JPS61235410A - Production of rigid gel molding containing isocyanuric ring - Google Patents

Abstract

PURPOSE:To facilitate the production of the title molding of an arbitrary shape, by irradiating a hydrophilic flowable photosensitive resin composition containing allyl (iso)cyanurate and a (meth)acrylate ester with ultraviolet rays. CONSTITUTION:A hydrophilic flowable photosensitive resin composition containing 5-50wt% allyl (iso)cyanurate of formula I or II, 20-90wt% (meth) acrylate ester and, optionally, a photosensitizer (e.g., diacetyl), a polymerizable monomer, a solvent, a plasticizer, a transparent filler, etc., is polymerized and crosslinked by irradiation with ultraviolet rays of a wavelength of #300-450mum at a temperature of -20-150 deg.C for several sec - several hr.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a hard gel molded product containing an incyanuric ring, and its object is to produce a hard gel molded product containing isocyanuric acid or an allyl ester of cyanuric acid. The present invention aims to extremely easily produce a hard gel molded product of any shape by irradiating a hydrophilic fluid photosensitive resin composition with ultraviolet rays. The hard gel moldings obtained by this method are made into printing materials, printing plates, sheets, plates, square materials, etc., and are further processed by cutting, gluing, composite, etc., and used for various industrial purposes.

[Conventional technology]

Regarding compositions containing isocyanuric acid or allyl esters of cyanuric acid that are cured by light, electron beams, radiation, etc., triallyl isocyanurate, polythiol,
A method for producing optical glass consisting of an organosilicon compound and a photosensitizer (Niji Publications, 1974-15974) and a kneaded mixture of triallyl cyanurate and poly(p-methylstyrene) are irradiated with γ-rays to generate electrons. A method for obtaining molded products for microwave ovens (Nichimo Kokka, 78421/1982) has been reported. In addition, molded products made by UV-curing aromatic polyamide polymers, triallyl isocyanurate, and silane coupling agents (Niji Publications, 1984-40528), photocurable acrylic polymers, triallyl isocyanurate, and mercaptan. A polymer consisting of
6-157408), Many methods of adding triallylisocyanurate to polyester and performing electron beam irradiation crosslinking (Niji Publications, 1982-210689. 1982-212)
024. Showa 57-212216. 1728), etc. have also been reported. In addition, ultraviolet curable resins made of diallyl phthalate/polythiol polymer and triallyl isocyanurate or triallyl isocyanurate (Niji Publications, 1982-213022), gel molded products made by adding triallyl isocyanurate to polycaprolactone or polyamide. A method of curing by electron beam irradiation (Nichichi Publications, 11315-1982, 12935-1980, 12936-1980, 12936-1982),) Reallyl (iso) cyanurate is cured by poly(meth) of polyoxyalkylene polyol. ) Ultraviolet curable paint containing acrylate (Niji Publishing Co., Ltd., 1984-25840. 1982-308)
10. Photo-cured film of a mixture of epoxy resin and diacrylate of trishydroxyethyl isocyanurate (Niji Publishing Co., Ltd., 1982-961)
15) has been announced.

The present inventors investigated the above-mentioned conventional techniques and found that in all of them, it is not easy to adjust the blending composition of the starting materials, and in particular, ultraviolet curing may result in a relatively thin coating film or a molded product in the form of a sheet or less. I learned that it is not easy to obtain thick molded parts that can be machined.

It has been found that the above-mentioned method also requires the use of special isocyanurates and cyanurates, which are economically disadvantageous.

[Problem that the invention seeks to solve]

The present inventors have continued to explore ways to economically obtain molded hard gels containing isocyanuric rings, regardless of their shape, and have finally succeeded in developing a new manufacturing method. It is.

[Means for Solving the Problem] and [Operation] That is, the present inventors used 5 to 50% by weight of allyl ester of isocyanuric acid or cyanuric acid and 20 to 90% by weight of ester of acrylic acid or methacrylic acid as essential components. It was discovered that a hard gel molded product containing an isocyanuric ring can be easily obtained by polymerizing and crosslinking a hydrophilic fluid photosensitive resin composition containing an isocyanuric ring by irradiating it with ultraviolet rays.

Allyl ester of isocyanuric acid (n) and cyanuric acid (
1) Allyl ester can be collectively expressed as (iso)cyanuric acid allyl ester (n)
(II) Cyanuric acid (1) and isocyanuric acid (II) are tautomers, but the esters in which the active hydrogen atoms of both are substituted are called cyanuric acid ester and isocyanuric acid ester, respectively, and exist as separate compounds. I can do it. However, isocyanuric acid ester has better thermal stability, and this corresponds to a Claisen rearrangement type compound of cyanuric acid ester. When cyanuric acid ester is used as a raw material, if appropriate rearrangement energy is given, Claisen rearrangement will proceed simultaneously during the polymerization reaction or crosslinking reaction, resulting in a stable isocyanuric acid ester. It has been found that this occurs particularly easily in the case of a hydrophilic fluid photosensitive resin composition such as the one of the present invention, and the hard gel molded product produced contains a large amount of isocyanuric rings. The product becomes a stable molded product that can be used for many purposes. Among the (iso)cyanuric acid esters, allyl esters and meta-allyl esters are particularly suitable for the method of the present invention. Specifically, tri(meth)allyl(iso)cyanurate, di(meth)allylalkyl(iso)cyanurate, di(meth)allylaralkyl(iso)cyanurate, and di(meth)allylalkoxyalkyl(iso)cyanurate.

At least one substance selected from the group consisting of di(meth)allylalkenyl(iso)cyanurate and oligomers thereof, which is one of the essential components of the present invention. If esters of acrylic acid or methacrylic acid are collectively expressed as (meth)acrylic acid ester, (meth)acrylic acid can be a component of a hydrophilic fluid photosensitive resin composition containing this as an essential component. Raw materials for the alcohol component of esters include the following.

That is, alkylene glycol, polyalkylene glycol, oxyacid ester of alkylene glycol, oxyacid ester of polyalkylene glycol, glycidyl alcohol, and glycerin.

Trimethylolmethane, trimethylolethane.

Trimethylolpropane, pentaerythritol.

Tetrahydroxyadipic acid, carbohydrates and their derivatives,
Polyvinyl alcohol and its derivatives, polysaccharides and its derivatives, methylolated products of amines, alkylene oxide adducts of amines, methylolated products of acid amides, alkylene oxide adducts of acid amides, alkylene oxide adducts of amino acids, methylolated products of melamine, Alkylene oxide adducts of melamine, polyhydroxybenzenes, polymethylolated benzenes, hydroxyalkylated phenols, hydroxyalkylated polyphenols.

It may be a phenol resin, an epoxy resin, a methylolated polyamide, etc. alone or a mixture of two or more thereof.

The hydrophilic fluid photosensitive resin composition referred to in the present invention refers to the above-mentioned isocyanuric acid or allyl ester of cyanuric acid from 5 to 50% by weight, particularly preferably from 10 to 40% by weight.
% by weight, esters of acrylic acid or methacrylic acid as mentioned above from 20 to 90% by weight, particularly preferably from 25 to 90% by weight.
A mixture containing 75% by weight as an essential component,
It may contain various polymerizable monomers, resinous substances, solvents, water, plasticizers, transparent fillers, etc. as components other than these. If the amount of isocyanuric acid or allyl ester of cyanuric acid and ester of acrylic acid or methacrylic acid used deviates from the above range, that is, the former is less than 5% by weight and more than 50% by weight, or the latter is 20% by weight or less.
If the content is less than 90% by weight or more than 90% by weight, polymerization and crosslinking will not occur effectively even when irradiated with ultraviolet rays, and in particular, a large amount of unreacted double bonds will remain, making it impossible to obtain a hard gel molded product of good quality. In particular, when cyanuric acid ester is used, isocyanuric ring formation by Claisen rearrangement is insufficient, which is undesirable because it increases the hydrolyzability of the hard gel molded product. Therefore, when implementing the present invention, the conditions specified in the present invention should be fully maintained.

Now, in polymerization and crosslinking by ultraviolet irradiation, it is important to reduce the remaining double bonds as much as possible by simultaneously carrying out the two types of reactions of resin molecules necessary for producing hard gel molded products. It is. In other words, in order to guarantee the elasticity, elongation, crack prevention, etc. of a hard gel molded product, it is necessary to allow the polymerization reaction to proceed so that the polymerization component in the resin composition increases the molecular weight as linearly as possible. be. In addition, in order to guarantee the rigidity, hardness, and prevention of secondary deformation of the hard gel, it is necessary to ensure that the polymerization components in the resin composition undergo a crosslinking reaction fairly homogeneously so that three-dimensionalization progresses sequentially. It is necessary to. When both the polymerization and crosslinking reactions are well balanced, a hard gel molded product can be obtained that can meet the various uses mentioned in the present invention. The amounts of the allyl ester of (iso)cyanuric acid and the ester of (meth)acrylic acid described above are necessary to achieve a balance between both the polymerization and crosslinking reactions described above and to obtain a good hard gel.

Ultraviolet rays are usually irradiated with a wavelength of 300 to 45 using an ultraviolet lamp.
This is carried out by exposing the photosensitive resin composition to light of 0 mμ for several seconds to several hours. At this time, a method is adopted in which a suitable photosensitizer is mixed into the resin composition in a catalytic amount so that the irradiation time is shortened to facilitate the formation of photoexcited decomposition radicals. Typical aggravating agents include diacetyl, benzyl,
Benzophenone, Michler Ketone, Benzoin, Acetoin.

Butyroin, benzoin methyl ether, benzoin ethyl ether, 2-methylanthraquinone.

Anthraquinone, 2-ethyl anthraquinone, 1゜2-
Benzoanthraquinone, benzoquinone, 2゜5-diphenylbenzoquinone, anthrone, penzanthrone, di-t-butyl peroxide, benzoyl peroxide 9 Azobisisobutyronitrile, azobenzene, 2-nitrofluorene, 5-nitroacenaphthene1. N-acetyl-4-di-0-1-su7-tyramine, benzenediazonium salt.

Dibutyl sulfide, dibenzyl disulfide.

Tetramethylthiuram disulfide, thiazole.

Diphenyl disulfide 1. Methylene blue, fluorescein, eosin, rose bengal, erythrosin, chlorophyll, acridine, cyanine.

Riboflavin, diaminobenzophenonimide.

Carbon tetrachloride, silver bromide, etc.

Polymerization and crosslinking by irradiation with ultraviolet rays occurs at a reaction temperature of -20 to
+150°C1 Normally carried out at 0-100°C either batchwise or continuously. In general, the thickness of the cured film of UV-cured paint is often 20 to 40 microns, but in the method of the present invention, the thickness can be adjusted to about 5C11 or more depending on the conditions. A plate-shaped product can also be obtained as a hard gel molded product. The hydrophilic fluid photosensitive resin composition of the present invention can be stored stably if it is stored while shielding from light, and this property is due to the fact that it contains a significant amount of isocyanuric acid or allyl ester of cyanuric acid. has been significantly strengthened by

It is not easy to explain theoretically why the method of the present invention is so convenient and the quality of the product is uniform and stable. They found that the products of the present invention can be used for various purposes such as printing materials, printing plates, sheets, board materials, and square materials. Therefore, in order to further clarify the content of the present invention, we have extracted a few representative examples from among the numerous experimental examples that are sufficient to explain the technical content of the present invention and the breadth of its application, and provide the following examples as examples. I will show you.

〔Example〕

Example 1 A diester is synthesized by reacting 2 moles of polyethylene glycol (average molecular weight 400) with 3 moles of citric acid using a strongly acidic ion exchange resin as a catalyst. When 2 moles of glycidyl methacrylate is ring-opened and condensed to this diester, the average molecular weight is 11,500 to 1,800 as shown by the following formula.
The degree of water-soluble polyester methacrylate mixture can be changed.

In this reaction, 1 mole of polyethylene glycol has 2 citric acid
When the moles are reacted, a water-soluble polyester methacrylate mixture having an average molecular weight of 800 to 1100 is obtained.

To 100 g of the water-soluble polyester methacrylate with an average molecular weight of 1030 synthesized as described above, 25 g of triallyl isocyanurate, 25 g of 2-hydroxyethyl methacrylate, and 2 g of benzoin ethyl ether were added.
g is added and mixed at 70°C until sufficiently homogeneous, and then degassed in vacuum to obtain a photosensitive resin composition. This photosensitive resin composition is cast onto a glass plate, a negative photographic film is adhered thereon to form a curing plate, and the plate is inserted into an ultraviolet irradiation device with the negative film facing upward. Next, apply ultraviolet i for 30 seconds from the glass side of the curing plate.
(3,650 people) were irradiated at room temperature, and then ultraviolet rays were irradiated from the negative film side for 5 minutes to complete photocuring of the negative image. After taking out the curing plate and peeling off the glass plate and negative film, place the plate in a stream of water, wash off the uncured parts outside the image, and dry it, allowing you to create a beautiful resin letterpress. In this method, if the raw material photosensitive resin composition is transparent, there will be no unevenness or devitrification of the contents of the cured letterpress material during the casting process and photocuring process, and clear and accurate images will be printed directly on the letterpress. was able to express it.

Example 2 2. 50 g of 2'-bis(4-acryloxyjethoxyphenyl)propane, 30 g of realyl cyanurate, 10 g of triacrylate of pentaerythritol, 30 g of 2-hydroxyethyl methacrylate, and 2 g of benzoin ethyl ether were uniformly mixed. A photosensitive resin composition is obtained by mixing until the mixture is mixed and deaerating under vacuum.

On the other hand, a thin nonwoven glass fiber fabric is spread on the polyester film and impregnated with the above photosensitive resin composition,
After vacuum degassing again, a negative film with letters and designs drawn on the top surface is closely adhered to form a hardening sheet. After curing this curing sheet with ultraviolet rays in the same manner as in Example 1, peeling off the polyester film and the negative film and thoroughly washing it in an alcohol/water mixture, an FRP-type resin letterpress with a substrate reinforced with non-woven fabric can be obtained. It will be done.

Example 3 30 g of water and 30 g of ethanol were added to 100 g of alcohol-soluble modified nylon (AQ nylon manufactured by Toshi ■) and heated to 80°C to form a homogeneous solution. Next, this was mixed with 30 g of tripropylene glycol diacrylate and diallyl. 20 g of 4-hydroxybutyl isocyanurate and 3 g of Guicure 1173 manufactured by Merck & Co., Ltd. as a sensitizer are added and thoroughly mixed to prepare a homogeneous photosensitive resin composition. This composition can be made into a resin letterpress by the same operation as in Example 1. In addition, this composition can be used for glass and
A water-containing FRP sheet can be obtained by impregnating a cloth, covering both sides with a polyester film, and curing with ultraviolet rays in the same manner as in Example 2.

Example 4 80 g of urethane acrylate photosensitive oligomer (1:1 mixture of XP-300B and XP-7000B from Nippon Synthetic Chemical Industry Co., Ltd.), glycidyl acrylate Log
, 10 g of 4-hydroxybutyl acrylate.

Dimethallyl 2-butoxyethyl isocyanurate 50
g and 2 g of benzoin ethyl ether are mixed to form a homogeneous solution, which is poured into a glass mold and degassed under vacuum. Next, the glass formwork was inserted into the ultraviolet irradiation device, and an ultraviolet replacement light lamp (203-B A manufactured by Matsushita Electric Industrial Co., Ltd.) was installed.
-37-K, 20W), and then the resin plate is taken out from the mold. The resin plate obtained here (
It is transparent with a thickness of 35N, has a surface hardness of 95 or higher according to JISA, and can be cut and nailed in the same way as wood, making it extremely versatile.

Examples 5 to 15 If polymerization and crosslinking were carried out in the same manner as in Example 4, using the isocyanurate or cyanurate shown in the following table in place of dimethallyl 2-butoxyethyl isocyanurate in the amount shown in the table below, the resultant product would be similar to wood. A gel molded product that can be cut or nailed is made, and its appearance is shown in the table below.

[Effects of the Invention] The present invention relates to a method for producing a hard gel molded product containing an isocyanuric ring, and the product obtained by the method of the present invention is a transparent to translucent resin molded product with a colorless to yellowish brown appearance. This is something that does not show any stickiness or damage when touched with a finger. This molded product can be manufactured from small to fairly large products, and is used for printing materials, printing plates, sheet materials, square materials, etc. The product according to the invention is further processed by cutting, gluing, bending, and coloring.

Dyeing, nailing, etc. can be done. Furthermore, depending on the polymerization conditions, the process of the present invention can yield products with considerable elasticity and solvent resistance, and these products are useful as gaskets, banks, valves, shock absorbers, and the like.

The industrial use of the product according to the present invention is extremely effective, and it is highly expected that various uses will be created as a new material.

Claims (2)

[Claims] (1) A hydrophilic fluid photosensitive resin composition containing 5 to 50% by weight of allyl ester of isocyanuric acid or cyanuric acid and 20 to 90% by weight of ester of acrylic acid or methacrylic acid is irradiated with ultraviolet rays. A method for producing a hard gel molded product containing an isocyanuric ring, which comprises polymerizing and crosslinking. (2) Isocyanuric acid or allyl ester of cyanuric acid is tri(meth)allyl ester, di(meth)allylalkyl ester, di(meth)allylaralkyl ester, di(meth)allylalkoxyalkyl ester, di(meth)allylalkyl ester,
The method for producing a hard gel molded product containing an isocyanuric ring according to claim (1), characterized in that the material is at least one substance selected from the group consisting of meth)allyl alkenyl esters and oligomers thereof.