JPS6121126A - Ultraviolet-curable resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having high heat-resistance, curable to the core with low energy irradiation, and suitable as a resin for forming a block, by adding specific amounts of a triaryl sulfonium salt and an organic silicon compound composed of an alkoxysilane to an epoxy resin. CONSTITUTION:The objective composition is produced by compounding (A) 100pts.(wt.) of an epoxy resin [preferably a bisphenol A epoxy resin or a mixture of a cycloaliphatic epoxy resin (e.g. the compound of formula I ), etc.] with (B) a cationic polymerization catalyst comprising a triarylsulfonium salt (e.g. the compound of formula II) and (C) 1.0-50pts., preferably 2.0-40pts. of an organic silicon compound consisting of an alkoxysilane [e.g. methyltriethoxysilane of formula CH3Si(OC2H5)3]. The amount of the component B is preferably 0.2- 1.0pt. per 100pts. of the sum of the components A and C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field to which the Invention Pertains] The present invention relates to an ultraviolet curable resin composition, and in particular, a resin composition that rapidly hardens in deep areas when irradiated with a small amount of ultraviolet energy and also has excellent heat resistance. relating to things.

[Prior art and its problems]

Cationic polymerizable photocurable resin compositions such as epoxy resin compositions are polymerized and cured by irradiation with light energy such as ultraviolet rays, and the polymerization process is simple. Application to block-shaped resins having the following properties is strongly desired.

As this type of resin composition, resin compositions prepared by adding and mixing a triarylsulfonium salt as a cationic polymerization catalyst to various epoxy resin compositions are conventionally known.

This composition easily polymerizes and cures to form a resin when irradiated with light energy such as ultraviolet rays, but in order to proceed with deep curing, high energy irradiation must be continued for a long time. It is unsuitable for forming.

Furthermore, this composition also has the disadvantage of low heat resistance ('rg value) after polymerization and curing.

[Purpose of the invention]

The object of the present invention is to rapidly cure deep parts of the body by irradiating a small amount of ultraviolet energy, and to exhibit a high Tg value.
The object of the present invention is to provide an ultraviolet curable resin composition particularly suitable for forming block-shaped resins.

[Key points of the invention]

In order to achieve the above-mentioned object, according to the present invention, an organosilicon compound consisting of an alkoxysilane is further added to an ultraviolet curable resin composition consisting of an epoxy resin and a triarylsulfonium salt as a cationic polymerization catalyst. It is characterized in that the amount of the organosilicon compound added is 1.0 to 50 parts by weight based on 100 parts by weight of the epoxy resin.

[Detailed description of the invention]

Examples of the epoxy resin used in the present invention include conventionally known aromatic epoxy resins, cycloaliphatic epoxy resins, aliphatic epoxy resins, and the like.

Here, particularly preferable aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or their alkylene oxide adducts, such as bisphenol A or its alkylene oxide adducts and epoxy resins. Examples include glycidyl ethers and epoxy novolac resins produced by reaction with chlorohydridine.Particularly preferable cycloaliphatic epoxy resins include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, cyclohexene, and cycloaliphatic epoxy resins. It is cyclohexene oxide or a cyclopentene oxide-containing compound obtained by epoxidizing a cyclopentene ring-containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid. Typical examples of polyglycidyl ethers include glycidyl ethers produced by reacting hydrogenated bisphenol At& with its alkylene oxide adduct and evichlorohydrin. Typical examples of cyclohexene oxide or cyclopentene oxide-containing compounds include the following: Particularly preferable aliphatic epoxy resins include aliphatic polyhydric alcohols or polyglycidyl ethers of alkyl oxide adducts thereof; representative examples thereof include 1,4-butane, Diglycidyl ether of diol, diglycidyl ether of 1,6-hexanediol,
One or more aliphatic polyhydric alcohols such as triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, and glycerin. Examples include polyglycidyl ethers of polyether polyols obtained by adding alkylene oxides (ethylene oxide, propylene oxide). 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.

As the epoxy resin used in the present invention, these aromatic epoxy resins, R-shaped aliphatic epoxy resins, or aliphatic epoxy resins can be used alone, but they may be appropriately blended depending on the desired performance. desirable.

The triarylsulfonium salt as a cationic polymerization catalyst used in the present invention can decompose under ultraviolet irradiation to cause polymerization or crosslinking of the epoxy resin, and is used as a 50X solution of structural carbonate.

Furthermore, the organosilicon compound according to the present invention is an alkoxysilane, and specific examples include the following compounds.

Methyltriethoxysilane CHm Si (Q
Cs Ha )s Methyltrimethoxysilane CH
a Si (0CHI)s Propyltriethoxysilane Cs Ht Si (OCa Hs)s Butyltrimethoxysilane Ca Ha 8i (
0CHr)sr-rioopropyltrimethoxysilane CtCsHa8i (OCHi)sPhenyltrimethoxysilane Cs Hs Si (OCL)sDimethoxydiphenylsilane (CmFb)+8i
(OCH+)1diethoxydimethylsilane (
CHr )m S i (OC+ Hs )t Ethoxytrimethylsilane (CHs )s 8 i Q
Cs Hs polymethylphenylsilsesquioxane or polytylsilsesquioxane Of course, these may be used alone or in combination. In the present invention, the amount of the organosilicon compound added is equal to the epoxy The amount is 1.0 to 50 parts by weight, preferably 2.0 to 40 parts by weight, based on 100 parts by weight of the resin, and the effects of the present invention cannot be achieved outside this range. Furthermore, the amount of triarylsulfonium salt used as a cationic polymerization catalyst is an excess amount necessary to exhibit the catalytic effect.
Specifically, it is preferably 0.05 to 20 parts by weight, particularly 0.2 to 1.0 parts by weight, per 100 parts by weight of the composition comprising the epoxy resin and organosilicon compound.

The composition of the present invention prepared as described above can be used with weak ultraviolet energy such as sunlight (average ultraviolet intensity 0.3 to 2.0 m
W/ca) Deep curing progresses rapidly by irradiation, and the resulting resin has a high Tg value and excellent heat resistance.

Hereinafter, the present invention will be explained in more detail using Examples.

Example 1 Epicoat 828 (Shell Chemical ■, bisphenol A type epoxy resin)
...60 parts by weight Bakelite EIIJ, -4206 (union carbide, cycloaliphatic epoxy resin)
...To 100 parts by weight of an epoxy resin consisting of 40 parts by weight, predetermined amounts of various organosilicon compounds shown in Table 1 were added and mixed, and to each of these mixtures, UVE-1014 was added as a cationic polymerization catalyst. (manufactured by G-E. 50% propylene carbonate solution of triarylsulfonium salt) at 0.
4 parts by weight were added and mixed to prepare 123,000 samples y, lf, i, and p.

Table 1 A deep hardening test was conducted for each of the aforementioned samples 1.2.3.4. The test was conducted using the testing apparatus shown in Fig. 1. In Fig. 1, ■ indicates an inner diameter of 1011x.

An opaque polytetrafluoroethylene (PTFE) sleeve with a length of 40 W and a wall thickness of 2 mm is used, 2 is double-sided tape, and 3 is a stand.0 First, each sample was injected into sleeve 1, This was subjected to UV irradiation using a 4KW high-pressure water lamp (Cure Dride HMW-244.5), and the irradiation conditions were as follows.

UV irradiation conditions: Irradiation distance 15cm Irradiation time 10 seconds Irradiation intensity 200mW/lri Irradiation intensity is ■ Newly manufactured by Oak, UV illuminance meter UV-30
3 was used.

After UV irradiation, the sleeve 1 was left in a room for 5 minutes, and then the sleeve 1 was peeled off from the double-sided tape 2 and the cured state of the bottom portion was observed. The results are shown in Table 1. In Table 1, ◯ indicates cured, and X indicates uncured. This result shows that the addition of the organosilicon compound improved deep curing properties.

Example 2 Epicoat 828 (Shell Chemical ■, bisphenol A type epoxy resin)
...60 parts by weight Bakelite ERL-4206 (union carbide, cycloaliphatic epoxy resin)
・・・・・・・・・Methyltriethoxysilane (MTES,
Shin-Etsu Chemical Co., Ltd.) in 6 amounts shown in Table 2(a), and γ-chloropropyltrimethoxysilane (CPTMS).

6 amounts of Shin-Etsu Chemical Co., Ltd.) shown in Table 2(b) and 6 amounts of polyphenylsilsesquioxane (QR, -950, Owens-Illinois Co., Ltd.) shown in Table 3(C) were added. UVE-1014 (manufactured by G, E, Inc., propylene carbonate 50X solution of triarylsulfonium salt) was added as a cationic polymerization catalyst to 100 parts by weight of each composition consisting of an epoxy resin and an organosilicon compound.
0.4 parts by weight of was added.

Table 2 (a) Table 2 (b) Table 2 (c) *) Measurement was not possible because the compatibility limit was exceeded. Each sample in Table 2 (a), (bl, and (C)) sample&
5 to 23), the deep hardening speed was measured. This measurement was performed using the measuring device shown in Figure 2, and the time required to reach the maximum temperature (minutes)
This was carried out by measuring the maximum temperature reached (6).

That is, each sample was injected into sleeve 1, and 100W
High-pressure mercury lamp (Newly manufactured by Oak (OHD-110M))
This was done by irradiating ultraviolet rays from a distance of 16z above using a thermocouple and recording the temperature rise curve from thermocouple 4. The results are shown in Table 2. be. The recorder used was 5R-83126 manufactured by Kokotsu Seisakusho, and the chart speed was 300 bags/hour.

In the above experiment, the time to reach the maximum temperature is the deep hardening rate of each sample, and from the experimental results, the time to reach the maximum temperature is J5 when the amount of the organosilicon compound added is 1.0 to 50 parts by weight.
From this, it can be seen that the deep curing speed is fast within the range of the addition amount of the organosilicon compound.

Example 3 In this example, the Tg value was measured.
...60 parts by weight Bakelite ERL-4206 (union carbide, cycloaliphatic epoxy resin)
......100 parts by weight of an epoxy resin consisting of 40 parts by weight was prepared.

OBTMS using the following as organosilicon compounds
(Butyltrimethoxysilane, Shin-Etsu Chemical ■)C
PTMS (3-chloropropyltrimethoxysilane, 〃) DMDPhS (dimethoxydiphenylsilane, 〃
) DEI) IVIS (Ethoxydimethylsilane,
) GR, 950 (polyphenylsilsesquioxane.

(Owens-Illinois, Inc.) The various organosilicon compounds described above were added in the respective amounts shown in Table 3 to the parts by weight of the epoxy resin, and further,
As a cationic polymerization catalyst, 0.4 parts by weight of UVE-1014 (propylene carbonate 50X solution of triarylsulfonium salt manufactured by G.E. Co., Ltd.) was added to the composition of the epoxy resin and organosilicon compound.

Table 3 Measurements were performed according to Figure 3. That is, Fig. 3(a)
, sleeve 1 (inner diameter 5111. length 20 wm
.

Each sample was injected into a 4KW high-pressure mercury lamp (Newly manufactured by Oak Manufacturing Co., Ltd., CureDride HMW-2).
Ultraviolet rays were irradiated for 10 seconds from a distance of 15 m using 44.5). The UV intensity is 200 mW/cni.

In FIG. 3, 2 is double-sided tape and 3 is a stand.

Next, when the sample in the sleeve 1 is completely cured or gelled, the sleeve 1 is removed from the double-sided tape 2 as shown in FIG. When the river sand was irradiated with ultraviolet rays, the scattered ultraviolet rays hit the sample and the sample was completely cured. Next, as shown in FIG. 3(C), the cured sample 5 was taken out from the sleeve 1, and the taken out sample 5 was irradiated with ultraviolet rays for 10 seconds from a distance of 15 m using the high-pressure mercury lamp, and was heated to a temperature of 25°C. After curing for 24 hours, the Tg value was measured. Tg value is manufactured by Shinku Riko ■ I) L-
1500°TA, -1500°C heating rate
/min, and the results are shown in Table 3.

From Table 3, samples of the present invention containing organosilicon compounds (trial *
It can be seen that samples No. 4 No. 25 to 29) have a higher Tg value than sample Nα24 which does not contain this sample, and are excellent in heat resistance.

Example 4 In this example, the curing status of the resin composition of the present invention by weak ultraviolet light (sunlight) was investigated.
...60 parts by weight Bakelite EELL-4206 (union carbide, cycloaliphatic epoxy resin)
......For 100 parts by weight of an epoxy resin consisting of 40 heavy lid parts, as an organosilicon compound, CPTMS (3-chloropropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) DMDPhS (dimethoxydiphenylsilane, Shin-Etsu Chemical Co., Ltd.) Chemical industry■) are shown in Table 4.6
Further, to 100 parts by weight of the composition consisting of these epoxy resins and organosilicon compounds, UVE-1014 (propylene carbonate 50X of triarylsulfonium salt manufactured by G and J Co., Ltd. solution) was added in an amount of 0.4 parts by weight.

Table 4 For each of these samples 30 to 32, the maximum temperature reaching time (minutes) was measured under the irradiation conditions shown in Table 5, and the deep hardening properties were evaluated. The experiment was conducted using the apparatus shown in FIG. Fourth
In the figure, la is a translucent cap made of polyethylene with a diameter of 30 xi and a depth of 10 mm, 2 is double-sided tape, 3 is a stand, and 4 is a thermocouple. First, each sample was injected into the cap 1a. This was left under sunlight, the temperature rise curve from the thermocouple 4 was recorded, and the time (minutes) to reach the maximum temperature was read. The results are shown in Table 5. The recorder and chart speed were the same as in Experiment 2. The illumination meter used was UV-303 manufactured by Oak Seisakusho.

Table 5 From Table 5, it can be seen that even with weak ultraviolet irradiation such as sunlight, the deep hardening rate is fast, and the rate of deep hardening is up to about three times higher in the sample containing an organosilicon compound than in the sample without it. It was found that a fast curing rate was obtained.

〔Effect of the invention〕

As mentioned above, since the photocurable resin composition according to the present invention has a predetermined amount of an organosilicon compound consisting of alkoxysilane added to the conventional component system of epoxy resin and catalyst,
With a small amount of light energy irradiation, deep hardening progresses quickly, the Tg value improves, and the composition has excellent heat resistance.It is an extremely useful composition in practical use, and is useful for household picture plates, stained glass, etc.
Can be widely used as a material for plaster bandages (glass fiber prepreg), light-emitting diodes for human resources, automobile body putty, resin mortar, etc.

[Brief explanation of drawings]

FIG. 1 shows an apparatus for measuring the deep hardening state of a composition;
Figure 2 shows an apparatus for measuring the deep hardening rate of a composition;
FIGS. 3(a), (b), and (c) are drawings showing the sample preparation process for measuring the Tg value, and FIG. 4 is an apparatus for measuring the state of deep hardening due to sunlight. 1... Sleeve, 2... Double-sided tape, 3... Stand,
4... Thermocouple, 5... Hardened sample, la... Cap Patent applicant Three Bond Co., Ltd. C) To the blind suicide meter

Claims (1)

[Claims] It is characterized in that an organosilicon compound consisting of an alkoxysilane is further added to an ultraviolet curable resin composition consisting of an epoxy resin and a triarylsulfonium salt as a cationic polymerization catalyst, and the amount of the organosilicon compound added is determined by An ultraviolet curable resin composition in an amount of 1.0 to 50 parts by weight based on 100 parts by weight of the resin.