JPS6357614A - Photocurable composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in long-term storage stability, by using a specified (meth)acrylate compound as an effective component. CONSTITUTION:0.5-2.5mol of the epoxy groups of glycidyl (meth)acrylate are reacted by an addition reaction with 1mol of an active ester of a polycarboxylic acid to obtain a (meth)acrylate compound of formula I or II, wherein Z is O or S, R1 is H or methyl, R2 is a group of formula III, IV or the like, R3 is -(CH2)4-, -(CH2)3- or a group of formula V, VI or the like, n is 2-4, Z1 is a polyphenol residue of formula VII, VIII or the like, R12 is a group of formula IX or X, -CH=CH2, -CH3, -C2H5, -C3H7 or the like. A photosensitizer (e.g., benzoin ethyl ether) and/or a solvent are optionally added to this compound.

Description

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

[Conventional technology]

Special Publication No. 44-31472, Special Publication No. 45-4069
As described in Japanese Patent Publication No. 45-15988, etc., unsaturated epoxy ester resins are unsaturated epoxy ester resins.
A basic acid and, if necessary, an unsaturated portion of the basic acid, 1 selected from a saturated dibasic acid, a saturated polybasic acid, an anhydrous saturated polybasic acid, an unsaturated polybasic acid, and an anhydrous unsaturated polybasic acid. An acid component substituted with a species or two or more species and an epoxy resin are subjected to a heating reaction in the presence of an esterification reaction catalyst and, if necessary, a polymerization inhibitor, a solvent, or a polymerizable monomer (hereinafter referred to as a monomer). Then, if necessary, a solvent or a sulfuric acid is added for synthesis. 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, prepreg, etc., and when using a monomer, it can be used as a reinforced plastic (F'
RP), casting, adhesion, paint, etc.

The above resin is a modified epoxy resin with 1 m of unsaturated polyester obtained by polycondensing acids such as maleic anhydride and phthalic acid with polyhydric alcohols such as ethylene glycol, and is made of 7 polymers such as styrene. It has the characteristic of being able to be cured with organic peroxides, just like unsaturated polyester resins that are formed by dissolving them. Moreover, this unsaturated epoxy ester resin has performance equivalent to or better than general amine- or acid-cured epoxy resins, especially in terms of chemical resistance, weather resistance, hardenability, workability, etc. In other words, it is superior to epoxy resin. For example, in terms of chemical resistance, epoxy resins require amines (
When cured at room temperature or heat curing is possible, it is classified as alkali-resistant, and when cured with acid (heat-cured), 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 occurs quickly or it does not harden. However, the above-mentioned unsaturated epoxy ester resin has the characteristic that it can be made to have roughly the same curability in summer and winter by using an accelerator for the organic peroxide as necessary and by changing the amount of organic peroxide used. have.

[Problem that the invention seeks to solve]

However, when unsaturated epoxy ester resins are cured, organic peroxides or accelerators are added to the resins as necessary, but if these are added, the curing progresses even at room temperature, making it possible to withstand storage. I can't. In other words, it has a short pot life, which is disadvantageous in industrial terms since it requires a long time. In addition, when this resin is heated and cured using a seven-layer resin, particles tend to scatter, so when used for lamination, paint, etc., the cured resin tends to become non-uniform. This has disadvantages, such as undesirable changes in the performance of the cured hardwood. These drawbacks often pose major problems when used industrially.

If this point can be solved, it is thought that the applications can be further expanded.

[Means for solving problems]

The present invention is based on the general formula [wherein 2 is an oxygen atom or a sulfur atom, R1 is a hydrogen atom or a methyl group, R2 is a group, and n is 2
is an integer of ~4] or a polyfunctional phenol residue represented by the general formula (where zl is the following group: is a hydrogen atom or a methyl group, R12 is selected from, and each R1 and RI2 may be the same or different from each other. The present invention provides a photocurable composition.

[For production]

Since the acrylic ester and/or methacrylic ester type compound represented by the above general formula (1) or (2) has photocurability, it solves the above-mentioned problems associated with conventional unsaturated epoxy ester resins. can do.

In addition, since the above-mentioned acrylic ester and/or methacrylic ester type compound has photocurability, it can be used alone, but in practical terms, it is preferable to use this compound as an active ingredient and add light to it as necessary. It is preferable to add a sensitizer and/or a solvent to form a photocurable composition.

General formula (1) which is an active ingredient of the photocurable composition of the present invention
Alternatively, the acrylic ester and/or methacrylic ester type compound represented by (2) can be produced according to the addition reaction shown below.

First, the addition reaction for producing the acrylic ester and/or methacrylic ester type composition of general formula (1) will be described for the case where the R3 group is divalent.

(In the above formula, Z, R, , R2 and R have the same meanings as above).

Next, the addition reaction for producing the acrylic ester and/or methacrylic ester type compound of general formula (2) will be described for the case where 21 groups are divalent.

I Melting medium CH2=0
10Ftj2oc-z, 7coF
t, 2-+++ (in the above formula, zl, R1 and RI2 have the same meanings as above).

In the above addition reaction, the reaction ratio of glycidyl acrylate and/or glycidyl methacrylate and active ester of polyfunctional carboxylic acid is epoxy group O, S~2 in glycidyl acrylate and/or glycidyl methacrylate. It is necessary that the active ester of polyfunctional carboxylic acid be 1 mole per .5 mole, and acrylic ester and/or methacrylic ester type compounds synthesized at a reaction ratio outside this range will not be curable or hardenable. This is not preferred because the film has poor hardness, solvent resistance, and water resistance.

Acrylic acid glycidyl ester and/or methacrylic acid glycidyl ester that can be used to produce the compound represented by general formula (1) or (2) can be represented by the following general formula (3): CH2=C (formula (R1 has the same meaning as above).

The active ester of a polyfunctional carboxylic acid that can be used to produce the compound represented by the general formula (1) can be represented by the following general formula (4): (wherein, 2% R2,
R5 and n have the same meanings as above).

Furthermore, the active ester of a polyfunctional carboxylic acid that can be used for producing the compound represented by the general formula (2) can be represented by the following general formula (5): Z+ (R+z)m (5
) (where z, R12 and m have the same meanings as above).

In addition, as a catalyst for the above-mentioned addition reaction, the general formula % (Rn) It is a quaternary onium salt, a tertiary amine, or a tertiary phosphine represented by an alkyl group, and X is α, Br, or tertiary phosphines.
8-crown-6, cyclohexyl-18-crown-
6. Dibenzo-18-crown-6 and KBr, K-technique,
KBCNloQ-OK, (XCOONa, K
Combinations such as α can be used.

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, polyfunctional acrylates such as ethylene glycol cyacrylate and ethylene glycol dimethacrylate are used as reaction solvents. lard, trimethylolpropane triacrylate,
Preferably, trimethylolpropane trimethacrylate or the like is used.

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.

Examples of the photosensitizer used in the photocurable composition of the present invention include benzoin ethyl ether, 2-ethyl anthraquinone, benzophenone, benzyl, and Michler's ketone.

For example, the photocurable composition of the present invention is applied to a target object or cast, and then used as a light source in the range of visible light to ultraviolet light, such as an incandescent lamp, a mercury lamp, an infrared lamp, and an ultraviolet band 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 nails. Regarding the degree of curability, although the thickness of the cured resin layer becomes thicker, long-term irradiation is required, but a thin film can be cured with 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, only the surface layer of the resin is photocured, and the interior is cured by heat, so adding an organic metal salt as an accelerator will further increase the layer advantage.

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 "examples" unless otherwise specified).

Isophthalic acid P-phenyl ester 20.429 (O,
OSmol) and glycidyl methacrylate (GMA) 1
4.229 (0.1 mol) was placed in a 100 ml separable flask, and 0.65 g (0.0
02 mol) and a small amount (o,
o o 5! Hydroquinone monomethyl ether (
MQ) was added and reacted at 120°C for 10 hours to obtain a viscous product. The reaction rate determined from the epoxy equivalent was 97.
It was 0%. Moreover, the molecular weight (GPC) of the product was about 600.

When the obtained product was subjected to engineering R analysis, it was found that 1720
C=○, 163o for ctIL-', C=01 for '-'
1520cIrL-' and 1640crrL-1-N
It exhibited a characteristic absorption of O2, and the absorption of the epoxy group of 910cIIL had disappeared.

CH.

Example 2 [Reference Example 2 Production example of compound of general formula (1) 0 Example 1
Adipic acid P-nitrophenyl ester 1
TEAB 0.659- and MQo, 005p in a mixture of 9.42P (0.05 mol) and glycidyl methacrylate (GMA) 14.22 i% (0-1 mol)
was added and reacted at 120°C for 10 hours to obtain a viscous product. The reaction rate determined from the epoxy equivalent was 94.4%. Moreover, the molecular weight (GPC) of the product was about 680.

When the obtained product was subjected to engineering R analysis, it was found that 1720
crIK-'C! =0.1630cm-”C=C,
It shows characteristic absorption of -NO2 at 1520z-' and 1340 cm-', and also 910c! The absorption of the n-1 epoxy group had disappeared.

CH5I Example 3 [Reference Example 2 Production example of compound of general formula (1)] Sebacic acid P-nitrophenyl ester 2 was prepared in the same manner as above.
2.22 g (0.05 mol) and glycidyl methacrylate (GMA) 14.22,! i' (0-1 mol)
To a mixture of TBAB O, 6s g and MQ, 0.
005g92.9%. Moreover, the molecular weight (GPC) of the product was about 720.

When the obtained product was subjected to IR analysis, it was found that 1720
− to G=0.1630c+++ to C=C.

The characteristic absorption of -N○2 was shown at 1520 cm and 1340 cTt-', and the absorption of epoxy group at 910 cm had disappeared.

Product structure: OH, CH3 I CH2= OC! =OH2 Isophthalic acid thiophenyl ester 1 in the same manner as above
TBAB O,65P and MQ, 0.002p were added to a mixture of 7.52fF (0.05mol) and glycidyl methacrylate (GMA) 14.22y-(0.1mol) and reacted at 120°C for 8 hours. A viscous product was obtained. The reaction rate determined from the epoxy equivalent was 97.8. Moreover, the molecular weight (Gpc) of the product was about 640.

When the obtained product was subjected to IR analysis, it was found that 1720
Characteristic absorptions of C=C at cr71-' and 0=C at 1630C'm-' were exhibited, and the absorption of the epoxy group at 910Crn-' disappeared.

Tetraethylammonium chloride (TEAc) o,s OP and MQ, 0.00 was added to a mixture of isophthalic acid P-nitrophenyl ester 20.42 fP (0.05 mol) and glycidyl acrylate (GA) in the same manner as above.
5fP was added and reacted at 120°C for 10 hours to obtain a viscous product. The reaction rate determined from the epoxy equivalent was 97.3
%Met. In addition, the molecular weight (OPC) of the product is approximately 67
It was 0.

IR analysis of the obtained product revealed that 172
o, 7+ C=0.16 S Ocm-' C=C11
52oCrn-1 and 1340crn-' Knee No.
2 (7) 4? shows sexual absorption and also 91ocrn″″
The absorption of the epoxy group in No. 1 had disappeared.

Example 6 Add 0.059 mm of benzoin ethyl ether to each of the 11 products obtained in Examples 1 to 5 above, apply the mixture to a thickness of 0.1 mm on a glass plate, and apply the mixture to 50 cm using a Son Watt ultra-high pressure mercury lamp. When light was irradiated from a distance for 1 minute, cured products with excellent hardness were obtained in all cases. Further, all of these cured products were insoluble in hydrofuran (THF).

Example 7 The product 11 obtained in Example 1 above was added to 0.0% as a photosensitizer.
Sensitive compounds were prepared by adding 039-2-ethylanthraquinone, benzophenone, benzyl, and Michler's Katone, respectively, and when irradiated with light in the same manner as in Example 6, all cured within 1 minute.

Example 8 The products obtained in Examples 1.2.2 and 5 were irradiated in the same manner as in Example 6 and cured within 3 minutes in each case.

This is presumed to be because the nitrophenyl group in the product generates radicals upon irradiation with light and initiates polymerization of the acrylate group or methacrylate group. That is, these products are considered to be a type of self-sensitizing compound having a sensitizing group within the molecule.

Example 9 [Reference Example 2 Production example of compound of general formula (2) p-nitrobenzoic acid ester of bisphenol A 28.15y
-(0,05 mol), glycidyl methacrylate (GM
(abbreviated as A) 14.22P (0.1 mol), tert-butyl azoisobutyronitrile (TBAB) 0.
65 P and methylhydroquinone (H) o, o 2 P
was placed in a 100 ml separable flask and reacted at 120°C for 10 hours to obtain a viscous product. The reaction determined from the epoxy equivalent was 76.7%. Molecular weight (GPC)
was about 850.

CH2=C The product was identified by infrared absorption spectroscopy (Engineering).

1720Crn-' (C=○), +630Crt1
-1 (C=c), 1520Crn-' and 1340cr
The absorption of the epoxy group of n-' (-No 2 ) and 9 j Qcm-' almost disappeared.

Benzoic acid ester of bisphenol A 21.83f (
o, o 5 mol), GMA 14.22% (0.1 mol), TBAB O,655' and hydroquinone (HQ
, ) 0.02 fi' was placed in a 1 oomA' separable flask and reacted at 120°C for 10 hours to obtain a viscous product. The reaction rate determined from the epoxy equivalent was 68.8. The molecular weight determined by GPC was about 715.

IR of the product showed the following absorption.

1720 cm-' (C=O), 16 a Ocm-'
(C=C), the absorption of the epoxy group of 910crn-1 had almost disappeared.

CH2=C Acetate ester of bisphenol A 11.69 P(0,
05f-E nyl), GMAl 4,221!1l-(
0,1 mo/l/ ), TBAB O0657, MQ,
0.02% was placed in a 100ml separable flask and reacted at 120°C for 12 hours to obtain a viscous product. The reaction rate determined from the epoxy equivalent was 87.5%. G
The molecular weight determined by PC was about 520.

Engineering R: 172 ocrn-' (0=O), 1640
Crn-' (C=C, 94 QCrn-' absorption of epoxy group disappears.

C) (2=C4 and chalcone methacrylate 29.235L (0,1
mol), Epicote 828 17.02 p (0,0
5 momol), TBAB O, 65L! -1MQ, 0.0
1y- was placed in a Mitsuro separable flask and reacted at 120°C for 10 hours to obtain a viscous product. The reaction rate determined from the epoxy equivalent was 94.2%. The molecular weight determined by GPC was about 950. Engineering radius: 1720cm-
' (0-0 ester), 1660crn-1 (C-O
ketone), 1640 cm-' (C=C), 910z
-' absorption of epoxy group disappears.

Example 16 0.031 of benzoin ethyl ether was added to each of the product beds 11 obtained in Examples 9, 10, 11 and 12,
When light irradiation was carried out under the same conditions as in Example 6, excellent cured coatings were obtained in all cases.

Example 14 The products 11 obtained in Examples 9, 10.11 and 12 were each combined with 0.037 benzophenone as sensitizer;
When 2-ethylanthraquinone, benzyl or furoin was added and exposed for 1 to 2 minutes under the same conditions as in Example 6, excellent cured products were obtained in all cases.

The product obtained in Example 12 is similar to Example 6 even without the addition of a sensitizer.
When exposed for 1 minute under the same light irradiation conditions as above, a corroded cured film was formed, and this cured film was insoluble in THF.

Example 16 The product obtained in Example 9 was cured even in the unsensitized state by a 3 minute exposure.

〔Effect of the invention〕

Since the photocurable composition of the present invention contains a photosensitizer rather than an organic peroxide, there is no longer a problem with the pot life as described above, and it can be stored for a long time if stored in a can or place shielded from light. It can be stored for a long time. 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 paints, printing materials, copy materials, display materials, reinforced plastics, and coatings for class fibers.

Claims (1)

[Claims] 1. General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, Z is an oxygen atom or a sulfur atom, R_1 is a hydrogen atom or a methyl group, and R_2 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, 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. ▼
, ▲ 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. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and R_3 is -(CH_2)-_4,
-(CH_2)-_8, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
A group selected from the group consisting of chemical formulas, tables, etc. ▼, ▲ mathematical formulas, chemical formulas, tables, etc. ▼ and ▲ mathematical formulas, chemical formulas, tables, etc. ▼, where n is an integer from 2 to 4. Acrylic ester and 1 or methacrylic ester type compounds, or general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (2) [In the formula, Z_1 is the following group: ▲ Numerical formula, chemical formula, table, etc. There are ▼, ▲mathematical formulas, chemical formulas,
There are 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.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ It is a polyfunctional phenol residue represented by R_1 is a hydrogen atom or a methyl group, and R_1_2 ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas,
There are 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. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CH=CH_2
, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, -CH=CH-
CH_3, -CH_3, -C_2H_5, -C_3H_
7. Acrylic acid and 1 or methacrylic acid ester type compounds represented by ▲ selected from ▼ mathematical formulas, chemical formulas, tables, etc., and each R_1 and R_1_2 may be the same or different from each other] are used as active ingredients. A photocurable composition.