JPS6198740A - Method of curing treatment of ultraviolet-curing type resin composition - Google Patents

Abstract

PURPOSE:To cure an article with a complicated shape or a hidden part easily without requiring irradiation after casting or coating, by irradiating a composition with ultraviolet light energy uniformly before casting or coating process so that a polymerization reaction is previously started. CONSTITUTION:In polymerizing and curing an ultraviolet-curing type resin composition with ultraviolet energy, the composition is uniformly irradiated with the ultraviolet light energy and a polymerization reaction is previously started at a stage before casting or coating process for applying it to a desired use of the composition is carried out. A mixture of an epoxy resin and a cationic polymerization catalyst is used as the composition.

Description

[Detailed description of the invention] [5.・, 4 Technical Fields] The present invention relates to a method for curing compositions of epoxy resin and cationic resins (ultraviolet ray curing L1v1 consisting of silicone media), and in particular, the method of curing compositions. The present invention relates to a method for curing an ultraviolet curable resin composition, which can omit a curing step by irradiating ultraviolet energy after the step.

[Prior art and its problems]

Cationic polymerization type photocurable resin compositions such as epoxy resin compositions are polymerized and cured after irradiation with source energy such as ultraviolet rays, so they are processed into the desired shape by pressing or applied to the desired construction site by coating. Then, it is irradiated with ultraviolet energy and subjected to a curing treatment, and is widely used in various applications such as molded products, coatings, and adhesive sealants.

Conventionally, when curing the composition of this building, for example, when manufacturing a molded article, the composition is pressed into a mold and processed into the desired shape, and then irradiated with ultraviolet energy. In addition, when applying the coating, the composition is applied to the desired 9 masonry parts using a coating machine, and then the coating is cured by irradiating ultraviolet energy, and further adhesion is achieved. When obtaining a sealant, the composition is discharged from the discharge port of the soybean to the desired construction site (disintegrability-).
This overlay was then cured by irradiating it with ultraviolet rays, as described above.

However, in all of the above-mentioned curing methods, the composition is irradiated with ultraviolet energy after being pressed into the desired shape or after being applied to the desired construction site, so it is difficult to make the cast product have a complicated shape. If there are areas that cannot be irradiated with ultraviolet energy, the composition in those areas will not be cured;
Furthermore, if the application location is a hidden location that cannot be irradiated with ultraviolet energy, the composition at that location will not be cured, and therefore, the above-mentioned curing method cannot be applied in any of these cases. Ta.

[Purpose of the invention]

The purpose of the present invention is to cure and last a long time without performing curing treatment by irradiating ultraviolet energy after casting or coating, so that even cast products with rigid shapes that cannot be irradiated with ultraviolet energy can Alternatively, the present invention provides a method for curing a 1q fat composition that is cured by ultraviolet light by improving the drawbacks of the above-mentioned known techniques, in which the coating film is easily cured even in a hidden place where it cannot be irradiated with ultraviolet energy. It's about doing.

[Key points of the invention]

In order to achieve the above-mentioned object, according to the present invention, an ultraviolet curable resin composition is polymerized and cured by irradiation with ultraviolet energy, and then the composition is cast or molded to apply it to a desired use. It is characterized in that the composition is uniformly irradiated with ultraviolet energy at a stage prior to the coating process to induce a polymerization reaction in advance.

[Embodiments of the invention]

The present invention will be explained below with reference to FIG. FIG. 1 is a block diagram of an apparatus for carrying out the method of the present invention. Ol is a quartz tube or glass tube loaded with ultraviolet curable resin composition A, and has a discharge port 2 at the tip. The part on the way to the tube is a thin tube Ia, and the composition A is irradiated with ultraviolet energy here as described later. At the time of irradiation, it is preferable that the quartz tube or the glass tube be a thin tube 1a because the composition A can be more easily irradiated with ultraviolet energy throughout the tube. Further, an ultraviolet lamp 3 is arranged on one side of the thin tube 1a, and an aluminum reflector 4 is arranged so as to surround this ultraviolet lamp 3. An aluminum reflector plate 5 is also disposed on the side of t[fK facing the ultraviolet lamp 3, and the bottom of the groove is grooved so that the ultraviolet energy from the ultraviolet lamp 3 is efficiently irradiated to the thin tube 1a.

When the resin composition A is passed through the quartz tube or the glass tube 1 using the above-mentioned apparatus, the composition A is passed through the quartz tube or the glass tube 1. Before it is shaped into the desired shape or applied to the desired armholes, it is uniformly and easily irradiated with ultraviolet energy to induce a polymerization reaction. When it is discharged from the discharge port 2, it is still in a liquid state, and is then cast into a desired shape or applied to a desired construction site, and then cured by propagation polymerization without irradiation with ultraviolet energy.

As mentioned above, the present invention does not require polymerization curing treatment by pressing or irradiation with ultraviolet energy after application, unlike conventional methods, and therefore can be used to wax cast products with complex shapes that cannot be irradiated with ultraviolet energy. It also cures easily in hidden areas where it cannot be exposed to ultraviolet energy.

The resin used in the present invention is an epoxy resin.

Examples of this include conventionally known aromatic epoxy resin, cycloaliphatic epoxy resin, and aliphatic epoxy resin.

Here, particularly preferable aromatic epoxy resins are polyglycidyl ethers of polybenzene phenols having at least one aromatic nucleus or their alkylene oxide adducts, such as bisphenol, bisphenols, or their alkylene oxide adducts. Examples include glyc/zyl ether and epoxy novolak resin produced by the reaction of Ebichlorohydrizine and Ebichlorohydrizine. Particularly preferred as the cycloaliphatic epoxy resin are cyclohexene oxide or cyclopentene oxide-containing compounds obtained by epoxidizing poly-11IIi alcohols having at least one alicyclic ring with a polyglycidyl oxidizing agent. A typical example of polyglycidyl ether is glycidyl x-f, which is produced by reacting hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin. Further, typical examples of cyclohexene oxide or cyclopentene oxide-containing compounds include those represented by the following formula: 〇〇oQ-C-〇-CH''Q.

Furthermore, particularly preferred aliphatic epoxy resins are j
There are polyglycidyl ethers of aliphatic polyalcohols or their alkylene oxide adducts, representative of which are B.
IJ includes diglycidyl ether of 1,4-butanediol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triclycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to polypropylene glycol nocyclidyl ether, ethylene glycol, and propylene glycol aliphatic polyhydric alcohols are mentioned. It will be done. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these can also be blended as diluents.

The epoxy resin used in the present invention may be any of these aromatic epoxy resins, cycloaliphatic epoxy resins, or aliphatic epoxy resins. This is desirable.

The cationic polymerization catalyst used in the present invention is a group of double salts, which are onium salts that release a Lewis acid capable of initiating polymerization upon irradiation or reaction. Such compounds basically have the general formula [81'al(,"bR3,)(+',
4Z]”[to・IXn+ml (In the formula, the cation is onium, 89, Z is N3N, S, 8c, 'f'c
, P, As, Sb, Mountain, Q, /% CI Gen(
For example, I, Br, CL) and I(,',
It2.11,3. It,' are organic groups which may be the same or different. a, b, and cd are each integers of 0 to 3, and are equal to the valence of a-)b-1-c-1-dFiz. M is gold M or a metalloid (+nctalloid), which is the central atom of the halide complex, and IJ, P,
As, Sb, Fe, Sn, Mountain, At, Ca, In, T
i, Zn.

These include So, V, Cr, Nin, Co, etc. X is /S halogen, m is the net charge of the . . . halogen complex ion, and n is the number of halogen atoms in the halide complex ion. ].

Specifically, triarylsulfonium salts or diaryliodonium salts are often used as cationic polymerization catalysts. These are compounds that can decompose under ultraviolet light and cause polymerization or crosslinking of epoxy resins, and the former are compounds with the general formula,
are Sb, P, As.

etc., X is a halogen element, and is an integer that can vary depending on nt'iM; for example, when M is sb and X is F, n is 6.

Further, the latter is a compound having the general formula, and %MI XI fl is the same as the former.

These catalysts are typically propylene carbonate 5ON
Used as a solution.

Example 1 The following formulation was prepared as an ultraviolet curable epoxy resin composition.

Formulation 1 *1 Epicoat 828 100 (parts by weight) *3 UVF2-1014 9. l
(n) Formulation 2 *1 Epicote 828 100 (
Parts by weight) *2KIIN1202.
4 (“ )*3UVE-10140,1(// )
*1) Bisphenol A type epoxy resin (Shell Chemical Co., Ltd. "lJ") *2) Diphenyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) *3) 1ffl of triallylsulfonium mound 50% propylene carbonate solution (manufactured by GE)
The above formulations 1 and 2 were added to the quartz tube 1 (thin 'f') shown in Figure 1, respectively.
R1a (0 diameter 11%, quartz/U wall thickness 0.3 mm
) and let it pass through, turning purple at the thin tube 1a.
The ultraviolet energy from Lamp 3 (newly manufactured by Oak), Nday 11300 type Q lamp with an output of 300 W (used for 1 year) is approximately IQ m W/c, with an energy amount of 1.
After irradiation for 0 seconds, it was discharged from the discharge port 2 into a polyethylene container of 20φ x 10cm, and left in a dark place with regular crystals.
The curing conditions were regulated and the results shown in Table 1-1 were obtained.

In addition, the amount of energy is ■ Newly manufactured by Oak, UV illuminance meter M-01. I kept it with a UV-25 sensor.

The amount of energy for Jin was determined by adjusting the discharge speed.

Table 1 *4) Time required for the resin to become a gel state after casting 〇 *5) Time required for the tack to disappear in Table 10I of the cast resin.

*6) Measured after standing for 24 hours (Shore D scale).

For comparison, the hardness of the compound after 3 hours was measured by irradiating it at the same energy gate for 0 seconds to completely cure it, and the results were &1-74, Na2 77. Therefore, the resin discharged by the above method is considered to be completely cured after the cooling time.

Practical Example 2 A practical experiment was conducted in the same manner as Practical Example 1, except that the discharge rate was adjusted to 2+3 so that the irradiation was performed for 15 seconds, and results of - to -2 were obtained.

Table 2 In this case, the open time after discharging was shorter, but there was almost no difference in the final flight K compared to the case of the implementation row I.
Cure was complete.

Example 3 Blend 2 of Example 1 was cast into a mold that had been subjected to mold release treatment in the same manner as in Example 1.

After a few minutes, the mold was removed and the cured product was released.

As a comparative example, the same formulation was injected into a mold according to the conventional curing method. : The mold was irradiated with ultraviolet rays of the same intensity for 5 minutes, and after 30 minutes, the mold was removed and the cured product was observed.

1) In the case of the former example, a cured product with a perfect shape according to the mold was obtained, but in the case of the latter comparative example, only the part exposed to ultraviolet rays was cured, resulting in a shadow. Example 4 The following formulation was prepared as an ultraviolet curable epoxy resin composition.

Ca=200 20 parts by weight Epicor'Nf'815 80 trThe above formulation was irradiated with ultraviolet energy in the same manner as in Example 1, and then discharged onto a test piece of iron and lauan material and superimposed.
The samples were allowed to stand for the respective times indicated in 3. Thereafter, a tensile shear test was conducted on each sample, and the results are shown in Table 3.

Table-3 Iron test, test piece: 8PCC-D (dull) 100X 25
X 1.6++++nJ IS--6850 Tensile speed: 1O Kolawan material sample: LOOX25 [Effects of the Invention] As described above, according to the hardening treatment method of the present invention,
The composition is exposed to ultraviolet i1 prior to the casting or coating process.
By irradiating m energy evenly, and by irradiating ultraviolet energy after casting or coating as in the past.
1 (75-etc. which omitted the curing process), even if the cast product has a complex shape that cannot be irradiated with ultraviolet scarlet energy, or if it is in a hidden place where it cannot be irradiated with ultraviolet energy. Even paint films can be easily cured.

[Brief explanation of drawings]

Fig. 1 shows a concrete groove bottom diagram of an apparatus for carrying out the method of the present invention.
...ultraviolet lamp, 4,5...anti((1saka, l
a... Thin tube, A... Resin composition patent applicant iJ-ThreeBond Co., Ltd. (II
The book is next ρ, 15 ri Otsu, and 2 corrections. 1985 9 J] Noah 1J 1'r, i' + Office Commissioner Uga Michibe Tonari, Incident Indication 1985 Patent Application No. 218577 2, Name of the invention Curing treatment of ultraviolet A'jli curable resin composition BuJ method 3.
1. Make a correction - 6. Relationship to the case Patent applicant Three Bon Co., Ltd., 1456 Hazama-cho, Hachioji-shi, Tokyo [4. Agent 5. TL of amendment order (=1 voluntarily. 6. Number of inventions increased by amendment) None. 7. Subject of amendment: “Detailed description of the invention”
41'A. (5) 1st: I Near 1'S! li+ ' *, 'l)
I", I 11', Ru: 1 ---- (1) Page 2, lines 11 to 12, ``Adhesive glue, etc.'' is corrected to ``Adhesive, sole agent, etc. J.'' (2) Page 12, line 2, chemical formula 2 (3) Page 12, line 8, chemical formula 2 (4) Page 12, lines 4 to 5 from the bottom ``These catalysts usually contain 50% of propylene carbon. ：Used as content, a.'' is deleted. Ram 1,41]*3]
"Salt," he corrected. (()) Page 13, line 18 “40 m w /
r: A 4 rl'J<. Correct it as m W, -' cd J. (7) 1st page 1'+9ii rNo 1-74, +2-771 to '1 r! 1 and 11 are 74, No, 2 or 77.”
and 1;1 positive Jru. (8) Correct "1rf!Iy" in No. C1-Table-2 to 1 hardness i4.5 hardness 1. (9) Line 16 of the same page [Example I... Type 11-F type was used. 1 using formulation No. 2 of Example 1.
Embodiment 1 BOLIE-SH・) Container release type (,',11
Same as Example 1, except that () was added to () in (10) Page 16 8-9 (1 (-The mixture was adjusted.J was corrected to [The mixture was adjusted to: Ii, I and examined whether it has an iT effect as an adhesive.'' (11) Same page. Correct rcR-200J in the 1st O line to rlH R-200CJ. (12) Correct the 11th line of the same page “Epicor 1 #8151 [
*8) Epinyl -L #8151 and: il'
+1. , i-ru. (13) Add ``three pieces of each'' between ``after irradiation'' and [iron and ko'' in +3f'i of the same page. (14) Add the following to the bottom line of the same page. "*7) Ultraviolet curing type epochino resin compound (Asahi Denka Kogyo Co., Ltd. +! Ri*8) Bisphenol A type epochino resin (manufactured by Neru Kagaku Co., Ltd.) 1 (15) Page 17, Table 3 ■ "Measured values" Correct it to "tensile shear strength". ■Correct rn=IJ as "test piece IJ." Correct rn=2J as "test piece 2." Correct rn=34 to "test piece 3". (16) Under Table 3 on page 17 "Iron test piece: 5PCC-D (dull) 100X25X1.6 m JIS-6850 Tensile speed: 10mm Lauan material test piece: 100 x 25 x 3 ss J" : 5PC according to JIS G3141
C-D (Dull) Large scale 1oOx25x1.6 n Lauan material test piece: Size 100x25x 3 +nJ
Tensile speed according to IS-K-6850: Corrected to 10 dragons/m1nJ. (17) 6th line from the bottom of the same page: “From the results of Table 3...
... I know it will harden. ” is corrected as follows. "It can be seen that the composition treated according to the present invention cures even when interposed between opaque materials, and is extremely effective as an adhesive.J

Claims (2)

[Claims] (1) When polymerizing and curing an ultraviolet curable resin composition by irradiation with ultraviolet energy, the ultraviolet rays are applied to the composition at a stage prior to the casting or coating process for applying the composition to the desired use. 1. A method for curing an ultraviolet curable resin composition, which comprises irradiating the composition uniformly with UV rays to induce a polymerization reaction in advance. (2) The treatment method according to claim 1, wherein the ultraviolet curable resin composition is a mixture of an epoxy resin and a cationic polymerization catalyst.