JPH0542445B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a method for producing a hard gel molding containing an isocyanuric ring, and its object is to produce a hydrophilic fluid photosensitive resin containing isocyanuric acid or an allyl ester of cyanuric acid. The object is to extremely easily produce a hard gel molded product of any shape by irradiating a composition with ultraviolet rays. The hard gel molded products 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. It is something. [Prior Art] Regarding compositions containing isocyanuric acid or allyl esters of cyanuric acid that can be cured by light, electron beams, radiation, etc., optical glasses consisting of triallyl isocyanurate, polythiol, organosilicon compounds, and photosensitizers are used. Manufacturing method (Nippon Publications, Akira)
55-15974) and a method for obtaining molded products for microwave ovens by irradiating a kneaded mixture of triallyl cyanurate and poly(p-methylstyrene) with γ-rays (Japanese Patent Publications, 1984-78421), etc. It has been reported. In addition, molded products obtained by curing aromatic polyamide polymers, triallyl isocyanurate, and silane coupling agents with ultraviolet light (Japanese Patent Publication Publication, 1984-40528), photocurable acrylic polymers, triallyl isocyanurate, and mercaptans. (Nippon Publication Publication, 157408, 1982), many methods of adding triallylisocyanurate to polyester and performing electron beam irradiation crosslinking (Nippon Publication Publication, 1982-157408)
210689, 1984-212024, 1982-212216, 1982-
1728) etc. have also been reported. In addition, an ultraviolet curable resin consisting of a diallyl phthalate/polythiol polymer and triallyl isocyanurate or triallyl isocyanurate (Nippon Publications, 1982-
213022), a method of curing a gel molded product of polycaprolactone or polyamide with triallylisocyanurate added to it by electron beam irradiation (Nippon Tokoku Publications, 1981-11315, 1982-12935, 1982-12936,
Ultraviolet curing paint containing triallyl(iso)cyanurate and polyoxyalkylene polyol (poly(meth)acrylate)
30813), and a photocurable film made of a mixture of epoxy resin and diacrylate of trishydroxyethyl isocyanurate (Japanese Published Publication, 1982-96115). 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, it is difficult to obtain a relatively thin coating film or a molded product in the form of a sheet or less by ultraviolet curing. He learned that it was not easy to obtain molded parts thick enough to be machined. It has been found that the above-mentioned method also requires the use of special isocyanurates and cyanurates, which are economically disadvantageous. [Problems to be Solved by the Invention] The present inventors have continued to explore ways to economically obtain molded hard gels containing isocyanuric rings, regardless of their shape, and have finally discovered a new method. They succeeded in developing a manufacturing method. [Means for solving the problem] and [effect] That is, the present inventors have determined that 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 are 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 ( ) and allyl ester of cyanuric acid ( ) can be collectively expressed as (iso)cyanuric acid allyl ester. Cyanuric acid () and isocyanuric acid () are tautomers, but esters of both in which the active hydrogen atom is substituted are called cyanuric acid ester and isocyanuric acid ester, respectively, and can exist as separate compounds. 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 cured 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, di(meth)allylalkoxyalkyl(iso)cyanurate,
At least one substance selected from the group consisting of di(meth)allylalkenyl(iso)cyanurate and oligomers thereof, and is one of the essential components of the present invention. Esters of acrylic acid or methacrylic acid (meth)
If expressed together with acrylic esters,
Examples of raw materials for the alcohol component side of (meth)acrylic acid ester that can be used as a component of a hydrophilic fluid photosensitive resin composition containing this as an essential component include the following. Namely, alkylene glycol, polyalkylene glycol, oxyacid ester of alkylene glycol, oxyacid ester of polyalkylene glycol, glycidyl alcohol, glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, pentaerythritol, tetrahydroxyadipic acid, carbohydrates. and its derivatives, polyvinyl alcohol and its derivatives, polysaccharides and their 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, melamine Methylolated products of melamine, alkylene oxide adducts of melamine, polyhydroxybenzene, polymethylolated benzene, hydroxyalkylated phenols, hydroxyalkylated polyphenols, phenolic resins, epoxy resins, methylolated polyamides, etc. alone or in mixtures of two or more. be. The hydrophilic fluid photosensitive resin composition according to the present invention includes 5 to 50% by weight, particularly preferably 10 to 40% by weight of isocyanuric acid or allyl ester of cyanuric acid as described above, acrylic acid as described above or A mixture containing ester of methacrylic acid in an amount of 20 to 90% by weight, particularly preferably 25 to 75% by weight, as an essential component, and other components include various polymerizable monomers, resinous substances, solvents,
It may contain water, a plasticizer, a transparent filler, etc. 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,
In other words, if the former is less than 5% by weight and more than 50% by weight, or the latter is less than 20% by weight and more than 90% by weight, effective polymerization and crosslinking will not occur even if UV irradiation is applied. A large amount of reactive double bonds remain, making it impossible to obtain a high-quality hard gel molded product. Particularly when cyanuric acid ester is used, isocyanuric ring formation through Claisen rearrangement is insufficient, and this is due to the hydration of the hard gel molded product. This is not preferable because it increases degradability. 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 using an ultraviolet lamp.
This is carried out by exposing the photosensitive resin composition to light of ~450 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 sensitizers include diacetyl, benzyl, benzophenone, Michler's ketone, benzoin, acetoin, butyroin, benzoin methyl ether, benzoin ethyl ether, 2-methylanthraquinone, anthraquinone, 2-ethylanthraquinone, 1, 2-benzoanthraquinone, benzoquinone, 2,5-diphenylbenzoquinone, anthrone, benzanthrone, di-t-butyl peroxide, benzoyl peroxide, azobisisobutyronitrile, azobenzene, 2-nitrofluorene, 5-nitroacenaphthene, , N-acetyl-
4-nitro-1-naphthyramine, benzenediazonium salt, dibutyl sulfide, dibenzyl disulfide, tetramethylthiuram disulfide,
Examples include thiazole, diphenyl disulfide, methylene blue, fluorescein, eosin, rose bengal, erythrosin, chlorophyll, acridine, cyanine, riboflavin, diaminobenzophenonimide, carbon tetrachloride, silver bromide, and the like. Polymerization and crosslinking by irradiation with ultraviolet rays is carried out batchwise or continuously at a reaction temperature of -20 to +150°C, usually 0 to 100°C. In most cases, the thickness of the cured film of UV-curable paint is 20 to 40 microns, but with the method of the present invention, the thickness can be about 5 cm or more depending on the conditions, as well as films and sheets. A thick plate-like 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 Although 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, the present inventors have demonstrated through many experiments that the method of the present invention is It was discovered that the products of the present invention can be used in various applications such as printing materials, printing plates, sheets, board materials, square materials, etc. 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 Polyethylene glycol (average molecular weight 400) 2
A diester is synthesized by reacting 3 moles of citric acid with 3 moles of citric acid using a strongly acidic ion exchange resin as a catalyst. When this diester is subjected to ring-opening condensation of 2 moles of glycidyl methacrylate, a water-soluble polyester methacrylate mixture having an average molecular weight of about 1,500 to 1,800 as shown by the following formula can be obtained. In this reaction, when 1 mole of polyethylene glycol is reacted with 2 moles of citric acid, the average molecular weight is 800~
1100 water-soluble polyester methacrylate mixture is obtained. 25 g of triallyl isocyanurate, 25 g of 2-hydroxyethyl methacrylate, and 2 g of benzoin ethyl ether were added to 100 g of the water-soluble polyester methacrylate with an average molecular weight of 1030 synthesized as described above until it became sufficiently homogeneous.
After mixing at 70°C, the mixture is degassed in vacuum to obtain a photosensitive resin composition. This photosensitive resin composition is cast onto a glass plate, a photographic negative film is closely adhered thereon to form a curing plate, and the plate is inserted into an ultraviolet irradiation device with the negative film facing upward. Next, ultraviolet rays (3650 Å) are irradiated for 30 seconds at room temperature from the glass side of the curing plate, and then ultraviolet rays are irradiated for 5 seconds from the negative film side to complete photocuring of the negative image. After taking out the curing plate and peeling off the glass plate and negative film, the plate is placed in a stream of water, the uncured parts outside the image are washed away and dried, and a beautiful resin letterpress can be obtained. 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 2,2'-bis(4-acryloxydiethoxyphenyl)propane 50g, triallyl cyanurate
30g, triacrylate of pentaerythritol
10g, 2-hydroxyethyl methacrylate 30
g and 2 g of benzoin ethyl ether are mixed until sufficiently homogeneous and degassed under vacuum to obtain a photosensitive resin composition. On the other hand, a thin non-woven glass fiber fabric is spread on top of the polyester film, impregnated with the above photosensitive resin composition, and after vacuum degassing again, a negative film with letters and designs drawn on the top surface is adhered to form a curing sheet. shall be. After curing this curing sheet with ultraviolet rays in the same manner as in Example 1, peeling off the polyester film and negative film and thoroughly washing it in an alcohol/water mixture, an FRP type resin letterpress with a non-woven fabric substrate is obtained. available. Example 3 Alcohol-soluble modified nylon (AQ manufactured by Toray)
nylon) 100g, water 30g and ethanol 30g
Add and heat to 80℃ to make a homogeneous solution. Next, 30 g of tripropylene glycol diacrylate, 20 g of diallyl 4-hydroxybutyl isocyanurate, and 3 g of Daikyure 1173 manufactured by Merck & Co., Ltd. as a sensitizer are added to this mixture 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. Alternatively, a water-containing FRP sheet can be obtained by impregnating a glass cloth with this composition, covering both sides with polyester film, and curing with ultraviolet light in the same manner as in Example 2. Example 4 Urethane acrylate photosensitive oligomers (XP-300B and XP-7000B manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.)
(1:1 mixture of) 80g, glycidyl acrylate
10g, 4-hydroxybutyl acrylate 10g,
50 g of dimethallyl 2-butoxyethyl isocyanurate 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 mold is inserted into an ultraviolet irradiation device, and after light curing is performed using an ultraviolet fluorescent lamp (20S-BA-37-K, 20W, manufactured by Matsushita Electric Industrial Co., Ltd.), the resin plate is taken out from the mold. The resulting resin board (thickness: 35 mm) is transparent, has a surface hardness of JISA 95 or higher, and can be cut and nailed in the same way as wood, making it extremely versatile. Examples 5 to 15 When polymerization and crosslinking are 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 polymerization and crosslinking are carried out in the same manner as in Example 4. A gel molded product that can be cut or nailed is made, and its appearance is shown in the table below.

【table】

[Table] [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 has a colorless to yellow-brown transparent to translucent appearance. This is a resin molded product that shows no adhesive or damage to the touch. This molded product can be manufactured from small to fairly large products, including printing materials, printing plates, sheets, etc.
It is used for plate materials, square materials, etc. The product according to the invention can be further processed by cutting, gluing, bending, coloring,
Dyeing, nailing, etc. can be done. Furthermore, depending on the polymerization conditions, the method of the present invention can yield products with considerably high elasticity and solvent resistance, and these products are useful as gaskets, packings, valves, shock absorbers, and the like. The industrial use of the product according to the present invention is tremendous, and it is highly expected that various uses will be created in the future as a new material.

Claims (1)

[Scope of Claims] 1. A hydrophilic fluid photosensitive resin composition containing 5 to 50% by weight of an allyl ester of isocyanuric acid or cyanuric acid and 20 to 90% by weight of an ester of acrylic acid or methacrylic acid is exposed to ultraviolet light. 1. A method for producing a hard gel molded product containing an isocyanuric ring, the method comprising polymerizing and crosslinking by irradiating with. 2. Allyl ester of isocyanuric acid or cyanuric acid is tri(meth)allyl ester, di(meth)allyl alkyl ester, di(meth)allyl aralkyl ester, di(meth)allyl alkoxyalkyl ester, di(meth)allyl alkenyl ester and 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 these oligomers.