JPS6315817A - Photocurable resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give a cured product excellent in electrical properties, heat resistance and weathering resistance, by mixing a specified alicyclic epoxy resin with an aluminum compound and a silicon compound which generates silanol groups upon irradiation with light. CONSTITUTION:Tetrahydrobenzaldehyde obtained by the Diels-Alder reaction of butadiene with acrolein is subjected to the Tishchenko reaction to obtain a diene. This diene is epoxidized with peracetic acid, and the product is purified by distillation to obtain an alicyclic epoxy resin (A) of the formula having an Na content <=2ppm. Component A is mixed with an aluminum compound (B) which is a complex compound of an organoaluminum in which an alkoxyl group, a phenoxy group, an acryloxy group, etc., are bonded to Al and 0.0001-1wt%, based on component A, silicon compound (C) which has any one of a peroxysilane group, an o-nitro-benzyloxy group and an alpha-ketosilyl group and generates silanol groups upon irradiation with light.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a photocurable resin composition.

More specifically, the present invention relates to a photocurable resin composition that provides a cured product with excellent electrical properties, heat resistance, and weather resistance.

[Prior Art] In recent years, ultraviolet curable resins that are cured by irradiation with ultraviolet rays are low-pollution type using S solvents.

■Curing speed is extremely fast and product productivity is high.

(2) Since it cures as a 100% solid content, the volume change before and after curing is extremely small.

■There is no heat loss through the material or thermal effects on the material.

Due to these characteristics, it is used in various fields.

Among them, the process of photo-curing epoxy resin is
It utilizes the properties of epoxy resin, such as heat resistance, gloss, adhesion, and water resistance, and is expected to have a wide range of applications.

This photocurable epoxy resin is made by adding a photodecomposition type catalyst to an epoxy resin.

It is already known that onium salts such as 3M's FC-508 and General Electric's UVE-1014 are used as catalysts.

However, the catalyst components of these catalysts become ionic waste materials, and when used in electric machines, the electrical properties may be affected or corrosion may occur.

Therefore, an epoxy photocuring catalyst characterized by comprising an aluminum compound and a silica compound that produces silanol groups upon irradiation with light was proposed in Japanese Patent Application Laid-Open No. 57-12521'2.
．． It has been proposed in Japanese Patent Application Laid-Open No. 59/138220.

Epoxy resins that can be cured with these catalysts include 3
,4-■boxycyclomethyl-3'.

It is typified by 4'-epoxycyclohexalypoxylate (Daicel Chemical 1411M Celloxide 2021, UCC ERL-4221, etc.). So-called,
Is cycloaliphatic epoxy T111 fat Q? It is considered suitable. Conventional shrimp-bis type epoxy resins and novolac epoxy resins manufactured from epichlorohydrin and bisphenol A or novolac phenol have slow curing speeds and are not used.

Again, the fat so far! Since F-type EBO resin is a liquid resin with low viscosity, the range of application of photocurable resin compositions (1) is narrow and is mainly used for liquid coating.Synthesis of this alicyclic epoxy resin is usually carried out by the following route. It will be held in

(1) Synthesis of tetrahydrobenzaldehyde by Diels-Alder reaction of butadiene and acrolein (2) Diene synthesis by Tishchenko reaction of tetrahydrobenzaldehyde (3) Epoxidation reaction of diene Epoxidation used in the epoxidation reaction of (3) As the agent, superacid resistance is commonly used industrially, and is manufactured by the following process.

The manufacturing process of the J-BOX resin after the epoxidation reaction is as follows.

Epoxidation reaction → Removal of low PJI → Removal of high boiling point → When performing an epoxidation reaction using product peracetic acid, phosphoric acid or An alkali metal salt of polyphosphoric acid is added in an amount of 1100 ppm to 100 ppm.

Typical alkali metal salts of polyphosphoric acid include, for example, sodium trioctyl tripolyphosphate, sodium dioctyl tripolyphosphate, and the like.

These are used by partially converting the alkali metal salt of polyphosphoric acid into an alkyl ester to increase its solubility in the reaction solution.

These salts are to be removed from the epoxy resin product in a high boiling process.

The equipment used in this high boiling point removing process is a forced stirring film evaporator such as a gravity flow type thin film evaporator or a Smith type evaporator.

Since it is a high-boiling point substance, it is purified under reduced pressure, but in such an evaporator, components with a high boiling point are inevitably mixed into the product due to droplet entrainment.

Therefore, the phosphate added during the reaction is also inevitably iI
Enter t.

Currently, the 3,4-
Ebony 1-dicyclo to 1-1-dicyclo-3'.

4-1 epoxy [-1 to 1 dilinecarbo: 1 dilate,
221, Daicel Chemical Industry i1 Kosha's l = I]I,
l: Lead 2021.

These epoxy resins contain tripolyphosphoric acid salts added during the 61 reaction.

When the sodium content is constant h11J, ERL-4221
, Serokirioid 2021 and b 5~50111111
1 included.

In this way]~3゜4- containing 5-50 ppm of lium
When epoxycyclo to 4=silmethyl-3,4-epoxycyclo to kirincarboxylene 1 is mixed with the above-mentioned organic aluminum compound J3 and a silica compound that generates silanol groups by light irradiation and cured, a large amount of catalyst is required. or with a small amount of catalyst, curing 11. ) In some cases, it took a long time or it did not harden.

(Problems to be Solved by the Invention) In view of the above circumstances, 1. As a result of intensive study, the present inventors discovered that the catalytic activity of organosilicon compounds is reduced by Na ions, and 2. The present inventors filed a patent application. Showa 61-4358
The present inventors have discovered that this problem can be solved by using an alicyclic epoxy resin that contains extremely little Na pigment, as proposed in .

[Configuration of the Invention] That is, the present invention provides the formula (
A photocurable resin composition characterized by comprising: (b) an alicyclic epoxy resin represented by I>; (b) an aluminum compound; and (C) a silicon compound that produces a silanol group upon irradiation with light.

(a) serving as the skeleton of the photocurable resin composition of the present invention
The component 3,4-epoxycyclohexylmedyl-3-,4''-epoxycyclohexane carpo 1:silay 1- represented by the formula (I) is a pro-hysyl compound as in the process described above, that is, (1) 1-tadiene and acrylate. Synthesis of detrahydrobenzaldehyde by the Diels-Alder reaction of 1-cholein (2) Synthesis of diene using Tiscienko reaction (3) Produced by 1-boxylation reaction of diene with peracetic acid.

When producing and returning the compound of formula (1) which is the backbone of the photocurable f1 resin composition of the present invention, the characteristics that occur are the final product 11 r, ffl fraction 1 is J: I, : $; L ” f tt
l: By using equipment with similar evaporation efficiency (d1), it is possible to prevent high boiling point components from being mixed in due to droplet entrainment.

-1o,- Here, the distillation column is a device consisting of a packed column, a scouring column, and a capping column used in ordinary chemical industrial processes,
As for the number of stages, one or two stages that exhibit efficiency are sufficient.

Further, as a device having a distillation efficiency similar to that of a distillation column, a device for preventing entrainment of droplets or a device simply made by elongating the upper pipe portion of the distillation line may be used.

Usually, Smith type evaporators, which are often used as forced stirring M film evaporators, often have a cooling device inside the evaporator, but this type causes a large amount of entrained droplets.

Therefore, a cooling device can be installed outside to improve separation efficiency.

During distillation, heating can be performed using high-pressure steam or a heating medium, but heating is carried out at a temperature of about 160''C! to 220°C.

The degree of vacuum is preferably a high vacuum of about 0.1 Torr to 3 Torr.

By distilling and purifying using these devices, the epoxy resin represented by formula (I) used in the photocurable resin assembly of the present invention becomes extremely pure.

In other words, the salts of polyphosphoric acid added in the process of over-acid oxidation will not be lost.

Distillation and purification to produce 1 low Na product! Yield L1. of distilled amount relative to the reaction crude liquid when +1 to -95%, preferably 80-85%.

If it exceeds 95%, the evaporation d1 efficiency will decrease, but
Is Na content ω rice 6 colors 1a up? I will do it.

If it is less than 80%, the purity of the FAIYI efficient distillate will be high, but the flowability will be poor.1. ■) N in the epoxy compound represented by the formula
For example, accurately weigh sample F-11 to 2rJ into a platinum crucible and take 500 to 600
The organic matter is burned in an electric furnace at a temperature of 0.degree. C., the residue is dissolved in an aqueous nitric acid solution, made into a flocculent form at an appropriate temperature of 14 degrees Celsius, and analyzed by atomic absorption spectroscopy, etc., to a value of 21111111 or less.

The aluminum compound which is the component (b) of the photocurable resin composition of the present invention is an organic compound in which an alkoxy group, phenoxy group, acyloxy group, β, -diketonate group, 0-carbonylphenolate group, etc. are bonded to an aluminum atom. Preferably, it is a lead compound of aluminum.

Here, the alkoxy group preferably has 1 to 10 carbon atoms, and includes methoxy, ethoxy, i:soproboxy, butoxy, pentoxy, etc.; and the phenoxy group includes phenoxy group, 〇-methylphenoxy group, 0-
Methoxyphenoxy group, p-itrophenoxy group, 2.
Examples of the acyloxy group include acetato, propionate, isopropionate, butylade, stearade, ethyl acetoacetate, propylacetoacetate, butylacetoacetate, diethylmalate, and dipivalo. Ligands such as ilmethanate are examples of the β-diketonate group.
Examples include acetylacetonate, trifluoroacetylacetonate, hexafluoroacetylacetonate, 00H30C113-C-C11-C-C113, and the 20-carbonylphenolate group includes, for example,
An example is lyritylaldehydate.

Specific examples of such aluminum compounds include trismethoxyaluminum, trisethoxyaluminum, trisethoxyaluminum, trisisobutiopo4nidialuminum, trisphenoxyaluminum, trisvaramedylphenoxyaluminum, isopropoxyjethoxyaluminum, 1-trisbutoxyaluminum, trisacetoxyaluminum, trisstearard aluminum, trisbutyladealuminum, trispropionate aluminum, trisisobrobionate 1-aluminum, trisacetylacetonatoaluminum, tristrifluoroacetylacetonatealuminum, 1
~Lis hexafluoroacetyl aluminium, tris ethyl acetate 1-aluminum, tris salicylaldehyder 1-aluminum, tris diethyl malorade aluminum, tris propyl acetoacetate 1-aluminum, tris butylaceto acetate tart aluminum, tris divivaloyl methanate 1-aluminum, diacedylacetonate dipiva 1"yl methanato aluminum 1 te - These aluminum compounds may be used alone or in a mixed system of two or more, The amount added is in the range of 0.0001 to 1%, preferably 0.001 to 09.9% by weight based on the epoxy resin.

If the amount is less than 0.0001% by weight, sufficient properties of the cured product cannot be obtained, and if it exceeds 1%,
This is not preferable because it not only increases cost but also tends to reduce moisture resistance.

-1 The third essential component of the composition of the present invention is a silicon compound that generates silanol groups upon irradiation with light.

Such a silicon compound is preferably a silicon compound having any one of a peroxysilane group, an O-nitrobenzyloxy group, and an α-ketosilyl group.

Among these silicon compounds, those having a peroxysilane group have the following formula: (l1l)n-3i(0-0-R2)
4-n (in the formula, R1 and R2 may be the same or different, each hydrogen atom, halogen atom, carbon number 1
~5 represents an alkyl group or aryl group: n is O
Represents an integer from ~3. ).

In the above formula, examples of the alkyl group having carbons W11 to W5 include methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, t-butyl group, 5ec-butyl group, n-pentyl group, Examples of the nearyl group include a methoxy group, an ethoxy group, and a chloromethyl group; examples of the nearyl group include a phenyl group, a naphthyl group, an anthranyl group, and a benzyl group;
It may have a substituent such as a single halogen-20 atom, a nitro group, a cyano group, or a methoxy group.

Specific examples of such silicon compounds include the following formula: %Formula% CH3-C-0-0-3i -0-0-C-CH3CH
Examples include compounds represented by 3-3i -0-0-C-CI-13CH3Cl-13 CH2C83CI-13 GH3-C-〇-○-8i-0-〇-C-CH3.

In addition, those having an O-nitrobenzyloxy group have the following formula: %Formula% (In the formula, whether 3 is the same or different in R1, R2, r, J:<, respectively, hydrogen atom: halogen Atom; Vinyl group; Allyl group: Unsubstituted or substituted alkyl group having 1 to 10 carbon atoms: Alkoxy group having 1 to 10 carbon atoms: Unsubstituted or substituted aryl group Niaryloxy group: Represents a siloxy group, R4 is hydrogen Atom: unsubstituted or substituted alkyl group having 1 to 10 carbon atoms: phenyl group; substituted) Jnyl group; R5, R6, R7, and R8 may be the same or different; each is a hydrogen atom; Nitrofurnidiano group: Hydroxyl group: Mercabuto group: Halogen atom niacetyl group: Allyl group; C1-C5 alkyl group:
Alkoxy group having 1 to 5 carbon atoms: represents a non-converted or substituted aryl group, and p, Q, and r are 0≦
Represents an integer that satisfies the following conditions: p, q, r≦3.1≦p+q+r≦3. ).

Examples of unsubstituted or substituted alkyl groups having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, t-
Examples include a butyl group, a pentyl group, a chloromethyl group, a fluoroethyl group, a fluoromethyl group, a cyanomethyl group, and examples of the alkoxy group having 1 to 10 carbon atoms include a methoxy group,
Examples include ethoxy group, n-broboxy group, and n-butoxy group.

Examples of unsubstituted or substituted aryl groups include phenyl group,
p-methoxyphenyl group, p-chlorophenyl group, p-
t-Lifluoromethylphenylvinylmethylphenyl (
0-nitrobenzyloxy)silane, t-butylmethylphenyl(0-nitrobenzyloxy)silane, triethyl(O-nitrobenzyloxy)silane tri(2-chloroethyl)-0-nitrobenzyloxysilane, tri(p-trifluoro Methylphin i7-Konjiru)-〇-2! ~Lopenzyloxysilane, trimethyl[α-(0-21~phenyl)-〇-nitropendyloxy]silane, dimethylphenyl[α-(0-21~phenyl)-〇-nitropenzyl oxy]silane, methylphenyldi[α-(0-nido-O-phenyl)-〇-nido-O-benzyloxy]silane, triphenyl(α-
Ethyl-〇-nitropenzyloxy)silane, trimethyl(3-methyl-2-nitropenzyloxy)silanedimethylphenyl(3,4,5-trimethoxy-2-nitrobenzyloxy)silane, triphenyl(4 ,5,6
-1-dimethoxy-2-ditropendyloxy)silane, diphenylmethyl (5-methyl-4-methoxy-2-
2I-penzyloxy)triphenyl(4,5-dimethyl-2-nitrobenzyloxy)silane, vinylmethylphenyl(4,5-dichloro-2-nitrobenzyloxy)silane, triphenyl(2,6- dinitrobenzyloxy)silane, diphenylmethyl(2,4-ditropenzyloxy)silane, triphenyl(3-methoxy-2-nitrobenzyloxy)silane, vinylmethylphenyl(3,4-dimethoxy-2-nitrobenzyl) oxy)silane, dimethyldi(0-nitrobenzyloxy)silane, methylphenyldi(0-nitrobenzyloxy)silane, vinylphenyldi(0-nitrobenzyloxy)silane, t-butylphenyldi(O-nitrobenzyl) oxy)silanediethyldi(0-nitrobenzyloxy)silane.

, 2-chloroethylphenyldi(O-nitrobenzyloxy)silane, diphenyldi(0-nitrobenzyloxy)silane, diphenyldi(3-methoxy-2-nitrobenzyloxy)silane, diphenyldi(3,4 -dimethoxy-2-nitrobe~ 29 ~ methyloxy)silane, diphenyldi(2,6-dinitrobenzyloxy)silane, diphenyldi(2,4-dinitrobenzyloxy)silane, methyltri(O-nitrobenzyloxy)silane .

Phenyltri(0-nitrobenzyloxy)silane, p
-bis(0-nido-0benzyloxydimethylsilyl)benzene1.1.3.3-te1-raphenyl-1,3-di(0-
nitrobenzyloxy)siloxane, 1°1.3.3.
．． Examples include 5-hexaphenyl-1,5-di(0-nitrobenzyloxy)siloxane and SI(4), a silicon compound produced by the reaction of a containing silicone resin and 0-nitrobenzylaltol.

Finally, the one having an α-ketosilyl group has the following formula: (wherein, m and n represent numbers of 0, 1.2.3, and J
L+Q+jQ cannot exceed 3: R1, R2
, R3, R4, may be the same or different,
Each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, a furyl group, a hydrogen carbonate group such as a vinyl group, an aryloxy group, or an alkoxy group having 1 to 10 carbon atoms, and these are halogen atoms, NO2, and CN.

-il! such as 0CH3! j! It is a compound represented by ) which may have a group in the molecule.

in particular C1~+30 H30 H3 H3 H30 H3 Compounds such as

These silicon compounds are added in an amount of 0.2 to 2.0%, preferably 1 to 10%, based on the epoxy resin.
is within the range of If the amount is less than 0.1% by weight, sufficient curing properties cannot be obtained, and although it is possible to use more than 20% by weight, it may result in high costs and decomposition products of the catalyst component. This is not desirable because there are cases where this is a problem.

The composition of the present invention has the above three components, that is, an epoxy resin, an aluminum compound, and a silicon compound, as essential components, but it is also preferable to add various rust-preventing pigments to improve the overall rust-preventive property. preferable. Examples of the rust-preventive pigment at this time include borate diphosphate; chromium M salt; and molybdate. The amount added is usually 10 to 50% based on the weight of the epoxy resin.

In addition, no inconvenience occurs even if various coloring dyes, pigments, or additives such as silica and alumina are blended.

The composition of the present invention can be put to practical use by being cured by a method such as room temperature photocuring, heating photocuring, or after-curing after photocuring after being applied to a substrate. At this time, the wavelength of the irradiated light varies depending on the composition of the lining composition, but is usually 180 to 7000 m. Irradiation with ultraviolet light is particularly effective. The light irradiation time varies depending on the composition of the epoxy resin, the type of catalyst, the light source, etc., but is usually 1.
The time is 0 seconds to 30 minutes, preferably 20 seconds to 1 minute.

The heating temperature in the case of heating photocuring varies depending on the composition of the epoxy resin and the type of catalyst, but is usually 20 to 200℃.
℃, preferably 60 to 100℃. As a light source,
Low pressure mercury lamps, high pressure mercury lamps, .

Carbon arc lamps, xenon lamps, argon glow discharge tubes, metal halide lamps, etc. can be used. After-curing after photocuring varies depending on the composition of the epoxy resin and the type of catalyst, but is usually 50 to 200°C, preferably 40°C.
Or at 100-180℃, usually for 1-10 hours,
It is preferably carried out for 2 to 5 hours.

[Effect of the invention] The photocurable resin composition of the present invention has excellent heat resistance.

It has electrical properties, especially tracking resistance and arc resistance,
It has the characteristic of being less corrosive to metals, making it particularly suitable for use in electrical materials.

7-' Hereinafter, the present invention will be explained in more detail with reference to Examples.

Synthesis Example 1 Allyl alcohol 58g (1 mol), 4-vinylcyclohexene-1-oxide 868g-3'/- (Effects of the invention) The photocurable resin composition of the present invention has excellent curability and electrical properties, especially 1jii51, which has excellent heat resistance and is less corrosive to metals, is particularly suitable for electrical materials.

The following is a detailed explanation of Kinai II) using six embodiments.

Synthesis Example-1 3-Schiff 0 Hexyl Medyl-3-Cyclohexene Lupoxyle-1~173N Ethyl acetate solution containing 9.30 wt% peracetic acid $450KSI, 1~A Acid-resistant solution 3 containing 20% sodium tripolyphosphate K9 1
The conversion rate of peracetic acid was continuously charged to a complete mixing tank and a piston flow tower in an hour, and while keeping the temperature at 35℃, the conversion rate of peracetic acid was 9.
The reaction was allowed to occur until the concentration reached 0% or more.

Acetic acid, ethyl acetate, and excess peracetic acid were evaporated from the resulting reaction crude liquid using a gravity thin film evaporator.

The (p) was purified using a Smith evaporator to remove high-boiling components.

It was heated under reduced pressure of 0.5 Torr using high-pressure steam at 180°C to 190°C, and the distillate amount was 1q at a ratio of 167/ry/llr.

At this time, the amount of bottoms containing high-boiling substances was 36/(g/Hr).

The resulting product had a hue of 8P 11 820 and an epoxy equivalent of 133.

Comparative Synthesis Example-1 The reaction was carried out in the same manner as in Synthesis Example-1, and in the final purification step, the same purification was carried out using an internal condenser type Smith evaporator.

The resulting product had a hue of APIIA 40 and an epoxy equivalent weight of 135.

Example-1 1 g of 3,4-epoxycyclohexylmethyl-3-,4--boxycyclohexanecarpoxylate obtained in Synthesis Example-1 and Comparative Synthesis Example-1 and commercially available UCC [formerly-4221] N a a lit (1) Perform all determination and ivy.

2 samples each! Precisely weigh I into a platinum crucible and heat at 411°C in an electric furnace at 60°C. Dissolve the combusted U1 residue with nitric acid and raise the volume to a volumetric flask at 50 m! 'Analyzed by atomic absorption spectrometry.

The results are shown in Table-1.

Table-1 Examples-1 to 6 Synthesis Example-1, Comparative Synthesis-1 and 100 Commercial Companies' IER
Each epoxy resin of L-4221 contains trisethylacetoacetatoaluminum (1'AAA) and i-lysethylacetoacetatoaluminum (TEAACA) as organoaluminum compounds, and triphenyl (0-nitrobenzyl) as an organosilicon compound. oxy) silane (
TBOPM) is used.

Table 2 shows the results of comparing the tack-free time of a 20 micron thick coating film, which was blended in the proportions shown in Table 2 and irradiated with an 80 W/Cm metal halide lamp at an irradiation distance of 6.5 cm.

-2-1-- , /-'~ 〆□□□□- -1l-1- It can be seen that the photocurable resin composition of the present invention has excellent curability. .

Patent applicant Dai-e Kagaku] Nigyo Co., Ltd. Agent
Person Patent Attorney Takashi Koshi - No. 2 [i]
−

Claims (1)

[Claims] (a) Alicyclic epoxy resin represented by formula (I) with Na content of 2 ppm or less ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (I) (b) Aluminum compound (c) Light A photocurable resin composition comprising a silicon compound that generates silanol groups upon irradiation. (2) The photocurable resin composition according to claim 1, wherein the aluminum compound is an organic aluminum compound. (3) The photocurable resin composition according to claim 1, wherein the silicon compound is a silicon compound having any one of a peroxysilane group, an o-nitrobenzyloxy group, and an α-ketosilyl group. (4) The blending ratio of the aluminum compound and the silicon compound is each 0.0 with respect to the weight of the epoxy resin.
001 to 1% by weight, and 0.01 to 2% by weight of the photocurable resin composition according to claim (1).