JPH03149216A - Photocurable material - Google Patents

Abstract

PURPOSE:To obtain a photocurable material improved in photocurable, electrical, antistaining, and adhesive properties by compounding an epoxy resin, a specific onium salt, an organoaluminum compd., and a sensitizer together. CONSTITUTION:A photocurable material which comprises 100 pts.wt. epoxy resin, 0.1-5 pts.wt. onium salt of the formula (wherein Q is N, P, S, O, Si, or C; R<1> to R<n> are each a group directly bound to Q, and area each an alkyl or acyl group optionally contg. an arom. group, an oxoalkyl group optionally substd. by an arom. ring, a aryl group such as a phenyl or naphthyl group, or an aryl group substd. by an alkyl or alkoxy group; and n is 1-5, and when Q is N or P, S or O, or Si or C, n is 4, 3, or 5, respectively) comprising a hydrogencarbonate ion as an anion and a central atom consisting of N, P, S, Si or C, 0.001-10 pts.wt. organoaluminum compd. [e.g. tris(ethylacetoacetato) aluminum], and 0.001-0.5 pts.wt. sensitizer having a polymerizable group.

Description

[Detailed description of the invention] [Summary] A resin composition with improved photocurability,
The purpose is to provide a photocurable material that has good photocurability with visible light and has excellent electrical properties, resistance to staining with various solutions used, and adhesiveness. (A) Epoxy resin 100 parts by weight (8)
Onium salt with hydrogen carbonate ion as an anion and nitrogen, phosphorus, sulfur, oxygen, silicon, or oxygen as the central atom (C) 0.1 to 5 parts by weight of aluminum organic compound (D) Polymerizable sensitizer o, oot~0 having a substituent
．． 5 parts by weight.

[Industrial application field]

FIELD OF THE INVENTION This invention relates to photocurable materials with improved curability. More specifically, the cured product has electrical properties and adhesive properties suitable for use as an insulating material for electrical equipment, a resist material, and especially as a sealing or sealing material in the manufacture of flat display devices such as liquid crystal cells. The present invention relates to photocurable materials.

[Conventional technology]

In recent years, the process of curing resin by light irradiation has attracted attention from the viewpoint of energy saving and workability. Among them, photo-force thionic polymerization of epoxy resins has a wide selection range of epoxy resins, and shrinkage during curing is less than that of photo-radical polymerization of acrylic resins, resulting in a high glass transition temperature Tg due to structural regularity. It is expected that adhesive strength will be developed (for example,
-14279, JP-A-55-65219, etc.)
.

However, when epoxy resins are cured using conventional acid generators and catalysts, although the resulting cured products have good mechanical properties and heat resistance, ionic impurities are generated from the acid generators and catalysts. This poses a problem in that it significantly deteriorates the electrical properties in insulation applications, the contamination of developing solutions, plating solutions, and etching solutions in resist applications, and the liquid crystal performance in liquid crystal sealing and sealing applications.

On the other hand, it is known that ionic impurities are extremely rarely generated from sensitizers or color formers having polymerizable substituents (Japanese Patent Laid-Open No. 147001/1983).

[Problems to be solved by the present invention]

Since the problem of the conventional technology is due to the inclusion of a large amount of ionic impurities in the cured product after photocuring, the present invention
By finding a composition that reduces ionic impurities remaining in the cured product, it has good photocurability under ultraviolet and visible light, and the resulting cured product has excellent electrical properties, stain resistance from various solutions used, and adhesion. The purpose of this invention is to provide a photocurable material with excellent properties.

[Means to solve the problem]

The present invention consists of the following components (A) to (D): (A) 100 parts by weight of an epoxy resin (8) An onium whose anion is hydrogen carbonate ion and whose central atom is nitrogen, phosphorus, sulfur, oxygen, silicon, or oxygen. Salt 0, 1 to 5 parts by weight (C) Aluminum organic compound 0.001 to 10 parts by weight (D) Sensitizer having a polymerizable substituent 0.001 to 0
．． A photo-curing material containing only 5 parts by weight as an essential component, which cures rapidly by irradiation with a single line of active energy including ultraviolet and visible light, has good internal curing properties, and contains no ionic impurities. It is a composition with a small amount of

The epoxy resin (A) used in the present invention is a compound having two or more oxirane rings either inside the resin, at the end, or in the cyclic structure. Particularly useful epoxy resins include bisphenol A epoxy resins, aliphatic epoxy resins, bisphenol F epoxy resins, novolac epoxy resins, hydrogenated bisphenol diglycidyl ether resins, and epoxidized polybutadiene. Further, resins obtained by chain-extending the above-mentioned epoxy resins with polyhydric alcohols, polyhydric amines, polyhydric carboxylic acids, etc. can be used.

These various epoxy resins as component (A) can be used alone or as a copolymer of two or more.

The onium salt (B) used in the present invention, in which hydrogen carbonate ion is an anion and nitrogen, phosphorus, sulfur, silicon, or carbon is the central atom, has the following formula; % formula % [where Q is a nitrogen atom, phosphorus atom, sulfur atom, oxygen atom, silicon atom, or carbon atom, R1 to R11
are each a substituent directly bonded to Q, such as an alkyl group, an acyl group (sometimes containing an aromatic group), an oxoalkyl group, an oxoalkyl group substituted with an aromatic ring, a phenyl group, or a naphthyl group. Represents a step aryl group, or an aryl group substituted with an alkyl group or an alkoxy group, where n is an integer from 1 to 5, 4 in the case of a nitrogen atom or phosphorus atom, 3 in the case of a sulfur atom or an oxygen atom, and 3 in the case of a sulfur atom or an oxygen atom. In the case of an atom or a carbon atom, it is 5]. The above-mentioned substance releases carbonic acid (H2C), which is a protonic acid, when irradiated with a single line of active energy such as ultraviolet or visible light, which initiates cationic polymerization of the epoxy resin. Carbonic acid does not contain atoms that generate ionic impurities such as halogens. Among these, diphenylsulfonium hydrogencarbonate (Ph2SHCO3) has a good synthesis yield.
is preferable. The blending amount of component (B) is 0.1 to 5 parts by weight, preferably 0.1 to 5 parts by weight, per 100 parts by weight of component (A).
It is 5 to 4 parts by weight. If the amount is less than 0.1 part by weight, sufficient curability will not be obtained, Tg will be low, and barrier properties will be insufficient. On the other hand, if it exceeds 5 parts by weight, the cost will be high and the electrical properties, contamination of various solutions used, adhesive properties and liquid crystal properties will deteriorate.

The aluminum compound (C) used in the present invention has an organic group such as an alkyl group, a phenyl group, a haloalkyl group, an alkoxy group, a phenoxy group, an acyloxy group, a β-diketonato group, or an 0-carbonylphenorad group. It is a compound formed by bonding to atoms. The above-mentioned substances are activated by irradiation with a line of active energy including ultraviolet and visible light, and therefore are catalysts that accelerate the rate of cationic polymerization of -epoxy resins. Among these, tris(ethylacetoacetate)aluminum (A I (CHsCOCHCOOCJs) s
) is preferred. The blending amount of (C) tr, is from o, oot to 10 parts by weight per 100 parts by weight of component (A),
Preferably it is 0.05 to 3 parts by weight. The amount added is 0.0
If the amount is less than 0.01 parts by weight, sufficient curability will not be obtained and T
g is low and barrier properties are insufficient. On the other hand, if it exceeds 10 parts by weight, the cost will be high and the electrical properties, contamination of various solutions used, adhesive properties and liquid crystal properties will deteriorate. These various aluminum compounds as component (C) can be used alone or in a mixed system of two or more.

The sensitizer having a polymerizable substituent (D) used in the present invention has the following formula; , methacryloyl group, allyl group, epoxyglycidyl group,
or represents a substituent containing a bicycloorthoester group, spiroorthoesters, or spiroorthocarbonates, and M represents a group of a polynuclear aromatic or polynuclear heterocyclic compound and its derivatives. The above substances have absorption in the ultraviolet and visible regions of 320 to 500 na+.

Select so that the absorption region can be set according to the wavelength of the exposure source. The blending amount of component (D) is 0.001 to 0.5 parts by weight per 100 parts by weight of component (A).

Preferably it is 0.05 to 0.1 part by weight. Blend amount is 0
．． If the amount is less than 0.001 parts by weight, the effect of adding the sensitizer will not improve the curability or improve the properties of the cured product. On the other hand, if it exceeds 0.5 part by weight, it will be eluted from the cured product, resulting in poor curability and deterioration of various properties.

In addition to the above-mentioned components (A) to (D), the following components (E) to (I) can be added to the resin composition according to the present invention, if necessary.

The color forming agent of component (E) is an aryl amine, a primary aromatic amine, a secondary aromatic amine, and a leuco dye.

The above substances change from colorless to colored upon exposure to light. Color development area can be set according to the exposure source. (E
) The blending amount of component (A) is 0.00 parts by weight per 100 parts by weight of component (A).
0001 to 0.005 parts by weight, preferably 0.0
005 to 0.001 parts by weight. Blend amount 0.0001
If the amount is less than part by weight, the color will not be clear. On the other hand, 0
．． If the amount exceeds 0.05 parts by weight, it will be eluted from the cured product, resulting in poor curability and deterioration of various properties.

Acrylic ester or methacrylic ester monomer is used as component (F) in order to carry out curing by photo-force thionic polymerization and photo-radical polymerization system using the radical polymerization initiating ability of radicals generated by photolysis of onium salt. The body can be incorporated within a range that does not impair the effects of the present invention.

The blending amount of the acrylic ester or methacrylic ester monomer is within 40 parts by weight per 100 parts by weight of component (A). If it exceeds this, the monomer remains and good film formation cannot be achieved.

In addition, ingredients (
It is possible to incorporate a solvent as G). As this solvent, various solvents belonging to ketone, ester, ether, aliphatic or aromatic hydrocarbons are used. The blending amount of the solvent is preferably within 20% by weight of the polymerization ratio contained in the composition. If this is exceeded, the viscosity will drop too much and it will flow.

Furthermore, in order to reduce the viscosity of the composition or adjust the reactivity, a reactive diluent having one or more epoxy groups in the molecule may be blended as component (H).

As this reactive diluent, for example, butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, etc. are used. The amount of the reactive diluent to be blended is within 20 parts by weight per 100 parts by weight of the ilE component (A). If it exceeds this range, good curability and various properties, which are the objectives of the present invention, will be impaired.

Furthermore, as component (I), various modifying additives can be blended as necessary for purposes such as modifying physical properties. For example, fillers such as silica or mica; Aerosil, which is a scaly silica to impart printability;
or a thixotropic agent such as bentone, which is a hydrate of aluminum oxide and silicon oxide; a leveling agent such as 3M's Fluorade; a silicone-based, titanate-based,
or other coupling agents.

In order to cure the resin composition according to the present invention, wavelength 3
Ultraviolet and visible light of 20 to 5QQnm are effective.

Examples of this exposure source include a mercury lamp, a metal palite lamp, and a gas laser. Other active energy sources that can be used for curing include X-rays, electron beams, and the like.

Further, the composition of the present invention is sufficiently cured by irradiation with an active energy source and exhibits properties suitable for the purpose, but even better properties can be obtained by leaving it in a heated constant temperature bath after irradiation. This temperature range is 50 to 80
An example is 0.5 to 5 hours at °C.

Furthermore, the photocurable material according to the present invention can be used in particular for protective and insulating coatings, printing inks, sealants, photoresists, solder resists, adhesives for botting or lamination, and glass cells of flat display devices such as liquid crystal cells. Used as a forming adhesive or various other adhesives.

[For production]

In the epoxy resin (A), the oxirane ring is opened by a cation to cause polymerization, but the main feature of the present invention is that it contains (B), a photoactive thionic polymerization initiator, and its action is An onium salt having bicarbonate as an anion is decomposed by light irradiation, releasing a protonic acid with cationic polymerization ability. This initiation mechanism is shown by the following formula using diphenylsulfonium hydrogencarbonate (Ph2511C03) as an example.

ph, s" HCO3--→ [Ph, S" HCO3
−) [Ph, S” HCO3−) −→PhS” 10ph +HCOs−) PhS++ZH−1→PhS”−
H+Z IIHc mouth.

PhS+-H--→PhS+H" 2ph--→ph-phPhJuZH,
PhH+z 2H is the organic solvent used in the practice of this invention.

A protic acid represented by HHCO3 in the formula is released.

This photodecomposition reaction occurs due to the absorption of ultraviolet and visible light by the cationic moieties represented by Ph and S'' in the formula. This cationic moiety usually has an absorption maximum below 300no+. [Journal
of Polymer Science, Polym
er Chemistry Bditjon.

17, 977 (1979)) Exposure sources such as mercury lamps, metal halide lamps, and gas lasers have an energy distribution in the ultraviolet and visible regions of longer wavelengths of 320 to 500 nm.

Therefore, a sensitizer is added to expand the sensitive wavelength range.

The compound having a polymerizable substituent of the sensitizer (D) is 3
Since it has absorption in the ultraviolet and visible regions of 20 to 500 rua, the absorption region can be set according to the exposure source. Although these sensitizers are polymerization systems involving radicals, their effectiveness in photo-forced thionic polymerization has also been recognized. (Photo
graphic science andBngine
ering, 23.140 (1979)) Furthermore,
The aluminum organic compound of the catalyst (C) is activated by light irradiation and accelerates the cationic polymerization rate of the epoxy resin. The activation mechanism is presumed to be that aluminum acts as a weak Lewis source and promotes the opening of the oxirane ring.

Moreover, it changes from a colorless state to a colored state by the action of radicals generated by photolysis of the onium salt of the color former (E).

The above composition has good photocurability. Moreover, since each component does not contain atoms such as halogens that generate ionic impurities, the resulting cured product is a photocurable material with excellent electrical properties, resistance to contamination from various solutions used, and adhesive properties. .

Furthermore, in the embodiments of the present invention, when components having a benzene ring in common are used, the compatibility of the components is very good.

Furthermore, storage stability can be ensured for more than half a year even considering dark reactions.

〔Example〕

Synthesis examples and examples of the present invention are shown below, but the present invention is not limited thereto.

Synthetic Nidiphenyliodonium Chloride (Ph, IC
f) 10g (0,03moj) of 300-300g aqueous solution and sodium bicarbonate (NaHC) sHOg (0,03moj)
A 50d aqueous solution of 12moj) was mixed at room temperature and left to stand for an additional hour, after which water as a solvent was removed using an evaporator. After washing the precipitate with a small amount of water, 95%
Recrystallized from ethanol.

9.0 g of diphenyliodonium hydrogencarbonate (PhzlllCOs) obtained in this way was dissolved in chlorobenzene 10071, and 8.0 g of diphenyl sulfide (PhzS) and 0.2 g of copper benzoate (anhydrous) were added thereto.
g was added thereto, and the mixture was stirred at -120 to 125° for 3 hours under a nitrogen stream. After cooling this by leaving it at room temperature, the precipitated crystals were
It was recrystallized from 5% ethanol. Diphenylsulfonium hydrogencarbonate (Ph2SHCO3) thus obtained
j; [The rate was 92.2%.

Example 1: 20 g of ethyl cellosolve (manufactured by Wako Pure Chemical Industries, Ltd.) A photosensitive liquid having this composition was spin-coded onto a 50×50 m silicon substrate to form a photosensitive plate having a dry film thickness of 511 m. Using this photosensitive plate, it was cured by irradiation with an ultra-high pressure mercury lamp (3 kml) for 20 seconds. No change was observed after conducting an electrolytic corrosion test for 500 hours.

Example 2: 20 g of ethyl cellosolve (manufactured by Wako Pure Chemical Industries, Ltd.) A photosensitive liquid having this composition was spin-coded onto a 50 x 50 x silicon substrate to form a photosensitive plate having a dry film thickness of 5 x 5 mm. Using this photosensitive plate, exposure was performed using an argon ion laser (4 kM) through a photomask, and a toluene/xylene mixture was used as a developer to confirm the reproduction of the 90j-line.

<Analysis of ionic impurities> Residual ions (n/g) were determined by ion chromatography. The results are shown in the table.

Table I Iozo 1 Example II Example 21 Comparative Example 11 Comparative Example 21
F <1 <1 <
1 <IC-<2 <2
5 4N02 < 5
< 5 < 5 (58r
< 2 < 2 < 2 < 2N
0. - <2 <2 10
10PO43-<5 <5
<5 <5SO, -5050150160 I-<50 <50 120
150N1,” 22 <5
28 15 Comparative Example 1 The same procedure as in Example 1 was carried out using 0.1 g of diphenyliodonium hydrogencarbonate (Ph21HCO,) in place of (B) and (C) in Example 1. Ultra-high pressure mercury lamp (3
kN) for 30 seconds. When the electrolytic corrosion test was conducted for 500 hours, blistering occurred.

Comparative Example 2 The same procedure as in Example 2 was carried out using diphenyliodonium hydrogencarbonate (PhzlHCDJ O,lg) in place of (B) and (C) in Example 2. Reproduction of the 130 square line could be confirmed. did it.

〔Effect of the invention〕

According to the present invention, there is provided a photocurable material which has good photocurability due to its composition containing few ionic impurities, and which also has excellent electrical properties of the obtained cured product, resistance to contamination with various solutions used, and adhesiveness. can.

Claims (1)

[Claims] Components of the following (A) to (D): (A) 100 parts by weight of epoxy resin (B) Hydrogen carbonate ion is an anion, and nitrogen, phosphorus, sulfur, oxygen, silicon or oxygen is the central atom Contains 0.1 to 5 parts by weight of an onium salt (C) 0.001 to 10 parts by weight of an aluminum organic compound (D) 0.001 to 0.5 parts by weight of a sensitizer having a polymerizable substituent A photocurable material characterized by: