JPS6071629A - Material for photo-setting plastic mold - Google Patents

Abstract

PURPOSE:The titled material that is composed of an epoxy resin, an aluminum compound and a silicon compound which forms silanol groups by light irradiation, thus forming a plastic mold with good flexibility and surface hardness with high storing stability at room temperature in dark places. CONSTITUTION:The material is composed of (A) an epoxy resin such as bisphenol-A type, (B) an aluminum compound, preferably an organoaluminum compound such as aluminum trismethoxide, and (C) a silicon compound which forms silanol groups by light irradiation, preferably a silicon compound bearing peroxysilane, o-nitrobenzyloxy and alpha-ketosilyl groups wherein the content of B is 0.1-5%; C, 1-10% based on component A by weight. EFFECT:The removed resin and waste are reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to a photocurable plastic molding material having a novel composition, and more particularly, to a material for photocurable plastic molds, which is made by impregnating or coating a substrate or substrate and curing it under actinic light. The present invention relates to a material for photocurable plastic molds, in which the obtained cured product becomes a base material and becomes a plastic mold having good flexibility and surface hardness.

[Technical background of the invention and its problems] In recent years, resins that are cured by light have been developed from the viewpoint of energy saving and productivity improvement. Compared to the conventional mainstream thermosetting resins, these photocurable resins have features such as reducing air pollution because they do not use solvents, saving energy (heat), and shortening curing time. Therefore, it is attracting attention as an excellent photocurable resin from the viewpoint of overall economic efficiency that takes into account these various factors.

Application examples of photocurable resin include plastic molds, printing inks, seven electronic parts, including traditional applications.
These include paints for printed circuits, canned paints, coil coatings, top coats for floor tiles, textile finishing, fillers for particle boards, and other paints for wood, paper, leather, and plastics.

By the way, these photocurable resins mainly have a high curing speed (short curing time), excellent adhesion of the resin to the base material, and the ability of the cured resin to have high continuity and a smooth surface. At present, photocurable resins, mainly used in coatings, are required to have properties such as excellent hardness and hardness. It is known that the resin itself is cured using a photodecomposition type catalyst.

Those belonging to the former category generally include epoxy-modified unsaturated polyester resins, polyester acrylate resins, and polyester urethane acrylate resins. However, these resins have the disadvantage of large shrinkage during curing, resulting in poor adhesion to the substrate due to distortion, and furthermore, the polymerization retardation effect due to oxygen in the atmosphere causes them to come into contact with the atmosphere. This results in an inconvenient situation in which the surface hardening does not progress sufficiently.

On the other hand, those belonging to the latter category are used because the epoxy resin itself is cured with a photodecomposition type catalyst, but such catalysts are of the following formula: (wherein A represents a phenyl group, Represents an atom, sulfur atom, diazo group, etc.
, PFs, AgF2, 8bFs, etc. )
The following complexes are given as follows: [Macromolecules, Vol. 10, p. 1307, 19774 [-(Ma
cromolecules, 30, 1307 (19
77)) ; Journal of Radiation Keyring, Vol. 5, p. 2, 1978.
f Radiotinn Curing-5, 2 (19
78));Journal of Polymers →J-Jens Polymer Chemistry Edition, No. 17
Volume, 2877 pages, 1979 (JournajofPo
lymer 5science Polymer Che
+n1stry Idition.

17, 2877 (1979)); Ibid., Vol. 17,
1000 pages, 1979 (Ibid., Collection, 1047 (19
7,9); Journal of Polymer Science Polymer Letters, Volume 17,
759 pages, 1979 (Journal of Pol
ymer 5science Polymer Lett
ersEdition, 17, 759 (1979)
); JP-A-55-65219; U.S. Patent No. 4
069054; British Patent No. 1,516,511; British Patent No. 1,518,141, etc.] However, when epoxy resins are photocured using these catalysts, good resin performance is obtained; Since the catalyst is a strong acid, for example, when the base material is metal, there is a risk that the base material (metal) will be corroded, which is disadvantageous.

Furthermore, in order to photocure conventional plastic molds, the height of the uneven image is high, and therefore a large amount of resin is removed from the non-image area, and cleaning of the removed resin and disposal of waste liquid are also problems.

[Object of the Invention] The present invention solves the above-mentioned drawbacks of conventional photocurable resins, has excellent storage stability at room temperature and in the dark, and is suitable for removal resins and waste liquid treatment. The object of the present invention is to provide a novel photocurable resin composition that can easily be used to form plastic molds with the required precision.

[Summary of the Invention] The present invention uses a resin consisting of an epoxy resin, an aluminum compound, and a silicon compound that produces silanol groups when irradiated with light as a material for a mold.

First, examples of the epoxy resin used in the present invention include -functional epoxy compounds and polyfunctional epoxy compounds. -Functional epoxy compounds include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, phenyl glycidyl ether, butyl glycidyl ether, and the like. The polyfunctional epoxy compound is not particularly limited, but includes, for example, bisphenol F-type epoxy resin; bisphenol F-type epoxy resin: phenol novolac-type epoxy resin; alicyclic epoxy resin; triglycidyl isocyanate, hydantoin epoxy, etc. Arocyclic epoxy resin; hydrogenated bisphenol A type epoxy resin; aliphatic epoxy resin such as brobylene glycol-diglycidyl ethyl, pentaerythritol-polyglycidyl ether; aromatic,
Epoxy resin obtained by reaction of aliphatic or alicyclic carboxylic acid with epichlorohydrin; Spiro ring-containing epoxy resin: glycidyl ether type epoxy resin which is the reaction product of a 0-roofenol novolak compound and epichlorohydrin. ; Glycidyl ether type epoxy resin, etc., which is a reaction product of a diallyl bisphenol compound having an allyl group at the 0-position of each hydroxyl group of bisphenol A and epichlorohydrin, etc.; You can use the name (().

The aluminum compounds that are the second component of the Jli7 composition of the present invention have an alkoxy group on the aluminum atom,
Phenoquine group, acyloxy group, β-diketonato group, 0
A complex compound of organoaluminium to which -carbonylphenolad group or the like is bonded is preferable.

Here, the alkoxy group preferably has 1 to 10 carbon atoms, and examples include methoxy, ethoxy, isopropoxy, butoxy, bentoxy, etc.; examples of the phenoxy group include phenoxy group, 0-methylphe/+cy group, 0- Methoxyphenoxy group, p-nitrophenoxy group, 2,6
-dimethylphenoxy group; examples of the acyloxy group include acetato, propionate, impropionate, butyrad, stearado, ethyl acetoacetate, probylacetoacetate, butylacetoacetate, diethylmalato, dipivalo Examples of the β-diketonato group include acetylacetonato, trifluoroacetylacetonato, hexafluoroacetylacetonato, and 0-carbonylphenorad group. Examples include salicylaldehydate.

Specific examples of aluminum compounds such as trismethoxyaluminum, trisethoxyaluminum, trisisopropoxyaluminum, trisphenoxyaluminum, trisparamethoxyaluminum, isopropoxyjethoxyaluminum, trisbutoxyaluminum, trisacetoxyaluminum, tris Aluminum stearado, aluminum trisbutyrad, aluminum aluminum trispropionate, aluminum aluminum trisbutyrad, aluminum aluminum trisacetylaceto, aluminum aluminum trisfluoroacetylacetonate, aluminum aluminum trishexafluoroacetylacetonate, aluminum aluminum trisethifacetaceta aluminum, trissalicylaldehydatoaluminium,
Examples include trisdiethylmaloradoaluminum, trisprobyl acetoacetatoaluminum, trisbutylacetoacetatoaluminum, trisdipivaloylmethanatoaluminum, diacetylacetonatodipivaloylmethanatoaluminum, and the like.

These aluminum compounds may be used alone or in a mixed system of two or more, and the amount added is from 0.001 to 10 inches, preferably from 0.1 to 5 inches, based on the weight ratio of the epoxy resin. It is within the range of If the amount is less than 0.00101% by weight, sufficient curing properties will not be obtained, and if it exceeds 10% by weight, it will cause increased costs and decreased adhesion.

The coating composition of the present invention is characterized in that it contains, as a third component, a silicon compound that generates silanol groups upon irradiation with light. Such a silicon compound is preferably a silicon compound having any one of a peroxysilane group, an 0-nitrobenzyloxy group, and an α-ketosilyl group.

Among these silicon compounds, those having a peroxysilane group have the following formula: %Formula%) (In the formula, R1 and R2 may be the same or different, and each has a hydrogen atom, a -.rogen atom, and a carbon atom. Numbers 1-5
represents an alkyl group or an aryl group, and n is O-3
0) representing an integer of .

In the above formula, examples of the alkyl group having 1 to 5 carbon atoms include:
Methyl group, ethyl group, isopropyl group, n-propyl group, n-butyl group, t-butyl convex, 5ee-butyl group, n
- Pentyl group, ethoxy group, ethoxy group, chloromethyl group, examples of the aryl group include phenyl group, naphthyl group, anthranyl group, benzyl group, and alkyl group having 1 to 5 carbon atoms. and aryl groups include IE' such as halogen atoms, nitro groups, cyano groups, and methoxy groups.
It may have a 71fi group.

Specific examples of such silicon compounds include the compounds shown below.

In addition, those having an 0-nitrobenzyloxy group have the following formula: Atom; vinyl group; allyl group; unsubstituted or substituted alkyl group having 1 to 10 carbon atoms; γ-alkoxy group having 1 to 10 carbon atoms;
Unsubstituted or substituted aryl group; f IJ -ruoxy group; represents a siloxy group, IL' is a water non-atom; Represents a group, R5, R6, B?
, R8 may be the same or different, and each is a hydrogen atom; a nitro group; a cyano group; a hydroxy group; a mercapto group; a perlokene atom; an acetyl group; an allyl group;
An alkyl group having 1 to 5 carbon atoms; an alkoxy group having 1 to 5 carbon atoms; an unsubstituted or substituted aryl group; an aryloxy group, p, q, and r are O≦p, q, r≦: U, ■- ≦
Represents an integer that satisfies the condition p+q+r≦3. ).

Examples of the non-substituted or substituted alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, t-
Examples include butyl group, pentyl group, chloromethyl group, chloroethyl group, fluoromethyl group, cyanmethyl group, and examples of alkoxy groups having 1 to 10 carbon atoms include butoxy group,
Examples include ethoxy group, n-propoxy group, and n-butoxy group.

Examples of non-substituted or substituted groups include phenyl v group, p-methoxyphenyl group, p-chlorophenyl JA,
I))! Examples include J fluoromethylphenyl groups,
Examples of the aryloxy group include a phenoxy group.

In addition, as a silicon compound, the terminal group is an 0-nitrobenzyloxysilyl group, and the chain has the following formula: and B2 has the same meaning as above; X and Y may be the same or different, and each , represents an oxygen atom, an alkylene group, an aryl group, etc. ) may be a compound consisting of a group represented by

Specific examples of silicon compounds having an unsubstituted or substituted O-nitrobenzyloxy group directly bonded to a silicon atom used in the present invention include trimethyl(0-nitrobenzyloxy)silane, dimethylphenyl(0-nitrobenzyloxy) Silane, diphenylmethyl(0-nitrobenzyloxy)silane, triphenyl(0-nitrobenzyloxy)silane, vinylmethylphenyl(0-nitrobenzyloxy)silane, t-butylmethylphenyl(0-nitrobenzyloxy)silane , triethyl (0
-nitrobenzyloxy)silane, tri(2-chloroethyl)-〇-nitrobenzyloxysilane,)IJ(1
)-)'J Fluoromethylphenyl)-〇-nitropenzyloxidryphenyl(α-ethyl-〇-nitrobenzyloxy)silano, trimethyl(3-methyl-2-nitrobenzyloxy)silane, triphenyl(4 ,5-
dimethyl-2-nitrobenzyloxy)silane, triphenyl(2,6-dinitrobenzyloxy)silane, diphenylmethyl(2,4-dinitrobenzyloxy)silane, triphenyl(3-methquine-2-nitrobenzyloxy) ) silane, methylphenyldi(0-nitrobenzyloxy)silane, vinylphenyldi(0-nitrobenzyloxy)silane, t-butylphenyldi(0-nitrobenzyloxy)silane, diethyldi(O-nitrobenzyloxy)silane , 2-chloroethylphenyldi(0-nitrobenzyloxy)silane, diphenyldi(
0-nitrobenzyloxy)silane, diphenyldi(3
-methquin-2-nitrobenzyloxy)silane, diphenyldi(3,4-dimethoxy-2-nitrobenzyloxy)silane, diphenyldi(2,6-dinitrobenzyloxy)silane, diphenyldi(2,4- dinitrobenzyloxy)silane, methyltri(0-nitrobenzyloxy)silane, phenyl) IJ (0-nitrobenzyloxy)silane, -nitrobenzyloxy)siloxane, 1.1,3,3,5,5-hexaphenyl -1
, 5-di(O-nitrobenzyloxy)siloxane, and a silicon compound produced by the reaction between a 5iC1-containing silicone resin and O-nitrobenzyl alcohol.

Finally, a) having an α-ketosilyl group has the following formula:
0% formula%) (In the formula, n represents a number of 0, 1, 2, 3; 1t represents a hydrocarbon group such as an alkyl group having 1 to 10 carbon atoms, a vinyl group, an allyl group, an aryl group, or an aryloxy group. group, carbon number 1~
10 alkoxy groups, these are halogen atoms,
It may have a radical group such as NO2, C'N, -0CH3, etc. in the molecule. ) is a compound represented by

Compounds such as

The amount of each silicon compound added is in the range of 01 to 20% by weight, preferably 1 to 10% by weight, based on the epoxy resin. If the blending amount is less than 0.1% by weight, sufficient curing properties cannot be obtained, and although it is possible to use 21111% by weight, the cost is high and decomposition products of the catalyst component are generated. This is not desirable as it may cause problems.

The material of the present invention has the above-mentioned three components as essential components, but in addition to the above-mentioned components, additives such as pigments or fillers that are usually used in resin compositions can also be added.

The resin composition of the present invention can be easily prepared by adding a predetermined amount of the above-mentioned three components and, if necessary, a pigment etc. After that, it can be cured by a method such as room temperature photocuring, heating photocuring, or after-curing after photocuring, and can be put into practical use. At this time, the wavelength of the irradiated light varies depending on the composition of the resin composition, but is usually 180 to 700n+n. Irradiation with ultraviolet light is particularly effective. The light irradiation time varies depending on the composition of the epoxy resin, the opening of the catalyst, the light source, etc., but is usually 1 to 1
80 minutes, preferably 1 to 60 minutes. The heating temperature in the case of thermal photocuring varies depending on the composition of the epoxy resin and the type of catalyst, but is usually 20 to 200°C, preferably 60 to 100°C. The light source may be any light source that is normally used for photocuring, such as low-pressure mercury lamps, high-pressure mercury lamps, carbon arc lamps, metal halogen lamps, gysenon-mercury lamps, xenon lamps, and hydrogen discharge. tubes, tungsten lamps, halogen lamps, sodium discharge tubes, neon discharge tubes, argon discharge tubes, He-Ne v-zer, Ar(
Examples include off-L/-f-1N2L/- laser, Cd ion laser-1He-Cd laser, and dye laser, and one or more types selected from the group consisting of these may be used as appropriate. After-curing after photocuring varies depending on the composition of the epoxy resin and the type of catalyst, but is usually carried out at 50 to 200°C, preferably 0 to 180°C, for 1 to 10 hours, and for 2 to 5 hours under heating. .

[Examples of the Invention] Example 1 Epoxy resins include Celoxide 2021 (trade name, manufactured by Daicel Corporation, alicyclic, epoxy equivalent weight 145) 50 parts, Ebicor) 828 (trade name, manufactured by Shell Chemical Co., Ltd., bisphenol A type) , epoxy (1190 to 210) Sekibe, 0.5 parts of trisbara methylphenoxyaluminum (TPMPA) as an aluminum compound, triphenylsilylketone as an organosilicon compound, and 50 parts of silica as a filler to form the present invention. A resin composition was prepared. The resin composition was applied to a thickness of about 20 μm onto a sculpture made of limestone, which served as a prototype. Then, add these to 5
Q w /Cm of air-cooled mercury lamp water was added to the egg-shaped dome, which was placed in an egg-shaped dome and exposed to a mercury lamp, resulting in a sculpture mold that accurately reproduced even the finest details. After solidifying and reinforcing the thin layer sculpture mold,
The internal calcareous part was removed by washing with water, and a precise sculptural mold was created.

Example 2 ERL4221 (trade name UCC) was used as the epoxy resin.
Co., Ltd., alicyclic, epoxy equivalent weight 145) 50 parts, Epicoat 828 (trade name, Shell Chemical Co., Ltd., bisphenol A type, epoxy equivalent-r7tic+o~210) (4
) 5 parts of trisethyl acetate aluminum (TEAACA) as an aluminum compound, 5 parts of diphenyl(0-nitrobenzyloxy)silane as a silicon compound, and 50 parts of calcium carbonate as a filler. An inventive resin composition was prepared. These resin compositions were applied by a conventional method onto a washed bronze relief. Next, these were exposed for 3 minutes in a light source with three 80w air-cooled mercury lamps placed at a height of 15 cm from the conveyor surface, and then fine relief was printed after reinforcement in the same manner as in Example 1. The prepared epoxy mold was easily and quickly completed.

Example 3 A resin material prepared in the same manner as in Example 1 was applied to a flat plate to a thickness of approximately 100 μm, a high-definition, V-LSI mask was applied, and the resin material was cured in the same manner as in Example 1. The part was washed and removed with acetone/triclene mixed solvent,
After reinforcement in the same manner as above, a plastic mold for V-LSI was completed.

Agent Patent Attorney Nori Chikutsu Yu (1 other person)

Claims (3)

[Claims] (1) A photocurable plastic molding material comprising an epoxy resin, an aluminum compound, and a silicon compound that forms a group into a sila when irradiated with light. (2) The photocurable plastic molding material according to claim 1, wherein the aluminum compound is an organic aluminum compound. (3) The silicon compound is a silicon compound having any one of a peroxysilane group, an 0-nitrobenzyloxy group, and an α-ketosilyl group.
y photocurable plastic mold material 0