KR840001676B1 - Photocurable composition - Google Patents

Abstract

Photo-hardenable, cationically polymerization org. material, (A), is deep-hardened by(i) adding 0.1-15 wt. % A, of a triarylsulphonium salt, )I), as photo-initiator, and (ii) irradiating the mixt. I has formula ((R)a(R1)b(R2)cs)(Y)(where R is a monovalent org. radical terminated with other than aryl); and (iii) 0.1-10 parts wt. of organo titanate; and (b) heating the mixt. at from the m.P of the copolymer to 200oC. Pref. the copolymer is of ethylene-ethyl acrylate, the difunctional compd. is decane-diol and the organo-titanate is tetraisopropyl titanate. The polymer can be cured at rapid rates without high pressure and prepd. without silane compds.

Description

Photocurable composition

The present invention relates to a photocurable composition. More specifically, the present invention relates to a photocurable composition consisting of a cationic polymerizable organic material and an effective amount of a specific triarylsulfonium salt photoinitiator.

Epoxy resins and other cationically polymerizable organics, along with various aryl sulfonium salts, rapidly cure in the presence of ultraviolet light, as described in Crivelo, US Pat. Nos. 4,058,401, 4,069,055, and 4,161,478. While valuable results can be obtained using such photocurable compositions and photoinitiators, conventionally mentioned cationically polymerizable organic materials become non-tacky to a thickness of about 10 to 15 mils in less than about 60 seconds. However, certain applications such as encapsulation and protective coating of electronic components require deep sections of various cationic polymerizable organic materials, i. Thus, the use of traarylsulfonium salt photoinitiators has been somewhat limited.

The present invention, when using the photoinitiator of the general formula (1) with a specific organic sensitizer to be described later in the presence of ultraviolet or visible light epoxy resin, phenolformaldehyde resin, vinyl ether, episulfide and cyclic amine It is based on the fact that it is useful for deep curing of a wide variety of cationically polymerizable organic materials such as:

[(R) _a (R ¹ ) _b (R ² ) _c (S) ⁺ [Y] ^- (1)

In the above formula,

R is a general formula

, -O-, -S-,

,

또는 -(CH₂)_e-(여기서, R⁵는 탄소수 1 내지 13의 유기라디칼이고, e는 1 내지 4의 정수이다)이며, d는 0 또는 1이다]의 1가 유기라디칼이고, R¹은 탄소수 6 내지 13의 1가 방향족 유기라디칼이며, R²는 헤테로시클릭 또는 융합환 구조를 형성하는 탄소수 6 내지 20의 2가 방향족 라디칼이고, Y는 MQn 비-친핵성 음이온(여기서, M은 인 및 비소로부터 선택된 금속 또는 비금속이고, Q는 할로겐이며, n은 4 내지 6이다)이며, a는 1 내지 3의 정수이고, b는 0 내지 2의 정수이며, c는 0 또는 1(단, a+b+c의 합은 3이다)이다.[Wherein R ³ is a monovalent or divalent aromatic radical having 1 to 13 carbon atoms, R ⁴ is a divalent or trivalent aromatic radical having 6 to 13 carbon atoms, X is -S- or -O-, and Z is

, -O-, -S-,

,

Or-(CH ₂ ) _e- (wherein R ⁵ is an organic radical having 1 to 13 carbon atoms, e is an integer of 1 to 4), d is 0 or 1], a monovalent organic radical, and R ¹ Is a monovalent aromatic organic radical having 6 to 13 carbon atoms, R ² is a divalent aromatic radical having 6 to 20 carbon atoms forming a heterocyclic or fused ring structure, and Y is an MQn non-nucleophilic anion wherein M is A metal or nonmetal selected from phosphorus and arsenic, Q is halogen, n is 4 to 6, a is an integer from 1 to 3, b is an integer from 0 to 2, and c is 0 or 1 the sum of a + b + c is 3).

The cure rate of the cationic polymerizable organic material described above is considerably faster when using the photoinitiator of the general formula (1) than when using the slag initiator of the prior art.

Examples of non-nucleophilic anions denoted by Y in formula (1) are MQn, where M is a metal or nonmetal, Q is a halogen radical and n is 4 to 6, with PF ₆ ⁻ and AsF being preferred. ₆ ^- same as MF ₆ . Also, examples of Y include ^{_{perchlorate, CF 3 SO 3 -, C}} 6 H 4 SO 3 -, Cl -, Br -, F -, I -, nitrate, phosphate, CF ₃ CO ₂ ^- and FPO ₄ ^- contain Can be.

The present invention provides a photocurable composition comprising an effective amount of a cationic polymerizable organic material and a photoinitiator of the general formula (1).

Examples of the radical represented by R in general formula (1) are

; And corresponding radicals substituted with 1 to 4 alkyl or alkoxy radicals having 1 to 8 carbon atoms such as methyl, methoxy, ethyl, propyl or butoxy, or 1 to 4 halogen radicals such as chlorine, bromine or fluorine. Derivatives. More specific examples of radicals designated as R ¹ are phenyl, tolyl, xylyl, naphthyl or anthryl. Examples of radicals represented by R ² are

(Where Z is the same as described above).

Examples of the triarylsulfonium salt of the general formula (1) include compounds of the following structural formula:

The triarylsulfonium salt of formula (1) may be prepared by the method described in US Patent Application No. 046,115, filed June 6, 1979 and currently pending. Diarylthioethers can be reacted with diaryl iodonium salts in the presence of a copper (II) catalyst as follows:

Wherein R, R ¹ , M, Q and n are the same as described above.

U.S. Patent No. 2,807,648 to HM Pitts describes a method of directly fryingel crafts condensation of aromatic hydrocarbons using AlCl ₃ . Methods that can be used to prepare some of the photoinitiators of Formula (1) are based on the use of sulfur monochloride and chlorine as follows:

The triarylsulfonium salt is a preferred photoinitiator of the general formula (1) wherein Y is MQn or MF ₆ by substitution reaction using an alkali metal MQn or MF ₆ salt such as KMQn, KMF ₆ or NaMF ₆ . You can switch.

Organic polymers that can be used in the photocurable compositions of the present invention include epoxy resins such as monomeric, dimeric or oligomeric or polymeric epoxy materials containing one or more epoxy functional groups. For example, a resin produced from the reaction of bisphenol-A (4,4-isopropylidene diphenyl) with epichlorohydrin or a reaction of a low molecular weight phenolformaldehyde resin (novolak resin) with epichlorohydrin The resin produced by the above may be used alone or in combination with an epoxy-containing compound which is a reaction diluent. Diluents such as phenyl glycidyl ether, 4-vinyl cyclohexene dioxide, limonene dioxide, 1,2-cyclohexene oxide, glycidyl acrylate, glycidyl methacrylate, styrene oxide, or allyl glycidyl ether, etc. It can be added as a viscosity regulator.

In addition, the scope of these compounds can be extended to polymeric materials having terminal or positioning epoxy groups. Examples of these compounds are vinyl copolymers containing methacrylate or glycidyl acrylate as one of the comonomers. Other classes of epoxy-containing polymers that can be easily cured using the catalysts described above are epoxy-siloxane resins, epoxy-polyurethanes and epoxy-polyesters. Typically, such polymers have epoxy functional groups at their chain ends. The following references describe epoxy siloxane resins and methods for their preparation in more detail. [References: E. P. Plueddemann and G. Fanger, J. Am. Chem. Soc. 80,632-5 (1959). Epoxy resins are amine, carboxylic acid, as described in U.S. Pat.Nos. It can also be modified by a number of standard methods such as reacting with thiols, phenols or alcohols. Another co-reactant that can be used with the epoxy resin is a hydroxy-terminated flexibilizer, such as the hydroxy-terminated polyester described in the following references. Encyclopedia of Polymer Science and Technology Vol. 6, 1967, Interscience Publishers, New York, pp. 209-271, especially p.238]

Examples of the formaldehyde thermosetting organic condensation resin that can be used in the present invention are urea resins, phenol-formaldehyde resins, and the like.

In addition, melamine thiourea resins, melamine or urea aldehyde resins, cresol-formaldehyde resins can be used, and these are carboxy-, hydroxyl-, amino- and mercapto-containing, such as polyesters, alkyds and polysulfides. It can also mix and use with resin.

Examples of vinyl organic prepolymers that can be used in the preparation of the polymerizable composition of the present invention include the structure CH ₂ = CH-O- (CH ₂ -CH ₂ O) _n '-CH = CH ₂ , wherein n Is a polyfunctional vinyl ether (eg, 1,2,3-propane trivinyl ether or trimethylol propane trivinylether) of up to about 1,000 or more positive integers,

And low molecular weight polybutadiene having a viscosity at 200C of 200 to 10,000 centipoise. Products obtained by curing such compositions can be used for printing and inks and other conventional applications of thermosetting resins.

Another example of an organic material that can be used in the polymerization composition of the present invention is a cyclic ether that can be converted to a thermoplastic resin. Examples of such cyclic ethers include oxetane, such as the alkoxy oxetane and 3,3-bis-chloromethyloxetane described in Schroeter, US Pat. No. 3,673,216; Oxolanes such as tetrahydrofuran, oxepane, oxygen-containing spiro compounds, trioxane or dioxolane and the like.

-락톤(예 ; 프로피오락톤)과 같은 시클릭 에스테르, 1,3,3-트리메틸-아제티딘과 같은 시클릭아민, 및 하기 구조식의 물질과 같은 오가노 실리콘 시클릭을 사용할 수도 있다.In addition to cyclic ethers,

Cyclic esters such as -lactone (e.g. propiolactone), cyclic amines such as 1,3,3-trimethyl-azetidine, and organo silicone cyclics such as the materials of the following structural formulas can also be used.

Wherein R ″ is the same or different monovalent organic radical, such as methyl or phenyl, and m is an integer from 3 to 8.

Examples of organosilicon cyclics include hexamethyltrisiloxane, octamethyl tetrasiloxane, and the like. The products prepared according to the invention are high molecular weight oils and rubbers.

The photocurable composition of this invention can be manufactured by mixing a cationically polymerizable organic substance with the triarylsulfonium salt of General formula (1) of 0.1-15 weight% of an effective amount, for example, a photocurable composition.

In some cases, organic solvents such as acetone, nitromethane and acetonitrile may be used to facilitate mixing of the various components. If necessary, the diaryl iodonium salt may be produced in situ. In addition, to the curable composition, inert components such as silica, talc, clay, glass fibers, extenders, hydrated alumina, carbon fibers, and processing aids may be added in an amount of 500 parts per 100 parts by weight of the cationic polymerizable organic material. The curable composition of the present invention can be applied to substrates such as metal, rubber, plastics, molded parts of films, paper, wood, glass, textiles, concrete or ceramics.

Uses of the curable compositions of the invention are, for example, protective, decorative and insulating coatings, potting compositions, printing inks, sutures, adhesives, molding compounds, wire insulation, fiber coatings, laminations, impregnated tapes or varnishes and the like. .

In order to enable those skilled in the art to more easily carry out the present invention, the following examples are provided, which are not intended to limit the present invention. All parts in the examples are by weight.

Example 1

A mixture of 19.6 parts of 86% potassium hydroxide, 33 parts of thiophenol and about 120 parts of dimethyl acetamide is heated to 120 ° C. while stirring to remove water. About 6.5 parts of water are collected, then 26.3 parts of para-dibromobenzene is added to the resulting mixture and heated to reflux. After refluxing for 6 hours, the reaction mixture is cooled and 300 parts of water is added. The resulting tan solid is filtered off, washed several times with water and then the product is dried. Using this method, 34.7 parts of 1.4-dithiophenoxybenzene are obtained.

내지 75℃의 융점을 갖는 매우 밝은 황갈색의 결정성 생성물을 45%의 수율로 수득한다.The mixture of 7.35 parts of disulfide described above, 11.75 parts of diphenyliodonium hexafluoroarcinate and 0.2 parts of copper benzoate is heated to 120 ° C. for 3 hours. The resulting reaction mixture was washed several times with about 50 parts of diethyl ether each time and the remaining solid was recrystallized from 95% ethanol to give 69

A very light tan crystalline product having a melting point of from 75 ° C. to a yield of 45% is obtained.

Elemental analysis of the product is as follows:

Calculated Value:% C, 51.3; % H, 3.50; % S, 11.43

Found:% C, 51.21; % H, 3.59; % S, 11.37

Using this method, the triaryl sulfonium salt of the following structural formula is obtained.

Prepare 3% solution of photoinitiator as described above in 4-vinylcyclohexene dioxide. Similar solutions are prepared for triphenylsulfonium hexafluoro arcinate. The sticky extinction time of each solution is then measured using a GE H3T7 mercury arc lamp at a position 6 inches apart from the substrate coated with a 1 mil thick film on a glass slide. The photoinitiators of the present invention have a sticky disappearance time of less than 1 second, while the triphenylsulfonium hexafluoroarcinate mixture has a sticky disappearance time of about 5 seconds.

Example 2

내지 87℃의 융점을 갖는 트리아릴 설포늄 염을 31%의 수율로 수득한다. 이상과 같은 방법에 의하여 하기 구조식의 염을 수득한다.A total of 9.5 parts of chlorine is added to 37.2 parts of diphenylsulfide and 13.34 parts of aluminum chloride with stirring. The reaction mixture is poured onto 500 parts of ice to decompose the aluminum chloride complex. The obtained white semi-solid was washed twice with 200 parts of hot water per time, and then 27.8 parts of potassium hexafluoro arcinate and 500 parts of hot water were added to the residue for 1 hour at a temperature of 30 ° C. Stir. The orange oil is separated and the aqueous solution is recovered by decanting. It is washed several times with water and finally purified by washing with anhydrous ethyl ether. The product is then dried at 60 ° C. under reduced pressure for 16 hours. The product was then recrystallized from 95% ethanol, 77

Triaryl sulfonium salts having a melting point of from 87 ° C. are obtained in a yield of 31%. The salt of the following structural formula is obtained by the above method.

Example 3

Consisting of 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxy cyclohexane carboxylate and triphenyl sulfonium hexafluoro arcinate (prior art) as photoinitiator and photoinitiator of the present invention (Example 2), respectively Prepare a 3% solution. An increasing thickness of film is applied on the glass plate and cured for 1 minute using a GE H3T7 medium pressure mercury arc lamp at a distance of 6 inches from the film. The maximum thickness of the film that can be cured in a non-tacky state using the photoinitiators described above is as follows:

TABLE I

From the above results, it can be seen that the photocurable composition of the present invention containing the photoinitiator of the general formula (1) is cured to a thickness of at least four times that of the photocurable composition of the prior art.

Example 4

Another photocurable composition is prepared using the photoinitiator of Example 2 and cyclohexene oxide as the cationically polymerizable organic material. The solution contains 0.021 moles of photoinitiator per liter of cyclohexene oxide. A portion (3 mL) of these photocurable mixtures are taken and irradiated under sealed conditions using a Hanovia 450 medium pressure mercury arc lamp. The aliquots are taken out periodically, quenched at various times and precipitated in methanol to separate the polymer. The photocured product is recovered by filtration and dried overnight at 60 ° C. under vacuum. The polymer is weighed to determine the% conversion. The table below lists the results obtained in% conversion.

TABLE II

Example 5

The procedure of Example 4 is repeated using 2-chloroethylene vinyl ether instead of cyclohexene oxide. A 4 ml aliquot of the mixture was irradiated according to the same method as in Example 4 to obtain the following% conversions:

TABLE III

From the above results, it can be seen that the photoinitiator of the present invention is superior to the photoinitiator of the prior art.

Example 6

The procedure of Example 4 is repeated using trioxane and methylene chloride, respectively, instead of cyclohexene oxide. A solution containing 1.386 × 10 ⁻¹ mole trioxane and 1.386 × 10 ⁻⁴ mole photoinitiator, respectively, was prepared. The mixture is then irradiated by the method of Example 5 to yield the following% conversions.

Table IV

Example 7

A 1% solution consisting of diethylene glycol divinyl ether and triphenyl sulfonium hexafluoroarcinate and a 1% solution of diethylene glycol divinyl ether and the photoinitiator of the invention in Example 2 were prepared. Take 10 grams from each of these solutions and pour into a 2 inch diameter cup and irradiate for 5 seconds using a GE H3T7 medium pressure mercury arc lamp at 23 cm apart. The cured solid polymer is taken out of the cup and washed with acetone to remove unreacted divinyl ether and dry. The weight of each of the anhydrous polymers is proportional to the curing thickness of the sample.

From the above measurement results, it can be seen that the photocurable composition of the present invention containing the photoinitiator of the general formula (1) is cured to a thickness of 2.6 times or more than the photocurable composition containing the photoinitiator of the prior art. On a molar basis, the compounds of the present invention are 3.2 times more effective than the compounds of the prior art.

Example 8

A 2% solution of Mehtylon 75201, phenol-formaldehyde resol of the following structural formula, and triphenylsulfonium hexafluoroarcinate (prior art) as a photoinitiator and the photoinitiator of the invention in Example 2, respectively:

The two solutions prepared were coated on a glass plate with a 3 mil thick film and irradiated with ultraviolet light using a GE H3T7 mercury arc lamp at a distance of 6 inches. The resin film containing the photoinitiator of the present invention takes 1.5 minutes to become non-tacky, whereas the film containing the photoinitiator of the prior art takes 5.5 minutes under the same conditions.

Example 9

The procedure of the above-described example is repeated using a silicone resin of the following structure instead of phenolformaldehyde:

When the sample containing the photoinitiator in Example 2 was irradiated for 10 seconds, it became non-tacky and was not removed even by washing with acetone. On the other hand, the sample containing triphenyl sulfonium salt is soft and is easily removed by acetone.

Example 10

The procedure of the above described example is repeated using a resin of the following structural formula (A-187 available from Union Carbide):

While curing of 3 mil thick films containing photoinitiators of the prior art requires irradiation for 75 seconds, curing of films of the same thickness containing the photoinitiator of the present invention requires only 30 seconds of irradiation.

Example 11

A 3% solution of each of the photoinitiators of the following structural formula in the substituted group epoxy resin (ERL4221) was applied onto a glass plate and cured according to the method of Example 7:

The resulting cured film is washed with acetone, then dried and weighed. The photoinitiator of the present invention provides a film twice the thickness of the photoinitiator film of the prior art.

Example 12

A 3% solution of the photoinitiator of Example 2 in 3,4-epoxy cyclohexylmethyl-3 ', 4'-epoxy cyclohexane carboxylate is prepared. The sample is divided into two portions, one of which is added 0.5% by weight of parylene and then exposed to visible light from a GE H3T7 lamp equipped with a filter to remove all ultraviolet radiation at wavelengths below 390 nm. Samples containing perylene dye sensitizers cure within 30 seconds, while samples not containing it do not cure after 5 minutes of irradiation. This example illustrates the use of a dye photosensitizer in combination with the photoinitiator of the present invention to provide a visible light curable composition.

Example 13

A mixture of 11.2 parts (0.02 mole) of diphenyl-4-thio phenoxyphenyl sulfonium hexafluoroarcinate, 20 parts of glacial acetic acid, and about 4 parts of 30% hydrogen peroxide is stirred at room temperature for 18 hours. The mixture is then poured into 200 parts of distilled water. The resulting crude product is washed with water and then with anhydrous ethyl ether. By elemental analysis, spectroscopic analysis, and the production method, the product has the following structural formula.

The 3% solution of the photoinitiator in 4-vinyl cyclohexene deoxyside cures to a non-tacky film when irradiated using a GE H3T7 lamp at a distance of 10 inches.

Example 14

내지 74℉의 융점을 가지며, 원소분석, 분광분석 및 제법등을 기초로 하여 하기의 구조식을 갖는다.11.2 parts (0.02 mole) of the sulfonium salt in Example 2 is added to about 15 parts of acetone, and then 2 parts of hydrogen peroxide are slowly added while cooling. The solution is stirred overnight and then poured into 200 parts of water. The oil obtained is washed with water and solidified by washing with anhydrous ethyl ether. After drying under vacuum overnight the product obtained is 70

It has a melting point of from 74 ° F., and has the following structural formula based on elemental analysis, spectroscopic analysis, and the like.

When the 3% solution of the photoinitiator in 4-vinylcyclohexene dioxide is cured by the method of the above-described example, it is cured into a non-tacky film within 2 seconds.

Although the embodiments described above illustrate only some of the many variations that can be used in the practice of the present invention, the present invention is broadly directed to UV-curable compositions, certain triarylsulfonium salts within the general formula (1) category, and these materials. It is clear that the present invention relates to a manufacturing method of. The expression "effective amount" as used in the present invention means an amount necessary for curing the organic material in the case of triarylsulfonium salt. 0.1 to 15% by weight of a triarylsulfonium salt may be used based on the weight of the photocurable composition.

Claims (1)

A photocurable composition comprising 85 to 99.9% by weight of a cationically polymerizable organic material selected from an epoxy resin, a phenol-formaldehyde resin and a vinyl ether and 0.1 to 15% by weight of a triarylsulfonium salt of the following general formula (1): [(R) _a (R ¹ ) _b (R ² ) _c S] ⁺ [Y] ^- (1) In the above formula, R is a general formula

[Wherein R ³ is a monovalent or divalent aromatic radical having 1 to 13 carbon atoms, R ⁴ is a divalent or trivalent aromatic radical having 6 to 13 carbon atoms, X is -S- or -O-, and Z is

Or-(CH ₂ ) _e- (wherein R ⁵ is an organic radical of 1 to 13 carbon atoms, e is an integer of 1 to 4), d is 0 or 1], a monovalent organic radical of R ¹ Is a monovalent aromatic organic radical having 6 to 13 carbon atoms, R ² is a divalent aromatic radical having 6 to 20 carbon atoms forming a heterocyclic or fused ring structure, and Y is an MQn non-nucleophilic anion, wherein M is A metal or nonmetal selected from phosphorus and arsenic, Q is halogen, n is 4 to 6, a is an integer from 1 to 3, b is an integer from 0 to 2, and c is 0 or 1 (where a the sum of + b + c is 3).