JPH0236221A - Production of curable resin composition - Google Patents

Abstract

PURPOSE:To easily obtain the subject composition without causing the coagulation of particles and the change of surface state, etc., by polymerizing a polyfunctional epoxy compound in a liquid compound containing a radically polymerizable functional group under stirring, thereby dispersing fine particles of the epoxy compound polymer. CONSTITUTION:The objective composition is produced by polymerizing one or more kinds of polyfunctional epoxy compound (e.g., vinylcyclohexene dioxide or bisphenol A diglycidyl ether) in a liquid compound containing one or more radically polymerizable functional groups in the molecule [e.g., beta-hydroxylethyl (meth)acrylate] under stirring, thereby dispersing fine particles of the epoxy compound polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Object of the Invention [Field of Industrial Application] The present invention relates to a novel method for producing a radically polymerizable curable resin composition in which crosslinked fine epoxy resin particles are dispersed. The radically polymerizable curable resin composition obtained by the present invention is cured by active energy rays such as ultraviolet rays, electron beams, X-rays, and radiation, or by heating, and specific applications include paints, resists, inks, There are adhesives, potting agents, sealants, etc.

[Prior Art] Physical properties such as tensile strength, hardness, adhesion, bending strength, and abrasion resistance of a cured product obtained from a radically polymerizable curable resin composition that is cured by irradiation with active energy rays or heating. As a method for improving the temperature, there is a known method of dispersing various particulate resin cured products with a size of several microns or less (Japanese Patent Application Laid-Open No. 63-17903, JP-A No. 62129355, JP-A No. 61-162501, JP-A No. 61-162501, JP-A-61-162501, (Sho 51-109942, etc.)

In this case, it is essential to disperse the fine particulate resin cured material, which has been previously produced in a separate process, into the curable resin by some method, and by synthesizing, separating and drying the fine particles for dispersion, - It must go through many steps, such as first taking it out as a solid and then dispersing it in a curable resin. In addition, during the drying process of fine particles manufactured in a separate process, undesirable phenomena such as particle aggregation and changes in the surface state of the particles may occur, which may affect the dispersion stability of the fine particles in the curable resin composition. etc., and may cause separation and precipitation in some cases.

On the other hand, in order to obtain fine particles dispersed in a curable resin, a method is known in which a radically polymerizable monomer, which is a component forming the fine particles, is polymerized in an epoxy compound (Japanese Patent Application Laid-open No. 6O-55023). However, there is no known method for polymerizing components that form fine particles in a radically polymerizable curable resin.

[Problems to be Solved by the Invention] The present invention is capable of stably dispersing fine particles without going through many steps such as synthesizing, separating and drying the fine particles in separate steps, and then dispersing them in a curable resin. An object of the present invention is to provide a method for producing a radically polymerizable curable resin composition.

(B) Structure of the Invention [Means for Solving the Problems] As a result of various studies conducted by the present inventors in order to solve the problems of the above-mentioned known methods, the present inventors have developed a radically polymerizable curable polyfunctional epoxy compound. Discovered the fact that it is possible to obtain a radically polymerizable curable resin composition in which fine particles of a crosslinked epoxy compound are dispersed without adversely affecting the radical curability of the curable resin even when polymerized in a resin. , we have completed the present invention.

That is, the present invention provides an epoxy compound polymer by polymerizing one or more polyfunctional epoxy compounds under stirring in a liquid compound having at least one radically polymerizable functional group in the molecule. The present invention relates to a method for producing a curable resin composition characterized by dispersion.

Hereinafter, the manufacturing method of the present invention and the curing method of the manufactured curable resin composition will be described.

Liquid compounds having at least one radically polymerizable functional group in the molecule> The above compounds are polymerized by irradiation with active energy rays or heating, and liquid compounds that polymerize by irradiation with active energy rays include: , a monomer containing at least one (meth)acryloyl group (acryloyl group and/or methacryloyl group, hereinafter the same) in the molecule,
Compounds include oligomers or polymers. Specific examples of such compounds include β-hydroxyethyl (meth)acrylate, β-hydroxypropyl (meth)acrylate, β-hydroxyethyl (meth)acryloyl phosphate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate. , ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, Tribrobylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,
dipentaerythritol tetra(meth)acrylate,
dipentaerythritol penta(meth)acrylate,
Dipentaerythritol hexa(meth)acrylate or tris [2(meth)acryloyloxyethyl]
Isocyanurates, polybasic acids and hydroxyalkyl (
Examples include mono-, di-, tri-, or higher polyesters with meth)acrylates or urethane (meth)acrylates.

On the other hand, specific examples of liquid compounds that can be cured by heating include unsaturated polyester resins, urethane acrylate resins, polyester acrylate resins, spiran acrylate resins, and polyether acrylate resins.

It is desirable that the above liquid compound having a radically polymerizable functional group be in a liquid state and not contain any solid matter at room temperature or at the fine particle synthesis temperature. If the compound itself is liquid, it can be used alone or in a mixture of two or more, and if it is not liquid itself, it can be combined with another liquid compound that can be cured by the same type of curing means. By mixing, it can be used as a liquid compound. In addition, the above-mentioned liquid compound is 300Q c
Those having a viscosity of less than ps are preferred.

<Polyfunctional epoxy compound> The polyfunctional epoxy compound used in the present invention is a liquid epoxy compound containing two or more epoxy groups that can be cured using a catalyst or a curing agent.

These polyfunctional epoxy compounds are preferably those that do not adversely affect the curability of the radically polymerizable liquid compound.
As such compounds, various compounds can be used, such as branched or straight aliphatic, cycloaliphatic, aromatic or heterocyclic [containing O and/or N heteroatoms]. Specific examples include vinyl cyclohexene dioxide, diglycidyl ether to bisphenol, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, dipentene oxide, 14-butanediol diglycidyl ether, and phenol formaldehyde resol. or polyglycidyl ether of Novolanc resin, resorcinol diglycidyl ether, 1
．． Examples include 3-bis(23-epoxypropyl-5,5-dimethyl-2°4-imidasyringedione).

<Monofunctional epoxy compound> In addition to the above-mentioned polyfunctional epoxy compound, a monofunctional epoxy compound having one epoxy group in the molecule can be used in combination as a component for forming fine particles made of a polymer of an epoxy compound. Specifically, propylene oxide, styrene oxide, glycidol, butadiene oxide, glycidyl propionate, etc. can be used.

<Dispersion stabilizer> When the above-mentioned epoxy compound is polymerized in a radically polymerizable liquid compound with stirring to obtain a particulate resin, a component that serves as a dispersion stabilizer for the particulate resin may be present if desired. It's okay. A suitable dispersion stabilizer has in its structure a part that is reactive with the epoxy compound that forms particulate resin and a part that is soluble in a radically polymerizable liquid compound. Examples include a graft polymer having an epoxy group in the trunk and a branch component soluble in a radically polymerizable liquid compound, and a macromonomer having an epoxy group at the end and a component soluble in a radically polymerizable liquid compound.

<Method for synthesizing fine particles> Specific preferable synthesis conditions are as follows. That is, 1 to 50 parts of one or more polyfunctional epoxy compounds and 0 to 50 parts of a monofunctional epoxy compound are added to 100 parts by weight of a radically polymerizable liquid compound (hereinafter "parts" refer to parts by weight).
70 parts, 90 parts or less as the total amount of the epoxy compound,
Optionally, 1 to 70 parts of a dispersion stabilizer, and optionally an appropriate amount of a radical polymerization inhibitor and an appropriate amount of a cationic polymerization catalyst are mixed all at once or by dropwise addition.

After bulk mixing or during dropwise mixing, the mixture is
“Hold at a reaction temperature of C for several hours to several days while stirring,
During this time, air may be blown in if desired. The above stirring operation is performed to form uniform fine particles, and the optimal stirring conditions can be easily determined experimentally. When stirring using a stirring blade, 20
Stirring at a rotational speed of 0 to 800 rpm is effective. By such a polymerization operation, a radically polymerizable curable resin composition in which crosslinked fine epoxy resin particles are dispersed can be obtained.

If desired, it is also possible to introduce various functional groups such as double bonds onto the surface of the micro epoxy resin particles. For example, as a method for introducing double bonds, glycidyl (
There is a method in which meth)acrylate is simultaneously charged with other epoxy compounds to form epoxy resin particles, or more preferably, the glycidyl (meth)acrylate is added once particles have been formed to a certain extent. In this way, the functional group having a double bond introduced into the surface of the epoxy resin particles polymerizes at the same time as the radically polymerizable compound of the matrix is cured, making it possible to strengthen the bond at the interface between the particles and the matrix. can.

The radically polymerizable curable resin composition in which minute epoxy resin particles are dispersed can be cured using active energy rays or heat in a conventional manner, and if desired, a suitable initiator and /Or a suitable amount of sensitizer may be added.

Specific uses of radically polymerizable curable resin compositions in which minute epoxy resin particles are dispersed include paints, resists, inks, adhesives, pottings, and the like. In particular, the radically polymerizable curable resin composition of the present invention has cross-linked micro epoxy resin particles dispersed therein, forming a so-called "sea-island structure", so that it has a variety of properties compared to a composition in which they are not dispersed. It has favorable physical properties. for example,
In addition to improving mechanical properties such as tensile strength, hardness, adhesion, bending strength, and abrasion resistance, shrinkage during curing due to active energy rays and heat can be reduced, and in the case of inorganic fillers, In comparison, it has advantages such as good transparency, excellent deep curability, and less viscosity increase because it is a non-uniformly dispersed system.

〔Example〕

The present invention will be explained in detail below with reference to Examples. Note that "parts" and "%" in the examples are based on weight.

Example 1 4 flasks (300m) equipped with a stirrer and thermometer
l) Toagosei Chemical Industry ■Product Aronics 7x M-30
9 () Limethylolpropane triacrylate) 100
and hydroquinone monomethyl ether (inhibitor) 0
．． I prepared 05 parts.

While stirring the contents of the flask, add 20 parts of Nagase Chemical Industries' product Denacol EX-192 (a mixture of dodecanyl glycidyl ether and tridecanyl glycidyl ether), and Nagase Chemicals' product Denacol EX-51.
2 (polyglycerol polyglycidyl ether) and 40 parts of the above-mentioned Aronix M-309, and a dropping solution consisting of 2 parts of boron trifluoride diethyl etherate and 20 parts of Aronix M-309. , respectively, were added dropwise simultaneously over 30 minutes at room temperature. After the dropwise addition started, the flask internal temperature rose by about 5°C, and after the dropwise addition was finished, the flask internal temperature gradually decreased. Continue stirring even after dropping, and after starting dropping
The synthesis was completed in 0 hours.

The product is a pale liquid with a viscosity of 12 at 25°C.
5 cps, and this product contained components insoluble in THE (tetrahydrofuran, hereinafter the same), acetone, and toluene. Particle size distribution measuring device (Ageba Seisakusho,
According to measurement using a centrifugal CAPA-500), fine resin particles with an average particle size of 0.15 μm were present.

The shrinkage rate of the curable resin composition in which this particulate resin was dispersed was measured by the following method. First, this composition was degassed several times in a Pelger using a vacuum pump, and then
JIS K-6833 (6,
When the specific gravity before curing was measured according to 1 and 2), 1.
It was 10. Separately, 2% of Irgacure 651 (photoinitiator), a Japanese Ciba Geigy flavor product, was added to this composition, and defoaming was repeated several times in the same manner as above. A sample was prepared by pouring this composition onto a polyester film with a 1 mm thick rubber frame attached thereto so as not to create air bubbles, covering it with a polyester film, and fixing it by sandwiching it between transparent glasses from above and below.

This sample was irradiated with ultraviolet rays for 3 minutes on each of the front and back surfaces at a distance of 25 cm under a high-pressure mercury lamp (manufactured by Ushio Inc., ozone-less thousand-light type) with an output of 5 parts w/cm.

Next, the glass plate and polyester film were removed, the mercury lamp was lowered to 20 cm, and the front and back sides were further irradiated for 3 minutes each to complete the curing operation, and a cured product of 1 mm x 30 mm l mm x 3 O was created. The cured product had good transparency. Using this cured product, the specific gravity after curing was measured according to JIS K-6911 (5, 28) and found to be 1.19.

The curing shrinkage rate was calculated from the specific gravity before and after curing according to the following formula, and was found to be 7.98%.

Shrinkage rate (%) = (DD,) Ta.

Example 2 Toagosei Chemical Industry Product Aronix M-5400 [Phthalic acid mono(acryloyl oxy)ethyl ester 14
Part 0 and Toagosei Chemical Industry ■Product Aroninox M-101
60 parts of (α-acryloyl-ω phenoxypolyoxyethylene) and 0.05 parts of hydroquinone monomethyl ether (inhibitor) were charged into a 4-tube flask similar to that in Example 1.

Among them, Nagase Chemical Industry ■Product Denacol EX-14
1 (phenyl glycidyl ether) 15 parts, 7 parts of Yuka Epoxy Product Epicoat E-828 (polycondensate of epichlorohydrin and diphenylolpropane),
A dropping solution consisting of 2 parts of glycidyl methacrylate, 20 parts of the above-mentioned mixture of 40% M5400 and 60% Mlol, and 2 parts of boron trifluoride diethyl etherate,
4 parts 6 mixture 20 of the above M-5400 and M-101
A dropwise addition solution consisting of 50% was added dropwise at room temperature over 30 minutes in the same manner as in Example 1, and the synthesis was completed 35 hours after the start of the dropwise addition.

The product is a yellow-white liquid with a viscosity of 190 at 25°C.
cps, and components insoluble in THF, acetone, and toluene were present. The average particle size of the internally crosslinked fine resin particles was 0.2 μm.

When the curing shrinkage rate was measured in the same manner as in Example 1, it was 8.3.
%Met. M-540 with no particulate resin dispersed
The curing shrinkage of a mixture containing 40% M-0 and 60% M-101 was 13.5%.

Example 3 100 parts of Aroninox M-220 (polypropylene glycol diacrylate) manufactured by Toagosei Chemical Industry Co., Ltd. and 0.05 part of hydroquinone monomethyl ether (inhibitor) were weighed into a 4-tube flask similar to that used in Example 1. Among them, Nagase Chemical Industries ■ product Denacol EX-121 (2
- Ethylhexylglycidyl ether) 48 parts, Nagase Kasei Kogyo Product Denacol Eχ-321 (limethylolpropane-polyglycidyl ether) 5 parts, glycidyl methacrylate 5 parts, Aroninox M-22 mentioned above
0, 5 parts of boron trifluoride dimethyl etherate, and 30 parts of Aroninox M-220 were mixed at room temperature for 30 parts in the same manner as in Example 1.
The mixture was added dropwise within minutes, and the synthesis was completed 45 hours after the start of dropping. The product is a yellowish white liquid with a viscosity of 40c at 25°C.
ps, and there were components insoluble in TF (F, acetone, and toluene). The average particle size of this internally crosslinked particulate resin was 0.35 μm. The curing shrinkage rate was measured in the same manner as in Example 1. The curing shrinkage rate of M-220 alone, in which no particulate resin was dispersed, was 11.5%.
It was 5%.

The tensile strength of the cured product of the radically polymerizable curable resin (Aroninx M-220) Mi product in which this internally crosslinked particulate resin was dispersed was measured by the following method. First, 2% of Merck's Dalcure 1173 (photoinitiator) was added to this composition and cured using the same curing method as in Example 1 to create a cured test piece for tensile testing with a total length of 100 mm and a parallel portion width of 10 mm. did.

Using this test piece, measurement was performed using a Tensilon tensile tester (model UTM-4L manufactured by Toyo θS) at a tensile speed of 10 mm/min in accordance with JIS K-7113.

As a result, the tensile strength was 320 kg/cffl.

On the other hand, the tensile strength of M-220 alone, in which no particulate resin was dispersed, was 240 kg/ci.

Example 4 100 parts of Aronix M-6300 (a polycondensate of diethylene glycol, phthalic acid, and methacrylic acid) manufactured by Toagosei Chemical Industry Co., Ltd. was weighed into the same 4-tube flask as in Example 1. Into it, a dropping solution consisting of 30 parts of Nagase Chemical Industries ■ product Denacol χ-111 (allyl glycidyl ether), 2 parts of Nagase Chemical Industries ■ product Denacol EX-313 (glycerol polyglycidyl ether), and dimethyl boron trifluoride. A dropwise solution consisting of 3 parts of etherate and 20 parts of the above-mentioned Aroninx M-6300 was added dropwise at room temperature over 30 minutes in the same manner as in Example 1, and the synthesis was completed 35 hours after the start of the dropwise addition.

The product is a white liquid with a viscosity of 23 at 25°C.
Qcps, and components insoluble in THF, acetone, and toluene were present. The average particle size of this internally crosslinked particulate resin was 0.25 μm.

A cured product is created by adding 3% hendyl peroxide (initiator) instead of a photoinitiator to this composition, and heating it in a hot air oven for 60 minutes at 100°C instead of using an ultraviolet irradiation device. The curing shrinkage rate was measured in the same manner as in Example 1 except for this, and was found to be 79%. On the other hand, the curing shrinkage rate of M-6300 in which fine particulate resin is not dispersed is 12.
It was 2%.

(c) Effects of the invention The production method of the present invention is a radically polymerizable curable compound in which crosslinked micro epoxy resin particles are dispersed by ionic polymerization of an ionic polymerizable epoxy compound in a radically polymerizable liquid compound. A method for obtaining a resin composition,
This is a new manufacturing method that is completely different from conventional methods.

This manufacturing method not only eliminates the step of blending and dispersing separately produced microscopic resin particles into a radically polymerizable resin, but also eliminates the separation of microscopic resin particles, agglomeration of particles during the drying process, and improvement of surface conditions. Undesirable phenomena such as changes can also be prevented.

In addition, the radical curable resin composition produced by the production method of the present invention has good transparency and excellent deep permeability,
In addition to the general effect of forming a cured product with little increase in viscosity, small shrinkage after curing, and improved various mechanical properties, as mentioned above, there is no aggregation of particles or changes in surface condition, and fine particles are formed. The dispersion state of the resin is stable.

Claims (1)

[Claims] 1. Dispersing fine particles of an epoxy compound polymer by polymerizing one or more polyfunctional epoxy compounds under stirring in a liquid compound having at least one radically polymerizable functional group in the molecule. A method for producing a characteristic curable resin composition.