at that time are -20 to 50. C. and a range of 1 to 40 hours are preferred. In the composition of the present invention, the sulfur-containing compound used as the component (B) is usually solid at room temperature. Therefore, it is preferable to dissolve one of these compounds in a combination of generally used organic catalysts, or to mix them in the cationically polymerizable compound as the component (A). The organic solvent used at this time is not particularly limited as long as it can dissolve the sulfur-containing compound in an arbitrary ratio. Examples of such a solvent include methylene chloride, chloroform, acetonitrile, dimethyl sulfoxide, dimethylformamide, carbon tetrachloride, methanol, ethanol,
Preferable examples include alcohol solvents such as isopropanol. Further, as a solvent for dissolving the sulfur-containing compound, a monoglycidyl ether of an aliphatic higher alcohol, a phenol, cresol or a monoglycidyl ether of a polyether alcohol obtained by adding an alkylene oxide thereof, further, tri A compound having a functional group such as a polyfunctional vinyl ether group such as ethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, diglycidyl ether or diglycidyl ester or a polyfunctional epoxy group is used as a reaction diluent, and the cation of the component (A) is used. It is also possible to add it to the polymerizable compound alone or in combination with the above-mentioned general-purpose organic solvent.

In the polymerizable composition of the present invention, it is possible to add the above-mentioned solvent for dilution and a non-reactive resin or prepolymer for modification within a range not impairing the cationic polymerization. is there. It is also possible to use an organic carboxylic acid or an acid anhydride for the purpose of improving the electrical properties, or to mix a polyol for the purpose of imparting rubber elasticity. In the cationically polymerizable composition of the present invention, when it is polymerized or cured by irradiation with energy rays and / or heating, (B) is added to 100 parts by weight of the cationically polymerizable compound as the component (A).
The sulfur-containing compound as a component is blended in a proportion of 0.001 to 50 parts by weight, preferably 0.01 to 10 parts by weight. The optimum blending amount of the component (B) is the cationic polymerization property of the component (A). It is appropriately selected depending on the properties of the compound (for example, epoxy equivalent), the amount of energy ray irradiation, the desired curing time, the curing temperature, the humidity and the like. The energy ray is not particularly limited as long as it has an energy that induces the decomposition of the sulfur-containing compound as the component (B), and, for example, high energy
150nm ~ obtained from low water pressure mercury lamp, xenon lamp, metal halide lamp, germicidal lamp, laser light, etc.
Electromagnetic energy beam or electron beam having a wavelength of 900 nm,
High-energy rays such as X-ray radiation are preferably used.

The exposure time to the energy rays depends on the intensity of the energy rays, but is usually selected in the range of 0.5 seconds to 10 minutes. For relatively thick coated objects,
It is possible to spend more time than that. Further, in order to accelerate the cationic polymerization reaction, it is possible to use heating in combination, and the heating temperature at that time is preferably in the range of 0 to 150 ° C. When the polymerizable composition of the present invention is polymerized or cured by heating, the curing temperature and time are preferably 0 to 200 ° C. and 10 seconds to 1 hour. Further, for the purpose of enhancing the thermal activity of the sulfur-containing compound or for shortening the curing time,
As the third component, thiophenols such as thiophenol and pentachlorothiophenol and their derivatives, weakly basic nucleophiles such as thiosalicylic acid, and organometallic compounds such as Cu, Co and Sn can be used as curing accelerators. In that case, it is preferable to add it in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the cationically polymerizable compound. The polymerizable composition of the present invention is usually in a liquid state, but it is an inert pigment, a dye, a filler, an antistatic agent, a flame retardant, an antigelling agent, a flow control agent, a surfactant depending on the use. It is also possible to mix and use an adhesion improver, a processing aid, a viscosity modifier, a sensitizer, an accelerator, an ultraviolet absorber, a surface modifier and the like.

[0016]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Production Example 1 Production of N-tosylmethylphenylsulfilimine 1.24 g (10 mmol) of thioanisole was dissolved in a mixed solution of 500 ml of methanol and 100 ml of 0.5N sulfuric acid aqueous solution, and methanol 100 was added.
A solution prepared by dissolving 2.50 g (11 mmol) of chloramine T in milliliter was added, and after reacting at room temperature for 0.5 hour, it was poured into 3 liter of dilute aqueous sodium hydroxide solution. Then, the reaction mixture was extracted twice with 300 ml of chloroform, washed with water, dried and evaporated to remove the solvent, and recrystallized from an acetone-hexane mixed solvent to give N-having the following structure in a yield of 50%. 1.46 g of tosylmethylphenylsulfilimine were obtained.

[0017]

[Chemical 6]

Production Example 2 Production of Np-tolyl-methylsulfonimide morpholide 1.69 g of Np-tolyl-methylsulfinamide
(10 mmol) was dissolved in 85 ml of carbon tetrachloride, cooled to 0 to 5 ° C., 1.8 g (10 mmol) of N-bromosuccinimide was added thereto, and the mixture was stirred at 0 ° C. for 30 minutes.
Stir for minutes. Further, 2.4 g (14 mmol) of morpholine was added, and the mixture was stirred at 0 ° C. for 3 hours and then at room temperature for 6 hours. The reaction mixture was washed with water, dried over magnesium sulfate, and then purified by column chromatography using 30 wt% ether-hexane as a developing solvent to give N having the following structure in a yield of 74%. -P-Tolyl-methylsulfonimide morpholide 2.
12 g was obtained.

[0019]

[Chemical 7]

The following Production Example 3 was carried out according to the method of Production Example 2.
The compounds shown in ~ 7 were prepared. Production Example 3 N-p-tolyl-3-chloropropylsulfonimide morpholide

[0021]

[Chemical 8]

Production Example 4 Np-tolyl-cyclohexylsulfonimide morpholide

[0023]

[Chemical 9]

Production Example 5 Np-tolyl-p-chlorophenylcyclopropylsulfonimide morpholide

[0025]

[Chemical 10]

Production Example 6 Np-bromophenyl-methylsulfonimide morpholide

[0027]

[Chemical 11]

Production Example 7 N-methylsulfonimide dimorpholide

[0029]

[Chemical 12]

Production Example 8 Production of Vinyl Ether Group-Containing Acrylic Resin 5000 equipped with stirrer, reflux tube, thermometer, nitrogen inlet
In a milliliter 4-necked flask, 1357 g of xylene was charged, the temperature was raised to 80 ° C., and methyl methacrylate 1 was added thereto.
115 g of azobisisobutyronitrile was dissolved in a mixture of 712 g and 682 g of butyl acrylate, and the mixture was added dropwise. After dropping, aging was continued for 4 hours to obtain a methyl methacrylate-butyl acrylate copolymer resin solution in a yield of 3870.
g (heating residue: 62 wt%). Then, 485 g of the obtained resin solution, 84 g of 4-hydroxybutyl vinyl ether, and 6.9 g of a 28 wt% methanol solution of sodium methylate were charged and reacted at 150 ° C. for 14 hours. After completion of the reaction, 15.0 g of Kyoward 700SN (manufactured by Kyowa Chemical Co., Ltd.) was added and reacted at 90 ° C. for 1 hour. Was removed a dispersion by a reaction after filtration, vinyl oxy butyl group _{[CH 2 = CHO (CH 2} ) 4 -] yield as the resin is a resin solution introduced in the ester group copolymer in 820 g (heating Residue: 35 wt%). In addition,
^When the introduction rate of vinyloxybutyl groups (introduction rate to the monomer in the resin) was determined by ¹ H-NMR, it was
It was mol%.

Example 1 0.1 g of the sulfilimine obtained in Production Example 1 was dissolved in 5 g of methylene chloride, and then 29 g of the vinyl ether group-containing acrylic resin solution obtained in Production Example 8 was added to the solution, and the vinyl ether group-containing resin solution was added. Was prepared. Apply this preparation on a tin plate by air spray coating (film thickness 35μ
m), and a 500 watt ultra-high pressure mercury lamp [USHIO INC.
USH-500D: Irradiation distance 400 mm] was irradiated for 45 seconds at room temperature to form a cured film. Table 1 shows the results of performing xylene rubbing on the obtained cured film and the results of measuring the Knoop hardness. Example 2 In Example 1, the photocuring was performed according to Example 1 except that the sulfonimidamide obtained in Production Example 2 was used instead of the sulfilimine obtained in Production Example 1. The results are shown in Table 1.

Comparative Example 1 Photocuring was carried out in the same manner as in Example 1 except that sulfimimine was not used. The results are shown in Table 1. Comparative Example 2 In Example 1, instead of sulfilimine, triphenylsulfonium tetrafluoroborate (Ph ₃ S ⁺
BF ₄ ^-) except using, was photocured according to Example 1. The results are shown in Table 1.

Examples 3 to 7 Photocuring was carried out according to Example 1 except that the sulfur-containing compounds produced in Production Examples 3 to 7 were used. The results are shown in Table 1. Examples 8 to 14 In Example 1, instead of the vinyl ether group-containing acrylic resin solution, the epoxy resin “Epicoat 828” was used.
[Oilized Shell Epoxy Co., Ltd.] is used and Production Examples 1 to
Except that each of the sulfur-containing compounds obtained in 7 was used.
Photocuring was carried out according to Example 1. The results are shown in Table 1. Examples 15 and 16 In Examples 1 and 2, heat curing (1
The same procedure as in Example 1 was carried out except that the heating was carried out at 00 ° C for 15 minutes. The results are shown in Table 1.

[0034]

[Table 1]

Note 1) Xylene rubbing: Xylene was dipped in five flannel cloths, fixed with a middle finger, and reciprocated over the coating film 20 times. Then, the state of the coating film was observed. ○: unchanged, △: partial damage,
X: Partially dissolved 2) Knoop hardness: Measured at 20 ° C. with an M-type micro hardness meter manufactured by Shimadzu Corporation. The larger the value, the harder it is. As shown in Table 1, it is apparent that the sulfur-containing compound used in the cationically polymerizable curable composition of the present invention has significantly higher cationic polymerization performance than conventionally known initiators and is highly practical. .

[0036]

INDUSTRIAL APPLICABILITY The polymerizable composition of the present invention is novel, does not generate bubbles even when the coating film is cured by the irradiation of energy rays, and has extremely high curing performance by the irradiation of energy rays. Thus, a thick coating film can be produced. Further, even by heating, a good cured coating film can be produced without requiring high temperature and long time curing conditions. The polymerizable composition of the present invention can be applied to materials for metals, rubbers, plastics, papers, ceramics, woods, and molded parts, and as a specific application, a durable paint for the purpose of aesthetics or protection is prepared. It has particular application to coating compositions for Further, the polymerizable composition of the present invention is excellent in adhesion, chemical resistance, abrasion resistance, insulation, etc., and therefore, ink, adhesive, photoresist,
It can be used in laminates, implant compounds, insulating paints and other applications.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08G 65/04 NQE 9167-4J C09D 5/00 PNV 6904-4J 163/00 PKB 8830-4J

Claims (1)

[Claims] 1. A cationically polymerizable compound (A), and (B)
General formula: (R ¹ , R ² and R ³ in the formula each have 1 to 30 carbon atoms.
Alkyl group, halogenated alkyl group, aryl group, halogenated aryl group, arylsulfonyl group, aralkyl group, alkenyl group, cycloalkyl group, cycloalkylalkyl group, arylcycloalkyl group, alkylene group, arylene group, aralkylene group or An oxaalkylene group, which may be identical to each other,
May be different, X is an oxygen atom or a nitrogen atom, m,
A cationic polymerization curable composition comprising as an active ingredient a sulfur-containing compound represented by n and p each being 0 or 1.