JPS61283614A - Curable resin composition - Google Patents

Abstract

PURPOSE:A photocurable resin composition excellent in moldability, weathering resistance, heat resistance, electrical properties, etc., and suitable as, e.g., a sealant for electronic parts, containing a specified cyclohexane skeleton- containing epoxy resin and a photoinitiator as principal components. CONSTITUTION:The purpose photocurable resin composition is obtained by using an epoxy resin of formula I (wherein R1 is an active hydrogen-containing organic compound residue, n<1>, n<2> and n<l> are each 9 or 1-100, and their sum is 1-100, l is 1-100, A is an oxycyclohexane skeleton, X is formula III, -CH=CH2 or the like, and R2 is H, alkyl or the like) and a photoinitiator as principal components. The epoxy resin of formula I can be produced by polymerizing 4-vinylcyclohexene-1-oxide by ring opening by using an active hydrogen- containing organic compound as an initiator and epoxidizing the obtained vinyl side chain-containing polycyclohexene oxide polymer with an oxidizing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photocurable resin composition. More specifically, photocurable J provides a cured product with excellent heat resistance and weather resistance.
The present invention relates to a boxy resin composition.

[Prior Art] In recent years, ultraviolet curable resins that are cured by irradiation with ultraviolet rays are (1) solvent-free and low-pollution type. ■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 these, the process of photo-curing epoxy resin 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. The catalysts are FC-508 obtained and sold from 3M Company, and LJVE-101 manufactured and sold by General Electric Company.
It is already known that onium salts such as 4 can be used.

Epoxy resins that can be cured with these catalysts include 3
,4-Epoxycyclomethyl-3',4'-epoxycyclohexanecarboxylate (Celoxide 2021 manufactured by Daicel Chemical Co., Ltd. E Rl--4 manufactured by UCC Company)
221>. So-called alicyclic epoxy resins are preferred. Conventional shrimp-bis type epoxy resins and novolac epoxy resins manufactured from T-bichlorohydrin and bisphenol A or novolac phenol have slow curing speeds and are not used. Furthermore, since the conventional alicyclic epoxy resins are liquid resins with low viscosity, the range of application of the resulting photocurable resin compositions is narrow, and they are mainly used as liquid coating agents.

On the other hand, epoxy resin utilizes its properties to provide 71J) t-
Electrical fields such as substrates, IC encapsulation, LED encapsulation, resistors, 3 capacitor encapsulation, paint fields, adhesive fields,
Widely used in the ink field such as solder resist ink.

The appearance of photocurable epoxy resins is desired in these various fields, but the molding methods are different, and epoxy resins in low viscosity liquid form and high viscosity liquid/solid form are required for each application.

[Problems to be Solved by the Invention] In view of the above circumstances, the inventors of the present invention have made extensive studies, and by using a new epoxy resin having a cyclohexane skeleton proposed in Japanese Patent Application No. 59-014859, various molding methods can be achieved. The present inventors have discovered that a photocurable resin composition can be obtained that has properties depending on the method and provides a cured product with excellent weather resistance and heat resistance.

[Structure of the Invention] That is, the present invention provides a photocurable resin composition containing an epoxy resin represented by the general formula (1) and a photoinitiator as main components.

However, R1 is an organic compound residue having one active hydrogen.

nl, n2 ----nA is O or an integer from 1 to 100, and the sum thereof is from 1 to 100.

1 does not represent an integer between 1 and 100.

A is an oxycyclohexane skeleton having a substituent,
It is expressed by the following formula.

R2 is any one of H1 alkyl group, carboaryl group, and carboaryl group, but \Cl-1-CI-1
Table 2 with at least 5 formulas (])\. / Contains one or more in the washed resin. ”.

Next, the present invention will be explained in detail.

In the novel 1-boxy resin represented by formula (1) of the present invention, R1 is an organic residue having active hydrogen, and examples of the organic substance having active hydrogen, which is a precursor thereof, include alcohols, phenols, and carboxylic acids. , amines, thiols, etc.

The alcohol may be a monohydric alcohol or a polyhydric alcohol.

For example, aliphatic alcohols such as methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol. ,1
．． 3-butanediol, 1.4-butanediol, pentanediol, 1.6-hekyrindiol, neopentyl glycol, oxypivalic acid neopentyl glycol ester, cyclohexane dimetatool, glycerin, diglycerin, polyglyphosphorus, trimethylolpropane, Examples include polyhydric alcohols such as trimethylolethane, pentaerythritol, and dipentaerythritol.

Examples of phenols include phenol, creso-), catechol, pyrogallol, hydroquinone, hydroquinone 7-methyl ether, bisphenol A, bisphenol F, 4,4°-dihydroxybenzophenone, bisphenol s1 phenol resin, and cresol novolac resin.

Carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecane 2M, trimellitic acid, pyromellitic acid, mipolyacrylic acid, phthalic acid, isophthalic acid, and terephthalic acid. etc. Also included are compounds having both a water M group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid.

Examples of amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4°-diaminodiphenylmethane, isophorone diamine, toluene diamine, hexamethylene diamine, xylene diamine. , diethylenetriamine, triethylenetetramine, ethanolamine, etc.

Examples of thiols include methyl mercaptan, ethyl mercaptan, phenyl mercaptan, polyhydric alcohol esters of mercaptopropionic acid, such as ethylene glycol bis(methyl mercaptopropione (mercaptopropionic acid) ester, pentaerythritol pentakis (mercaptopropionic acid) ester) etc. can be mentioned.

Other active hydrogen-containing compounds include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose aretate, cellulose acetate butyrate, hydroxyethyl cellulose,
Examples include acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene-maleic acid copolymer resin, alkyd resin, polynisder polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol, polytetramethylene glycol, and the like.

In addition, the compound having active hydrogen may have an unsaturated double bond in its skeleton, and specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, and tetrahydrophthalic acid. There is. The unsaturated double bonds of these compounds may also have an epoxidized structure.

nl in general formula (1), n... nl is 0
Or, it is 1 to 100, but if it is 100 or more, it becomes a resin with a high melting point, which is difficult to handle, and it cannot be used in practice.

g is an integer from 1 to 100.

Among the substituents X of A in formula (1), the fewer the number, the more preferable.

That is, in the present invention, the substituent X is mainly δ7.

Specifically, the novel epoxy resin represented by formula (1) of the present invention is produced using an organic compound having active hydrogen as an initiator.
A polyether resin obtained by ring-opening polymerization of vinylcyclohexene-1-oxide, that is,
It can be produced by converting a polycyclohexene oxide polymer having vinyl group side chains with an oxidizing agent such as peracid.

4-vinylcyclohexene-1-oxide is butadiene I
It is obtained by partially epoxidizing vinylcyclohexene obtained by a duplication reaction of cyclohexene with peracetic acid.

When 4-vinylcyclohexene-1-oxide is polymerized in the presence of active hydrogen, it is preferable to use a catalyst.

Examples of catalysts include amines such as methylamine, ethylamine, propylamine, and piperazine; various basic acids such as pyridines and imidazoles; organic acids such as formic acid, acetic acid, and propionic acid; inorganic acids such as sulfuric acid and hydrochloric acid; and sodium Alcolades of alkali metals such as methylate, KOH, Na
0 +-1-1 anolkali F, ZnCj12,
Examples include Lewis acids such as All CM and S n CM 4 or King's complexes, and organometallic compounds such as triethylaluminum and diethylzinc.

These catalysts can be used in an amount of 0.01 to 10%, preferably 0.81 to 5%, based on the reactants. The reaction temperature is -70 to 200°C, preferably -30°C to 10°C.
It is 0°C.

The reaction can also be carried out using a solvent. As the solvent, only those containing active hydrogen can be used.

i.e., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene,
Aromatic solvents such as xylene, ethers, aliphatic hydrocarbons, esters, etc. can be used.

Now, in order to epoxidize the polycyclohexyl oxide polymer having a vinyl group side chain synthesized in this way and to produce the new epoxy resin of formula (1) which is the main component of the fiber-reinforced plastics of the present invention, Either acids or hydroperoxides can be used.

As peracids, performic acid, peracetic acid, perbenzoic acid, trifluoroperacetic acid, etc. can be used.

Among these, peracetic acid is a particularly preferred epoxidizing agent because it is industrially available at low cost and has high stability.

As the hydroperoxides, hydrogen peroxide, tert-butyl hydroperoxide, cumene peroxide, etc. can be used.

A catalyst can be used during epoxidation if necessary. For example, in the case of a peracid, an alkali such as soda carbonate or an acid such as sulfuric acid may be used as a catalyst. In the case of hydroperoxides, catalytic effects can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with tarjabdel hydroperoxide. can.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature depending on the equipment and physical properties of the raw materials.

Depending on the conditions of the epoxidation reaction, a substituent group in the raw material is generated at the same time as the olefinic bond is epoxidized, and is included in the target compound. Substituents in the target compound 1
It is determined by the type of lamp, the molar ratio of olefin bonds in the epoxidizing agent, and the reaction conditions.

1 Transmuted! For example, when the epoxidizing agent is peracetic acid, the 2-substituent group mainly has the structure shown below. , the target compound can be removed from the reaction phase liquid.

A typical compound of the photoinitiator of the present invention is represented by the following formula.
It is a reaction catalyst that generates Lewis acid using light.

(Aromatic diazonium salt) (Louis Kari 1...
・・・・・・m ・・・・・・・・・(iii) '/-11: Solvent For example, U.S. Pat. No. 4.231.051: No. 4,256
, No. 828: No. 4.138,255 and No. 4,058
, No. 401, any one of the well-known photopolymerization initiators may be used. Preferred photoinitiators include triarylsulfonium complex salts as described in U.S. Pat. No. 4,231,951;
Aromatic sulfonium salts or aromatic iodonium salts of halogen-containing complex ions as described in U.S. Pat. Nos. 4,058,401 and 4.138.
．． No. 255, aromatic onium salts of group v1 group a groups as described in each specification: US Pat. No. 4, . It includes aromatic onium salts of Va group radicals as described in No. 069,055 Mei 1I1m. Such salts include FC-508 and FC-
509 (manufactured by Minenta Mining and Manufacturing Co., Ltd.), and LIV E-1014
(manufactured by General Electric Company).

In the present invention, the epoxy resin represented by the general formula (1) may be used in combination with the Haku-no-1 oxy resin as long as the properties of the epoxy resin are not impaired. Here, other epoxy resins may be any commonly used epoxy resins, such as Ebis type epoxy, bisphenol F epoxy, novolac type epoxy, and resin type J boxy.

Photoinitiators are used in conventional amounts such as about 0.1 to 30 parts by weight per 100 stitches of epoxy resin.

The photocurable resin composition of the present invention may contain various additives other than those mentioned above, if necessary. It goes without saying that the coating may contain fillers, pigments, stabilizers, and flow control agents.

[Effects of the Invention] The photocurable resin composition of the present invention obtained as described above takes advantage of the characteristics of the epoxy resin represented by the general formula (1), and therefore has excellent heat resistance and weather resistance. Due to its excellent electrical properties, it is useful as a coating agent for electronic parts, as a sealant, as a powder dye, and as a molding material.

The present invention will be explained below with reference to Examples.

Synthesis Example 1 Allyl alcohol 58y (1 mol), 4-vinylcyclohexene-1-oxide 868g (7 mol) and B
4.7 g of F3 etherate was mixed at 60°C, and gas chromatography analysis revealed that 4-vinylcyclohexene-1-
The reaction was continued until the conversion of the fourth side reached 98% or more.

Ethyl acetate was added to the obtained reaction carrier solution, washed with water, and then the ethyl acetate layer was soaked to obtain a viscous liquid.

In the infrared absorption spectrum of the product, the absorption due to the epoxy group at 810.850 cm-1 observed in the raw material has disappeared, the absorption due to Needel bond at 1080.1150 cIR-' is present, and gas chromatography analysis shows that the production Although the allyl alcohol in the product was in a trace amount, it was confirmed that the compound had the structure shown by the above formula since there was an absorption of -1 group at 3450 cm-1 in the infrared absorption spectrum. Compound 429 of engineering/manpower ←! J was dissolved in ethyl acetate and charged into a reactor, to which 395 g of peracetic acid was added dropwise as an ethyl acetate solution over 2 hours. During this time, the reaction temperature was maintained at 40°C. After the addition of peracetic acid was completed, the mixture was aged at 40°C for roughly 6 hours.

Add ethyl acetate to the reaction crude liquid and add 416g of soda carbonate.
and then thoroughly washed with distilled water.

The ethyl acetate layer was evaporated to yield a viscous transparent liquid. The oxirane oxygen content of this compound was 9.27%, and characteristic absorption due to epoxy groups was observed at 1260 crx'' in the infrared absorption spectrum.

Furthermore, absorption due to residual vinyl groups is observed at 1640 cm-', and similarly to Synthesis Example 1, this compound 492
J and 395 g of peracetic acid were reacted to obtain a viscous transparent liquid.

This compound has an oxirane oxygen content of 9.27% and an infrared absorption spectrum of 1260C11-
Characteristic absorption due to epoxy groups was observed in No. 1.

Furthermore, absorption due to residual vinyl groups was observed in 1640C11-1, and as in Synthesis Example 1, this compound 49
A reaction between 2 g and 395 g of peracetic acid M was performed to obtain a viscous transparent liquid.

This compound had an oxiranic acid content of 9.27%, and a characteristic absorption due to epoxy groups was observed at 1260 cm in the infrared absorption spectrum. Furthermore, absorption due to residual vinyl groups is observed at 1640α-1, and OH at 3450n-1.
I, 1730crx shows absorption by O group CO- This compound has the structure of general formula (1) (R nigericidyl group or allyl group, n = 7 on average, contains a group in which one part of acetic acid is added to an epoxy group) ).

Synthesis Example-2 In the same manner as in Synthesis Example 1, trimethylolbuO pan 13
4s, 4-vinylcyclohexene-1-oxide 18
63 g was reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the main component, the absorption due to epoxy groups at 810.850 cm-' that was observed in the original amount has disappeared, the absorption due to ether bonds exists at 1080.1150 cm-', and NfVIR
Analysis shows that this compound has nc + , fvlt , f
573 U of this compound was reacted with 387 g of suitable aged M in the same manner as in Synthesis Example 1 to obtain a viscous transparent liquid.

This compound has an oxirane oxygen content of 9.03% and an infrared absorption spectrum of 1260 cm-
Characteristic absorption due to epoxy groups was observed in No. 1. Furthermore, 1
This compound has the structure of general formula (1,) (R nitrimethylo- It was confirmed that the lupropane residues were N=3, n, r+2.n3=5 on average, including one group in which acetic acid was added to an epoxy group).

Claims (2)

[Claims] (1) A photocurable resin composition containing an epoxy resin represented by general formula (I) and a photoinitiator as main components. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, R_1 is an organic compound residue with 1 active hydrogen. n1, n2...nl is 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100. l represents an integer from 1 to 100. A is an oxycyclohexane skeleton having a substituent,
It is expressed by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ , a carboalkyl group, or a carboaryl group, and the resin represented by formula (I) contains at least one ▲ which has a mathematical formula, chemical formula, table, etc. ▼. (2) The photoinitiator is selected from the group consisting of triarylsulfonium complex salts, aromatic sulfonium or iodonium salts of halogen-containing complex ions, aromatic onium salts of Group V_a or Group VI_a elements, or mixtures thereof. A photocurable resin composition according to claim 1.