JPS62207309A - Photocurable composition - Google Patents

Abstract

PURPOSE:To form a photocurable composition which can be stored for a long time, by an addition reaction of an epoxy resin with a phenyl acrylate and/or a phenyl methacrylate. CONSTITUTION:This photocurable composition is one having, as an effective component, an acryloyl and/or methacryloyl group-containing compound having ether groups as side chains, which is obtained by an addition reaction of a compound (a) of formula I (wherein R1 is H or methyl, Y is oxygen or sulfur, Z is a group selected form among groups of formula II, X is H, alkyl, a halogen, nitro or methoxy and n is an integer of 1-5) with an epoxy resin (b) and represented by formula III (wherein R1, Y1 and Z are the same as defined above and R2 is an epoxy residue). This photocurable composition can be cured by irradiation with light in the region of form visible light to ultraviolet rays after it is applied to a substrate or cast.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photocurable composition that is cured by light irradiation.

[Prior art] Japanese Patent Publication No. 44-31472, Japanese Patent Publication No. 45-4089
As described in Japanese Patent Publication No. 45-15988, etc., unsaturated epoxy ester resins are unsaturated epoxy ester resins.
Basic acid and optionally unsaturated - partially saturated basic acid -
An acid component substituted with one or more selected from basic acids, saturated polybasic acids, anhydrous saturated polybasic acids, unsaturated polybasic acids, and anhydrous unsaturated polybasic acids and an epoxy resin are esterified. The compound is synthesized by carrying out a heating reaction in the presence of a reaction catalyst, a polymerization inhibitor, a solvent, or a polymerizable monomer (hereinafter referred to as a monomer) if necessary, and then adding a solvent or monomer if necessary. This resin can be cured at room temperature or by heating by using an organic peroxide as a curing catalyst and, if necessary, a metal salt or the like as an accelerator.

When using this resin with a solvent, it can be used as paint, 1 repreg, etc., and when using a monomer, it can be used as a reinforced plastic (F
RP'), casting, adhesion, paint, etc.

Although the above resin is a type of modified epoxy resin, it is an unsaturated polyester obtained by polycondensing acids such as maleic anhydride and phthalic acid with polyhydric alcohols such as ethylene glycol, and is dissolved in monomers such as styrene. Like unsaturated polyester resins, it has the characteristic of being able to be cured with organic peroxides. Moreover, this unsaturated epoxy ester resin has performance equivalent to or better than -ffi-type amine- or acid-cured epoxy resins, especially chemical resistance, weather resistance, curing properties,
In terms of workability, it is superior to epoxy resins. For example, in terms of chemical resistance, epoxy resins have alkali resistance when cured with amines (can be cured at room temperature or by heating), and are resistant to acids (heat curing). When it is hardened, it is classified as acid-resistant. Therefore, it is difficult to obtain a material that has both of these characteristics by curing at room temperature.

However, unsaturated epoxy ester resins have excellent acid resistance and alkali resistance no matter which curing catalyst system is used.

In addition, regarding curability, in epoxy resins, the amount of curing agent used is limited, so it is not very flexible to adjust the curability at a certain temperature, and most of the time it is adjusted by the curing temperature. This is the current situation. Therefore, when curing at room temperature,
In summer or winter, there are many problems because gelation is fast or it does not harden. It has the characteristic that by changing the amount used, it is possible to achieve roughly the same curing properties in both summer and winter.

[Problems to be Solved by the Invention] However, conventionally, when unsaturated epoxy ester resins are cured, organic peroxides or accelerators are added to the resins as necessary. However, it hardens and cannot withstand storage, which means that the pot life is short, which is disadvantageous in industrial applications since it requires a long period of time. In addition, when this resin that uses monomers is heated and cured, the monomers tend to scatter, so when used in lamination, paints, etc., the cured resin tends to become uneven, which may change the performance of the cured resin. Therefore, it has disadvantages such as being undesirable.

These drawbacks often become a big problem when used industrially, and if these points can be resolved, it is thought that the applications can be further expanded.

[Means for solving problems] PolYIler, J., Vol. 16, p. 371 (
Nishikubo et al. (1984) revealed that epoxy groups in polymer side chains and various esters react quantitatively under relatively mild conditions when a specific quaternary ammonium salt is used as a catalyst. Ta. In order to solve the above-mentioned problems, it was discovered that a compound synthesized by applying this reaction has photocurability, and the present invention was completed.

Accordingly, the present invention provides a compound of the following formula [wherein R3 is a hydrogen atom or a methyl group, Y is an oxygen atom or a sulfur atom, and Z is a group selected from the group consisting of (Y(X)n, where X is a hydrogen atom, an alkyl group, a halogen atom, a nitro group, or a methoxy group, and 11 is an integer of 1 to 5] and has an ether group in the side chain by an addition reaction with an epoxy resin. , 1I Z-0-CH2H, C-0-Z (wherein R,, Y and Z have the same Ha as above, and R2 is an epoxy residue) and/
Another object of the present invention is to provide a photocurable composition containing a methacryloyl group-containing compound as an active ingredient.

[For production]

Since the above-mentioned acryloyl group- and/or methacryloyl group-containing compound has photocurability, it is possible to solve the above-mentioned problems associated with conventional unsaturated epoxy ester resins.

In addition, since the above-mentioned acryloyl group- and/or methacryloyl group-containing compound has photocurability, it can be used alone, but in practical terms, it is necessary to add a photosensitizer and/or solvent to the compound. It is preferable to add the following to form a photocurable composition.

The acryloyl group- and/or methacryloyl group-containing compound used in the photocurable composition of the present invention can be produced according to the general formula described below: (In the above formula, R1, R2, Y and Z are (same meaning as above).

In the above-mentioned addition reaction, the reaction ratio of the epoxy resin and the acrylic acid phenyl esters and/or the methacrylic acid phenyl esters is 0.0.
It is necessary that the total ester group of acrylic acid phenyl esters and/or methacrylic acid phenyl esters is 1 mol per 5 to 2.0 mol, and acrylic ester group-containing synthesized at a reaction ratio outside this range. Compounds are not preferred because they have poor curability, hardness of cured films, solvent resistance, and water resistance.

Epoxy resins that can be used in the above addition reaction include Epicote 828 (manufactured by Shell), higher molecular weight Ebibis type epoxy resin, epoxy novolak type epoxy resin, N,N-diglycidylaniline, and alicyclic type epoxy. Various epoxy compounds such as resins and ethylene glycol diglycidyl ether can be mentioned.

In addition, examples of acrylic esters and/or methacrylic esters that can be used in the above addition reaction include p-nitrophenyl methacrylate, 2,4-dichlorophenyl methacrylate, and phenyl methacrylate used in the examples described below. In addition to p-methoxyphenyl methacrylate and p-methoxyphenyl methacrylate, the following compounds may be mentioned:
In the formula, R3 and Z have the same meanings as above.

CIl□-d o-o-z In the formula, R1 and Z have the same meanings as above.

Also, R.

R.

R+ R+ (wherein R1 and R2 have the same meanings as above, A is -c
It is also possible to synthesize self-sensitizing oligomers such as o-Q or 100CH*).

Furthermore, some of the acrylic esters and/or methacrylic esters having aromatic or other active ester groups can be converted into di(p-nitrophenyl)adipic acid, diphenylthioadipate, di(p-nitrophenyl)
It is also possible to change to polyfunctional esters such as isophthalic acid ester and tri(4-chlorophenyl) trimellitic acid ester, and in this case, a high molecular weight telechelic oligomer can be obtained.

In addition, various tertiary amines, quaternary onium salts (phosphonium salts, ammonium salts), and crown ethers (KBr) can be used as catalysts for the above-mentioned addition reaction. In order to advance the process, it is preferable to use quaternary onium salts rather than tertiary amines.Furthermore, quaternary onium salts are those in which the total number of carbon atoms in the alkyl groups represented by R9 to R is 8 or more. Furthermore, some of the alkyl groups may be substituted with phenyl groups or benzyl groups, and the counter ion of the quaternary onium salt is preferably Br-1C1-1■- or F-. .

Furthermore, in order to prevent gelation during the above-mentioned addition reaction, phenols, quinones, and other compounds having a polymerization-inhibiting effect can be used as polymerization inhibitors, if necessary. These polymerization inhibitors can also be added after the reaction.

Examples of these polymerization inhibitors include hydroquinone,
Examples include hydroquinone monomethyl ether, benzoquinone, phenothiazine, thiosemicarbasite, acetone thiocarbazone, copper salt, and the like.

In the examples described below, the addition reaction was carried out without a solvent from the viewpoint of confirming the structure and reactivity of the product, but a reaction solvent can usually be used in the addition reaction. Furthermore, from the viewpoint of controlling heat generation during reaction, adjusting the viscosity of the product, and application as a photocurable material,
It is preferred to use polyfunctional acrylates such as ethylene glycol cyacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, etc. as the reaction solvent.

Although the photocurable composition of the present invention is easily cured by light irradiation, an organic metal salt or the like may be added to further promote curing.

The photocurable composition of the present invention can be prepared by, for example, applying the composition to a target object or casting the composition, and then using a light source ranging from visible light to ultraviolet rays, such as an incandescent lamp, a mercury lamp, an infrared lamp, and an ultraviolet fluorescent lamp. When light irradiation is performed using a carbon arc, a xenon lamp, etc., the resin layer is easily cured if it is not too thick.

The thickness of the resin layer that can be cured can be adjusted to some extent by adjusting the intensity and distance of the light source, the container containing the resin, etc., but it can be cured up to a thickness of about 20 cm. Regarding the degree of curability, although the thickness of the cured resin layer becomes thicker, long-term irradiation is required, but if it is a Wl film, it can be cured by short-time irradiation.

Therefore, when the resin layer becomes thick due to casting, it can be cured by irradiating light to photocure only the surface layer and then heating it, which is economically advantageous from an industrial perspective and requires less ventilation. You'll worry less.

At this time, since only the surface layer of the resin is photocured and the interior is cured by heat, it is even more advantageous to add an organic metal salt as an accelerator.

Furthermore, since the photocurable composition can be stored for a long period of time if stored in a can or place protected from light, there is no need for mixing at the time of use, which is very advantageous industrially.

[Example] The present invention will be further explained with reference to Examples (hereinafter simply referred to as "Example" unless otherwise specified).

憇-”-p-nitrophenyl methacrylate 20.73g (0,
1 mol) and Epicote 828 (bisphenol type epoxy resin 17.83y) (0.1 mol including epoxy groups) were placed in a 100 ml separable flask, and tetrabutylammonium bromide (TBAB) was added as a catalyst.
1.64i9 (0,005 mol) was added, and a small amount (0,019> of hydroquinone monomethyl ether (MQ) was added as a heavy inhibitor, and the reaction was carried out at 120°C for 5 hours. The zero reaction rate was determined from the epoxy equivalent. 99.5 mol%
Met. The molecular weight (according to GPC) of the product obtained was approximately 600.

Further, when the same reaction was carried out at 110° C. for 5 hours, the reaction rate was 94.7 mol%.

When the obtained product was subjected to IR analysis, it was found that 3300
Almost no absorption based on 10H at c + s-' is observed, and ester c = o (1730 cm-' for p-nitrophenyl methacrylate) is observed in 1720c Kasumi-1.
, 1640e+e-', C=C11240cm- and 1
A characteristic absorption of C-0-C (ester and ether) was shown at the 160c ring-', and the absorption of the epoxy group near 910c++-' completely disappeared.

0.3 g of benzoin ethyl ether was added as a photosensitizer to a solution of 10 fI of the obtained product in a small amount of ethyl acetate, and the mixture was coated on a glass plate at a thickness of 0.1 ms, and after the solvent was volatilized, it was heated for 500 ms. 30cm using Watt's ultra-high pressure mercury lamp
When irradiated with light for 1 minute from a distance of , the pencil hardness was 2H.
A cured product was produced that was insoluble in solvents such as THF.

[2,4-dichlorophenyl methacrylate 23.13y
(0.1 mol) and Epicote 82817.83t (0.1 mol as epoxy group),
g (0,005 mol) and a small amount (0,019) of M
The zero reaction rate obtained by conducting the reaction at 120° C. for 8 hours in the presence of Q was 99.4 mol % as determined from the epoxy equivalent. The molecular weight of the product obtained <according to a p c) is approximately 6
It was 00.

When the obtained product was subjected to IR analysis, it was found that 3300
There is almost no absorption based on 10H in cm-', and 1
720c+*'''I with ester C=O51640cm
-'C=C11240c+*- storehouse and 1160cm-
The characteristic absorption of C-0-C<ester and ether was shown at 910ef', and the absorption of epoxy groups around 910ef' completely disappeared.

The obtained product was dissolved in a small amount of ethyl acetate, 3x 1% benzoin ethyl ether was added as a photosensitizer, and the product was applied in the same manner as in Example 1 and irradiated with light. However, the coating film was cured, and a coating film with a pencil hardness of 3H was obtained.

9-1 16.18 g (0.1 mol) of phenyl methacrylate and 17.83 g of Epicote 828 <0 as epoxy group
．． 1 mol) of TBABl, 64 g (0,005
mol) and a small amount (0.01 g) of MQ were added and reacted at 120° C. for 8 hours. The zero reaction rate determined from the epoxy equivalent was 94.8 mol%.

The average molecular weight (according to GPC) of the product obtained was approximately 550.

When the obtained product was subjected to IR analysis, it was found that 3300
There is almost no absorption based on 10H in cm-', and 1
720c+*-' with ester c=o, 1640cm-
'to C=C11240cm-' and 1160c++-'
It showed a characteristic absorption of c-oc<ester and ether), and the absorption of epoxy groups around 910eel-' completely disappeared.

The obtained product was dissolved in a small amount of ethyl acetate, and 3% by weight of ProCure #11 manufactured by Merck & Co. was added as a photosensitizer.
73 was added and the product was coated in the same manner as in Example 1 and irradiated with light, the coating film was cured and its pencil hardness was 3H.

Takumi-1 p-methoxyphenyl methacrylate 19.12y (0
, 1 mol) and 17.83y of Epicote 828 (0.1 mol as epoxy group) was added TBABl, 64y.
(0,005 mol) and MQo, 01g were added and heated to 120°C.
The zero reaction rate after 10 hours of reaction was determined from the epoxy equivalent and was 91.9 mol%.

The molecular weight (according to GPC) of the product obtained is approximately 60
It was 0.

When the obtained product was subjected to IR analysis, it was found that 3300
A weak absorption based on 10H was observed at cm-', and 17ZO
cm-'C=C11640cm-'C=C1123
Characteristic absorption of C-0-C was shown at 0 cm-' and 1180e Kabura-1, and the absorption of epoxy groups near 910 cm-' (1) almost disappeared.

From the above, it is presumed that in the reaction between ρ-methoxyphenyl methacrylate and Epicote 828, in addition to the reaction between the epoxy group and the ester group, there is a slight reaction between the epoxy group and water in the air as a side reaction. Ru.

The obtained product was dissolved in a small amount of ethyl acetate, and 3% by weight of Irgacure #65 (manufactured by Ciba) was added as a photosensitizer.
1 and apply the product in the same manner as in Example 1,
When irradiated with light, the coating film was cured and its pencil hardness was 2H.

(Effects of the invention) Since the photocurable composition of the present invention contains a photosensitizer rather than an organic peroxide, there is no problem with pot life as described above, and it can be placed in a can or in a place shielded from light. It can be stored for a long time if stored.

Furthermore, since it can be made into a one-component resin, the trouble of mixing during use can be saved, which is very advantageous from an industrial perspective.

The photocurable composition of the present invention can be expected to be applied to various uses such as coating T+, printing materials, copying materials, display materials, and reinforced plastics.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [In the formula, R_1 is a hydrogen atom or a methyl group, Y is an oxygen atom or sulfur atom, Z is ▲ Numerical formula, chemical formula, table, etc. There are ▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
a group selected from the group consisting of, where X is a hydrogen atom, an alkyl group, a halogen atom, a nitro group, a methoxy group, and n is 1
is an integer of ~5] and a general formula that has an ether group in the side chain due to an addition reaction with an epoxy resin, ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, R_1, Y, and Z have the same meanings as above. With, R_
2 is an epoxy residue) A photocurable composition containing an acryloyl group- and/or methacryloyl group-containing compound as an active ingredient.