JPH0379685A - Releasable material and production thereof - Google Patents

Abstract

PURPOSE:To obtain the subject material having excellent releasability and free from the action to lower the adhesivity of the tacky adhesive by laminating a composition composed of a thermoplastic resin, etc., a dimethylpolysiloxane, a polyfunctional compound and an antioxidant to a substrate and curing the composition. CONSTITUTION:The objective material can be produced by laminating a substrate with a resin composition composed of (A) (i) a polyolefin thermoplastic resin preferably selected from PE, ethylenic copolymer and polybutene or a mixture of (ii) a low-density PE having a density of 0.850-0.035 and (iii) a monoolefinic copolymer rubber, (B) a dimethylpolysiloxane preferably blocked at both terminals with trimethylsilyl group or hydroxydimethylsilyl group, (C) a polyfunctional compound especially preferably consisting of triallyl isocyanurate, etc., and (D) an antioxidant especially preferably consisting of octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate. etc., and curing the composition with radiation.

Description

[Detailed description of the invention]

[Industrial Application Field 1] The present invention is a radiation-curable resin composition that can be used mainly for imparting releasability to the base surface of adhesive labels, office supplies, etc. or the back surface of wound packaging tape. The present invention relates to objects and removable bases. [Conventional Technology J Conventionally, release paper used as the base of adhesive sheets for adhesive labels and office supplies, or the back side of wrapped adhesive tapes for packaging, etc., has been used to develop release properties. In addition, expensive reactive silicone is applied directly or onto a polyolefin-laminated base surface, and then heat-cured. [Problem to be Solved by the Invention 1] However, the process of applying the silicone and further heat-treating requires not only a large-scale process with a length of equipment reaching several tens of meters, but also a process of applying reactive silicone. Since a solvent such as toluene is used in this process, a large amount of equipment and energy is required to recover it. In this case, it may be possible to omit a large-scale process by mixing silicone with thermoplastic resin, but
This method not only does not sufficiently exhibit the releasability required for release paper or releasable sheets, but also causes the fatal defect that silicone that bleeds onto the surface transfers to the adhesive layer of patches, stickers, etc., reducing the adhesive strength. There is. As a method to solve this problem, a method has been proposed in which a radiation-curable reactive organopolysiloxane is mixed with a resin, molded by lamination and inflation, and then irradiated with radiation (Japanese Patent Laid-Open No. 57-1872
However, this method requires the use of expensive organopolysiloxane containing mercapto groups, vinyl groups, etc., and when molding is performed at high temperatures, During the process, the organopolysiloxane reacts with the polyolefin thermoplastic resin that is the matrix, or the organopolysiloxanes react with each other, making it difficult for the organopolysiloxane to properly bleed onto the surface of the molded product, resulting in no release properties. There is. In addition, the present inventors have developed a method for manufacturing a releasable material by first molding a composition obtained by mixing a polyolefin thermoplastic resin with dimethylpolysiloxane and a polyfunctional compound, and then applying electron beam irradiation. However, when using this composition, it was necessary to keep the molding temperature below the deterioration and thermal reaction temperature of the polyfunctional compound. The present inventors solved the above-mentioned problems of the conventional method, and created a releasable material by molding a composition obtained by adding and mixing an organopolysiloxane and a polyfunctional compound to a thermoplastic resin, and irradiating it with radiation such as an electron beam. Taking into consideration the problems in the manufacturing method of We have succeeded in developing a resin composition and a releasable material that can be used to produce a releasable material that has excellent releasability and does not reduce the tackiness of the adhesive. [Means for Solving the Problems] In order to achieve the above object, the present invention provides a release resin composition comprising (a) a polyolefin thermoplastic resin or a mixture of low density polyethylene and monoolefin copolymer rubber (b) ) We have developed a radiation-curable release resin composition characterized by comprising dimethylpolysiloxane (C1 polyfunctional compound (d) and an antioxidant. In addition, the release resin composition described above is laminated on a base material. Later, they developed a removable material that was cured by radiation.Furthermore, one finding was that the performance of this removable material could be improved by treating it at a temperature below the melting point of the constituent resin components of the removable resin composition. Achieved the invention. [Structure and operation of the invention] Among the resin components (a) used as raw materials, the polyolefin thermoplastic resins include high-density polyethylene,
Medium-density polyethylene, low-density polyethylene, polypropylene, copolymers mainly composed of these, copolymers of ethylene and vinyl esters or α,β-unsaturated carboxylic acid esters, or mixtures thereof can be used. Density polyethylene, ethylene copolymer, ethylene-
Butene copolymers and polybutenes are preferred. These can be used alone or in combination of two or more specific types, and in addition, other commonly used additives 1
For example, light stabilizers, lubricants, antiblocking agents, pigments, fillers, etc. may be added. Melt index (MI) or melt flow index (MFR) of the above polyolefin thermoplastic resin
) is 0.01-200g/10mln, 0. 'l=1
00g/lomin is preferable, 1-30g/10m1
n is preferred. The low density polyethylene referred to in the present invention has a density of 0.
850 to 0.935 g/cm", linear low density polyethylene, or a copolymer of ethylene with other comonomers such as vinyl acetate. Also, a mixture thereof may be used. It is natural that it may be present. Melt index (MI) or melt flow index (MFR) is 0.O1 to 200g/lomin
, preferably 0. , l~loog/10mln, particularly 1~30g/10mln, is suitable. Furthermore, the monoolefin copolymer rubber referred to in the present invention includes two or more monoolefin copolymer rubbers having 2 to 15 carbon atoms, or 2 to 15 carbon atoms! Copolymer rubbers of olefins having a molecular weight of 281 or higher and polyenes, such as ethylene-propylene copolymer rubbers and ethylene-propylene-nonconjugated diene rubbers, can be used. Examples of the non-conjugated diene include 1, for example dicyclopentadiene, 1,4-
Examples include hexadiene, dicyclooctadiene, ethylidenenorbornene, and the like. The above monoolefin copolymer rubbers can be used alone or as a mixture of two or more. In addition, the Mooney viscosity of the monoolefin copolymer rubber is M
L, 5-300° at 4100°C, especially 20-25
A range of 0 is desirable. If the Mooney viscosity at 100° C. is less than 5, it will be difficult to mix, and if it exceeds 300, fluidity will be insufficient. The mixing ratio of the above low density polyethylene and monoolefin copolymer rubber is 20 to 90% by weight of low density polyethylene.
80-80% by weight of monoolefin copolymer rubber, preferably 40-80% by weight of low-density polyethylene.
Monoolefin copolymer rubber 60-20I! A preferred amount is 50 to 30 iU of monoolefin copolymer rubber based on 50 to 70 percent by weight of low-density polyethylene. If the low density polyethylene is less than 20% by weight and the monoolefin copolymer rubber exceeds 80% by weight, there will be no problem in terms of release performance, but the moldability will be markedly reduced, and if the low density polyethylene exceeds 90% by weight, the monoolefin copolymer rubber will be more than 80% by weight. If 10% by weight of the olefin copolymer rubber is left undropped, the stability of the peeling performance will decrease. General additives such as light stabilizers, lubricants, antiblocking agents, pigments, fillers, etc. may be added to the mixture of low density polyethylene and monoolefin copolymer rubber. A mixture of the above polyolefin thermoplastic resin or low density polyethylene and monoolefin copolymer rubber (hereinafter referred to as
The dimethylpolysiloxane in which both are mixed with the resin component (referred to as al) has terminals of 15iR'R"R' (however, R', R", and R' each independently contain a methyl group, a hydroxyl group, a CI A dimethylpolysiloxane consisting of a Cs alkoxy group (selected from Cs alkoxy groups) is particularly preferred, with dimethylpolysiloxane having both terminals end-blocked with trimethylsilyl groups or hydroxydimethylsilyl groups being end-blocked. The kinematic viscosity (hereinafter referred to as viscosity) of the above dimethylpolysiloxane is 50 to 8 x 10"c at 25°C.
If the viscosity at 25° C. is less than 50 cs, it is difficult to mix with the polyolefin thermoplastic resin, making it difficult to mold, and also to exhibit sufficient peeling performance. This requires a large radiation dose, lowers the mechanical strength of the resin component lal of the matrix, and is disadvantageous in terms of cost. Furthermore, if the viscosity exceeds 8XlO'cs, it becomes difficult to exhibit sufficient peeling performance. Further, the mixing ratio of dimethylpolysiloxane to the resin composition is 0.1 to 30% by weight, preferably 1 to 15% by weight, and particularly preferably 2 to Gffi% by weight. If the mixing ratio is less than 0.1% by weight, sufficient peeling performance cannot be obtained,
If it exceeds 30% by weight, it will be difficult to mix and mold, and it will be disadvantageous in terms of cost. In addition, the polyfunctional compounds added together with the resin component (a) and dimethylpolysiloxane include vinyl groups, acrylic groups,
What about functional groups that tend to react with radiation, such as methacrylic groups and mercapto groups? Examples of compounds having a plurality of vinyl groups include divinylbenzene, etc.
Examples of compounds having multiple acrylic groups include polyethylene glycol diacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, 1.3 butylene glycol diacrylate, 1. Examples of compounds having multiple methacrylate groups include polyethylene glycol dimeta, 6-hexanediol diacrylate, 1.4-butanediol diacrylate, pentaerythritol tetraacrylate, dipentaerythritol (monohydroxy) pentaacrylate, and dipentaerythritol hexaacrylate. acrylate, trimethylolpropane trimethacrylate,
Tetramethylolmethanetetramethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1.3 butylene glycol dimethacrylate,
1.6 hexanediol dimecacrylate,! , 4-butanediol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol (monohydroxy) pentamethacrylate, dipentaerythritol hexamethacrylate, etc. Compounds having multiple allyl groups include diallyl terephthalate. , diallyl adipate, triallyl cyanurate, triallyl isocyanurate. pentaerythritol triallyl ether,
Glycerin diallyl ether, trimethylolpropane diallyl ether, diglycerol diallyl ether,
Diglycerol triallyl ether 5 allyl methacrylate, diallyl phthalate, diallyl maleate. diallyl isophthalate, triallyl trimellitate,
Examples of compounds having a plurality of mercapto groups, such as tetraallyl pyromellitate, allyl glycol acrylate, and allyl glycol methacrylate, include trimethylolpropanetolyl-3 mercaptopropionate. Preferably trimethylolpropane trimethacrylate. Tetramethylolmethanetetramethacrylate. triallyl cyanurate, triallyl isocyanurate, particularly preferably triallyl isocyanurate,
Trimethylolpropane trimethacrylate. What is the mixing ratio of the above-mentioned polyfunctional compound with the composition? It is 0.01 to 30% by weight, preferably 0.5 to 15% by weight, and preferably 1 to 5% by weight. The amount is 0.01
Less than % by weight is enough! I) Stability of release performance cannot be obtained, and if the amount exceeds 30% by weight, sufficient release performance cannot be obtained, making molding extremely difficult and further disadvantageous in terms of cost. In addition, as the antioxidant used in the present invention, those that are numerically added to thermoplastic resins can be used. Examples of these include 2,6-dit-butyl-p-cresol, pentaerythrityl, -tetrakis(3-(3,5dit)
butyl-4-hydroxyphenyl)propionate),
4.4' Thiobis(3-methyl 6-t-butylphenol). 1.3.5. Tris(3,5-t-butyl-4-hydroxybenzyl)S-triazine, 2.46-(I
I-1,38,5F()trione, 1,3,5-trimethyl-2,4,6-1-lis(3,5-di-butyl-4-hydroxybenzyl)benzene, pentaerythritoltetrakis(β-lauryl-diprobiotic) Tetrakis (2,4-di-butylphenyl), 4,4-biphenylene siphosphite, Calcium (3,5-di-t-butyl-4-hydroxybenzyl monoethylphosphonate), Distearylthiodipropio 2.6-di-t-butyl-p-cresol, octadecyl-3-(3,5-di-t-butyl-4), bis(2,4-di-t-butylphenyl)pentaerythritol,
-hydroxyphenyl)propionate, pentaerythrityltetrakis (3-(3,5-di-t-butyl-4-
Preferred are octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythrityltetrakis(3-(3,5-di-t-butyl-4-hydroxyphenyl)) Propionate) is particularly preferred. The mixing ratio of the above antioxidant with the composition depends on the resin composition and the amount of dimethylpolysiloxane added and mixed. It varies depending on the type of polyfunctional compound, amount added, molding temperature, etc., but mainly the type of polyfunctional compound added and mixed and 1
1 determined by the molding temperature of the composition. For example, when a large amount of polyfunctional compounds are blended. Alternatively, when the molding temperature is high, it is preferable to increase the amount of antioxidant, but - for boat fishing, it is 0.001 to 1.0% by weight, preferably 0.01 to 0.5% by weight, more preferably It is about 0.05 to 0.25% by weight. Adding more than necessary not only wastes expensive antioxidants, but also causes them to remain in the product after molding, which may impair the effects of radiation irradiation. To mix the resin component (a), dimethylpolysiloxane, polyfunctional compound, and antioxidant, an apparatus generally used for mixing and mixing synthetic resins can be used. W4: For example, melt mixing is performed using a Banbury mixer, a kneader-1 twin-screw extruder, a single-screw extruder, a roll mill, or the like. Especially when using dimethylpolysiloxane with low viscosity. Normal mixing is difficult, so dimethylpolysiloxane is mixed by pumping it into the middle of the cylinder of an extruder, or dimethylpolysiloxane is added little by little in a Banbury mixer, and then radiation curing is performed. A resin composition for sexual exfoliation can be obtained. To mold the above composition, there are conventional extrusion lamination methods, coextrusion lamination methods, inflation methods, coextrusion inflation methods, T-die methods, and multilayer T-die methods, which are appropriately selected depending on the purpose and use. A releasable surface is formed by irradiating the composition surface of a molded article such as a film or a laminated film thus produced, thereby forming a releasable material. The laminated film or the like as the above-mentioned releasable material may be in the form of a sheet, a belt, or a single item, but will be described below as a sheet. As the base material for the releasable sheet, paper or a two- or three-layer structure of paper/polyolefin-radiation curable resin composition is often used because it is easy to use. Other embodiments of the laminated film include polyamides, polycarbonates, polyolefins, combinations of vinyl chloride/polyolefin/radiation curable resin compositions, combinations of volier or chill/polyolefin/radiation curable resin compositions, and the like. Methods for performing the above-mentioned radiation irradiation treatment include α, β-, and γ-rays, and β-9γ-rays are desirable, and β-rays are preferred. What is the radiation dose? It can be varied within a wide range depending on the required performance of the irradiated object. Generally, it is 1 to 30 megarads, and 1
-15 megarads are desirable, and 1 to 10 megarads are particularly preferred. irradiation dose. If it is less than 1 megarad, there is no effect, and if it exceeds 30 megarad, the mechanical properties of the matrix polymer will be significantly reduced and practicality will be lost. The irradiation atmosphere is preferably an inert gas, and examples of the inert gas include M, carbon dioxide, helium, and the like. The reason why it exhibits excellent peeling performance when irradiated with radiation is not clear, but polyolefin thermoplastic resins that have the property of crosslinking or decomposing due to radiation
By coexisting with dimethylpolysiloxane and a polyfunctional compound, the radicals generated in the polyolefin thermoplastic resin, the radicals generated in dimethylpolysiloxane, and the radicals generated in the polyfunctional compound subtly and complexly influence each other, Promotes grafting reactions and crosslinking between dimethylpolysiloxanes via polyfunctional compounds,
It seems that this is connected to the special performance. In addition, although it is unclear why the moldability can be increased by using a composition containing a predetermined amount of an antioxidant, the coexistence of a polyfunctional compound and an antioxidant in the composition increases the polyfunctionality. Thermal reaction of compounds (molding a resin component (at) containing a polyfunctional compound and measuring the melt index of the molded product. Temperature at which the melt index is significantly lower than the reference)! 3 and decomposition, suppressing Even after molding, there is sufficient mold polyfunctional compound in the molded product,
It is presumed that the object of the present invention can be achieved by radiation irradiation. By further subjecting the radiation-irradiated composition to heat treatment, the stability of peelability and the stability of changes over time are promoted. Heat treatment methods include a method of leaving the roll in a circulating oven or a stationary oven after irradiation;
Alternatively, there is a method of passing the material through a hot roll, but it is particularly preferable to leave it in a circulating or stationary oven in a rolled form. The temperature of the heat treatment is below the melting point of the resin component (al) constituting the composition, and varies depending on the type of resin, but a temperature lower than the melting point of 10°C or less is particularly desirable. It varies depending on the amount of polysiloxane, the composition of the resin, and the amount of radiation irradiated in the previous process, but it is mainly determined by the correlation with the heat treatment temperature. Depending on the type 8, the mechanical properties may deteriorate if it is not continued for a long time.
0 seconds to 3 days is preferable. It is believed that the reason why the peelability is promoted by the heat treatment is that the reaction that could not be completed by radiation irradiation is further promoted. By using the radiation-curable resin composition of the present invention, there is no need for conventional large-scale coating, dry crosslinking steps, or solvent recovery steps, and the mixing ratio of dimethylpolysiloxane and polyfunctional compound to be used, The peeling performance expressed can be adjusted by combining radiation irradiation conditions, heat treatment conditions, etc. Further, by adjusting the type and amount of the antioxidant added to the resin composition, the temperature at which the composition is molded can be increased. This is very useful, especially in the case of extrusion lamination and coextrusion lamination, since it can improve the adhesion to the base material. [Examples] The present invention will be specifically explained below by showing Examples and Comparative Examples. In Examples and Comparative Examples, the peel strength, residual adhesion rate, and stability of samples prepared under various conditions were measured. The peel strength and residual viscosity on skewers were measured as follows. (a) Peel strength: As a standard tape on the laminate surface of a sample that was irradiated with radiation after molding the composition of the present invention. Scotch No. 28 tape (tape width 25 mm) was pasted and a tape roller weighing 2 kg was made to reciprocate once. Next, a double load of g/c- was applied to the tape and the tape was heated in an atmosphere of 65°C for a predetermined period of time. After leaving it for one day, one week, one month,
The sample was cooled to 25° C. for 3 hours, then pulled using a tensile tester at a pulling speed of 0.3 m/min and a pulling angle of 180', and the force required for peeling was measured, and this was taken as the peel strength. (b) The sample whose residual adhesion rate and peel strength were measured was pasted on a #280 stainless steel plate and passed through a 2 kg tape roller once.
A load of 20 g/am'' was applied to the tape, and the tape was left in an atmosphere of 65°C for 20 hours, then cooled to 25°C for 3 hours).
The tape was peeled off from the stainless steel plate and the force required to do so was measured. On the other hand, a standard tape that was not subjected to peel strength measurement was attached to a stainless steel plate in the same manner as above, and it was peeled off from the stainless steel plate under the same conditions, and the force required for this was measured. Expressed as a percentage of This was defined as the residual adhesion rate. (Example 1) MI is 12g/10m1n, density is 0.916g/c1
The high-pressure low-density polyethylene (hereinafter referred to as LD-A) has a viscosity of 60,000 at 25°C.
5% by weight (hereinafter referred to as 1%) of dimethylpolysiloxane with trimethylsilyl group capped at both ends of cs, 2% triallylisocyanurate (hereinafter referred to as TAIC) and octadecyl 3-(3,5-di-t-butyl). A resin composition containing 0.15% of -4-hydroxyphenyl)propionate was prepared with an MI of 8 g/lomin and a density of 0.
．． The resin composition temperature was 290°C, the LD-13 temperature was 310°C, and the lamination thickness was the same for resin compositions You and LD-B20u. extrusion laminated,
A three-layer laminate of paper/LD-B/resin composition was formed and then subjected to electron beam irradiation at a line speed of 30 m/min and an irradiation dose of 5 Mrad in an atmosphere with an oxygen concentration of 10 ppm or less. Properties related to the release material were measured. (Example 2) MI is 20 g/10 m1n, density is 0.916 g/cm
high-pressure low-density polyethylene, 5% dimethylpolysiloxane with trimethylsilyl group-blocked ends and a viscosity of 60,000 cs at 25°C, 2% TAIC and octadecyl-3-(3,5-di-t-butyl-4-hydroxy). A resin composition containing 0.1% phenyl)propionate has an MI of 12 g/mfn and a density of 0.917 g/C1.
Samples were prepared in the same manner as in Example 1, except that the resin composition was coextruded onto low-density polyethylene and kraft paper at 270°C and the polyethylene resin at 290°C, and each measurement was performed. (Example 3) MI is 12g/10m1n, density is 0.960g/cm
” high-density polyethylene (hereinafter referred to as HD) and LD
The viscosity at 25°C is 3000 cs in a mixture obtained by melt-mixing -A at a ratio of HD/LD-A = 60/40 (%).
4% trimethylsilyl-blocked dimethylpolysiloxane, 2% TAIC and octadecyl-3-(3,5
Samples were prepared in the same manner as in Example 1, except that a resin composition containing 0.15% of -di-t-butyl-4-hydroxyphenyl) propionate was added and mixed, and the irradiation dose was set to lOMrad. I did this. (Example 4) Ml is log/10mln, vinyl acetate concentration is 9
% of ethylene-vinyl acetate copolymer (hereinafter referred to as EVA), 5% of dimethylpolysiloxane blocked with trimethylsilyl groups at both ends and having a viscosity of 10,000 cs at 25°C, 2% of TATC and octadecyl-3-(3,5
- Di-t-butyl-4-hydroxyphenyl) propionate 0.10% mixed resin composition was extruded onto the polyethylene surface of commercially available polyethylene-laminated kraft paper at a resin temperature of 260°C and a lamination thickness of 20μ to laminate. Samples were prepared in the same manner as in Example 1, except for the following, and each measurement was performed. (Example 5) Polypropylene with an MFR of 30 g/10 m1n (hereinafter referred to as
PP-A) and high pressure low density polyethylene (LD
- A) is melt-mixed at a ratio of PP-A/LD-A = 90/10 (%) and the viscosity at 25°C is 1oo.
5% dimethylpolysiloxane with trimethylsilyl group capped at both ends of ooOcs, 5% trimethylolpropane trimethacrylate (hereinafter referred to as TMPTMA)
and pentaerythrityltetrakis (3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate) in an amount of 0.2%.
5g/10m1n polypropylene (hereinafter referred to as PP-B), Ml is 2g/10m1n, and the density is 0.925
7cm” high-pressure low density polyethylene (hereinafter referred to as L D
−C, ) is PP-B/LD-C=80/20 (
%), the mixture was melted and mixed at a resin temperature of 300°C.
, the resin surface of the base material was made by extruding it onto kraft paper with a lamination thickness of 20μ, and the resin temperature was 250°C. A sample was prepared in the same manner as in Example 1, except that the composition was extruded and laminated under the condition that the lamination thickness was 20 μm, and each measurement was performed. (Example 6) Ml is 12g/lo+nin, density is 0.917g/a
Low-pressure process low-density polyethylene (hereinafter referred to as LLD-A) containing butene-■ of s' as a comonomer and LD-A are L
A mixture melt-mixed at a ratio of LD-A/LD-A = 70/30 (%) has a viscosity of 30000c at 25°C.
5% and 74102% of dimethylpolysiloxane with trimethylsilyl group capped at both ends of s and octadecyl-
A sample was prepared in the same manner as in Example 1 except for using a resin composition containing 0.15% of 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate.
Each measurement was performed. (Example 7) A sample was prepared in the same manner as in Example 1, except that 1% dimethylpolysiloxane having a viscosity of 60,000 cs at 25° C. and blocked with trimethylsilyl groups at both ends was used, and various measurements were performed. (Example 8) A sample was prepared in the same manner as in Example 1, except that 8% dimethylpolysiloxane endblocked with trimethylsilyl groups at both ends and having a viscosity of 60,000 cs at 25° C. was used, and each measurement was performed. (Example 9) A sample was prepared in the same manner as in Example 1 except that 0.5% TAIC was used, and each measurement was performed. (Example 10) A sample was prepared in the same manner as in Example 1, except that 6% TAIC was used, and each measurement was performed. (Comparative Example 1) A sample was prepared in the same manner as in Example 1 except that TAIC was not added, and each measurement was performed. (Comparative Example 2) A sample was prepared in the same manner as in Example 4, except that TMPTMA was not added, and each measurement was performed. (Comparative Example 3) A sample was prepared in the same manner as in Example 1, except that octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was not added, and each measurement was performed. (Comparative Example 4) Irradiation 1! A sample was prepared in the same manner as in Example 1, except that the amount was changed to 0.5 Mrad, and each measurement was performed. (Comparative Example 5) A sample was prepared in the same manner as in Example 1, except that irradiation III was set to 40 Mrad, and each measurement was performed. (Comparative Example 6) A sample was prepared in the same manner as in Example 2, except that octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was not added, and each measurement was performed. In this case, the adhesion to the kraft paper was insufficient,
A sample was prepared by subjecting the base material to a corona treatment in order to separate it from the surface of the base material. (Comparative Example 7) 5% dimethylpolysiloxane with a viscosity of 20 cs at 25°C and blocked with trimethylsilyl groups at both ends was used.
Molding was impossible. (Comparative Example 8) A sample was prepared in the same manner as in Example 1, except that 5% dimethylpolysiloxane endblocked with trimethylsilyl groups at both ends and having a viscosity of 1.2×10'cs at 25° C. was used, and each measurement was performed. (Comparative Example 9) Example 1 except that 5% of pentaphenyltrimethyltrisiloxane with a viscosity of I 75cs at 25°C was used.
Samples were prepared in the same manner as above, and each measurement was performed. (Comparative Example 10) A sample was prepared in the same manner as in Example 1 except that electron beam irradiation was not performed, and each measurement was performed. The measurement results of Example 1-to and Comparative Example 1-10 are collectively shown in Table 1. (Margins below) Table ■ Comparative Example 5: Unavoidable unevenness on the surface, lack of smoothness and unmeasurable Comparative Example 7: Unable to form and unmeasurable Comparative Example 1O: Poor peelability (due to poor peelability of the base laminate) (The following is a margin) (Example 11) In LD-A, 5% dimethylpolysiloxane with a viscosity of 60000CS at 25°C and blocked with trimethylsilyl groups at both ends, 2% TAfC, and octadecyl-3- A resin composition containing 0.15% of (3,5-di-t-butyl-4-hydroxyphenyl) propionate was applied to Il, D-B and kraft paper at a resin composition temperature of 290°C and an LD-B temperature of 310°C.
℃, the resin composition was coextruded with a lamination thickness of 10 u and LD-820 μ to form a three-layer laminate of paper/LD-B/resin composition, and then the line speed was 30 m in an atmosphere with an oxygen concentration of 10 ppm or less. ,,/min, irradiation dose 3M
After electron beam irradiation with rad. Samples were prepared by heat-treating the rolls in a gear oven at 80° C. for 3 days, and used for each measurement. (Example 12) To a mixture melt-mixed at a ratio of HD/LD-A = 60/'40 (%), 4% dimethylpolysiloxane with a viscosity of 3000 cs at 25°C and blocked with trimethylsilyl groups at both ends, 2% TAIC, and Octadecyl-3-(3
, 5-di-t-butyl-4-hydroxyphenyl) propionate, using a resin composition mixed with 0.15%,
Example 11 except that the irradiation dose was 6 Mr.
Samples were prepared in the same manner as above, and each measurement was performed. (Example 13) Ml is 1Og/l0m1n, vinyl acetate concentration is 9
% of ethylene-vinyl acetate copolymer, 5% of dimethylpolysiloxane endblocked with trimethylsilyl groups at both ends and having a viscosity of I 0000 cs at 25°C, 2% of TAIC and octadecyl-3-(3,5-di-t-butyl-4). - A resin composition mixed with 0.15% of hydroxyphenyl) propionate was applied to the polyethylene surface of polyethylene-laminated kraft paper at a resin temperature of 260'C and a lamination thickness of 2.
Samples were prepared in the same manner as in Example 11, except that extrusion lamination was carried out under conditions of 0μ, and each measurement was performed. (Example 14) A mixture melt-mixed at a ratio of PP-A/LD-A = 90/IO (%) had a viscosity of 100QOO at 25°C.
5% dimethylpolysiloxane capped with trimethylsilyl groups at both ends of cs, 5% 'rM P T MA and pentaerythrityltetrakis (3-(3,5-di-t-
A resin composition to which 0.2% of butyl-4-hydroxyphenyl) propionate was added had an MFR of 30 g/
10ml polypropylene (PP-B) and 2g Ml
PP-B/LD-C=
A mixture melted and mixed at a ratio of 80/20 (%) was extruded onto kraft paper at a resin temperature of 300°C and a lamination of 11!20μ.
Samples were prepared in the same manner as in Example 11, except that extrusion lamination was carried out at a temperature of 20 μm, and each measurement was performed. (Example 15) A mixture melt-mixed at a ratio of LLD-A/LD-A = 70/30 (%) had a viscosity of 30,000 at 25°C.
5% dimethylpolysiloxane capped with trimethylsilyl groups at both ends of cs, 2% TAIC and octadecyl-3
- Samples were prepared in the same manner as in Example 11 except for using a resin composition containing 0.15% of (3,5-di-t-butyl-4-hydroxyphenyl)propionate, and each measurement was carried out in the same manner as in Example 11. I did this. (Comparative Example 11) A sample was prepared in the same manner as in Example 1 except that TAIC was not added, and each measurement was performed. (Comparative Example 12) A sample was prepared in the same manner as in Example 11 except that the electron beam was not irradiated, and each measurement was performed. The results of Example 11=15 and Comparative Example I1.12 are collectively shown in Table 2. (Margins below) Table (Note) Comparative Example 12: Peelability Q (Paper and LD-B peel off (blanks below)) (Example 16) Ethylene/propylene/ethylidene norbornene = 60
/3515 (%), an ethylene-propylene-nonconjugated diene copolymer rubber (hereinafter referred to as EPDM-1) with a Mooney viscosity ML1◆◆ of 50 and an MT of 15 g/lom
EPDM-1/LD-D=40/
To a mixture melt-mixed at a ratio of 60 (%), 5% dimethylpolysiloxane endblocked with trimethylsilyl groups at both ends and having a viscosity of 3000 cs at 25°C, 2% TAIC, and octadecyl-3-(3,5-disabtyl- 4-
The resin composition mixed with 0.15% hydroxyphenyl)propionate was processed into high-pressure low density polyethylene LD-8.
and kraft paper, resin composition temperature 290℃, LD-8 lag degree 310℃, lamination thickness 10μ of resin composition, LD-B 20μ
Co-extrusion laminated sheet 1 paper/LD-8/* fat composition 3
The laminated body was molded and then subjected to electron beam irradiation at a line speed of 30 m/min and an irradiation dose of 5 Mrad in an atmosphere with an oxygen concentration of 10 ppm or less, and the properties of this sample regarding the release material were measured. (Example 17) Lr)-A/EP/EPDM-1=60/30/10(
%), the viscosity at 25°C is 6.
0000cs dimethylpolysiloxane 5% with trimethylsilyl group capped at both ends. TAIC 2% and octadecyl-3-(3゜5-di-
A resin composition containing 0.1% of t-butyl-4-hydroxyphenyl) propionate. MI is 12g/10m1n, density is 0.917g/c-
It was coextruded and laminated on kraft paper with the high-pressure low-density polyethylene of No. 1. In this case, the resin composition temperature is 270°C
The polyethylene was extruded at 290° C., and a three-layer laminate was obtained so that the laminate thickness was 10μ of the resin composition and 20μ of the polyethylene. Subsequently, electron beam irradiation was performed at a line speed of 30 m/mir and an irradiation amount #i of 5 Mrad in an atmosphere with an Ill element concentration of 10 ppm or less to prepare a sample, and various measurements were performed. (Example 18) Propylene content 15M%, MFR 10g 710min
The ethylene-propylene copolymer rubber (EP) of
A mixture with a viscosity of 6 at 25°C was added to the mixture melt-mixed in the ratio of D/EP/EPDM-1 = 60/30/10 (%).
A sample was prepared in the same manner as in Example 16, except that 5% dimethylpolysiloxane of 0000cs with trimethylsilyl groups blocked at both ends was used, and each measurement was performed. (Example 19) Ml is 30 g/10 m1n, density 0.918 g/clI
LD-E/EP/EPDM-1=60/30/1
To a mixture melt-mixed at a ratio of 0 (%), 5% dimethylpolysiloxane with a viscosity of 10000 cs at 25°C and TMPTMA blocked at both ends with trimethylsilyl groups was added
% and pentaerythrityltetrakis (3-(3,5-
A resin composition containing 0.1% of 4-hydroxyphenyl propionate was extruded onto the polyethylene side of commercially available polyethylene-laminated kraft paper at a resin temperature of 270°C and a lamination thickness of 20 u. Except for this, a sample was prepared in the same manner as in Example 16, and each measurement was performed. (Example 20) LLD-A is LLD-A/EP/EPDM-1=60/
Add 2 to the mixture melt-mixed at a ratio of 30/10 (%).
5% of dimethylpolysiloxane containing trimethylsilyl groups at both ends and having a viscosity of 100,000 CS at 5°C, TA
IC2% and octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate 0.1
A sample was prepared in the same manner as in Example 16, except that a resin composition containing 5% of the above amount was used, and each measurement was performed. (Example 21) A sample was prepared in the same manner as in Example I8, except that 1% dimethylborisiloxane having a viscosity of 60,000 cs at 25° C. and having trimethylsilyl groups blocked at both ends was used, and various measurements were performed. (Example 22) A sample was prepared in the same manner as in Example 18, except that 8% dimethylpolysiloxane endblocked with trimedelsilyl groups at both ends and having a viscosity of 60,000 cs at 25° C. was used, and each measurement was performed. (Example 23) A sample was prepared in the same manner as in Example 16 except that 0.5% TAIC was used, and each measurement was performed. (Example 24) A sample was prepared in the same manner as in Example 16 except that 6% TAIC was used, and each measurement was performed. (Comparison f51113) A sample was prepared in the same manner as in Example 16 except that TATC was not added, and each measurement was performed. (Comparative Example 14) A sample was prepared in the same manner as in Example 19 except that TMPTMA was not added, and each measurement was performed. (Comparative Example 15) A sample was prepared in the same manner as in Example 16, except that octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was not added, and each measurement was performed. (Comparative Example 16) Irradiation! Example 18 except that Im was set to 0.5 Mrad.
Samples were prepared in the same manner as above, and each measurement was performed. (Comparative Example 17) A sample was prepared in the same manner as in Example I6, except that the irradiation dose was 40 Mrad, and each measurement was performed. (Comparative Example 18) A sample was prepared in the same manner as in Example 17, except that octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was not added, and each measurement was performed. (Comparative Example 19) In place of the dimethylpolysiloxane in Example 16, 5% dimethylpolysiloxane having a viscosity at 25° C. of 20 cs and having trimedelsilyl groups blocked at both ends was used, but molding was impossible. (Comparative Example 20) A sample was prepared in the same manner as in Example 6, except that 5% dimethylpolysiloxane having a viscosity of 1.2×10'cs at 25° C. and having trimethylsilyl groups blocked at both ends was used, and various measurements were performed. (Comparison N21) A sample was prepared in the same manner as in Example 16, except that 5% pentaphenyltrimethyltrisiloxane having a viscosity of 175 cs at 25° C. was used, and each measurement was performed. (Comparative Example 22) A sample was prepared in the same manner as in Example 16 except that electron beam irradiation was not performed, and each measurement was performed. Examples 16-24 above. The measurement results of Comparative Examples 13 to 22 are collectively shown in Table 3. (The following is a margin) Table (The following is a margin) (Example 25) EPDM-1 and MI are 15g/[0m1n, density is 0.
916g/Cm'' high pressure low density polyethylene (LD-
D) was melt-mixed in a ratio of EPDM-1/LD-D=40/60 (%), and a mixture with a viscosity of 30
00cs dimethylpolysiloxane endblocked with trimethylsilyl groups at both ends, 2% TAIG, and octadecyl-
A resin composition mixed with 0.15% of 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate had an MI of 12g710mln and a density of 0.917.
g/cm” high-pressure low-density polyethylene (hereinafter referred to as LD-
), and the resin composition temperature is 270℃ on kraft paper.
, LD-F temperature 290℃, laminate thickness 10LL resin composition
, coextrusion laminated with LD-F20u, 1 paper/LD-F
/ A three-layer laminate of the resin composition is molded, and then an oxygen concentration of 1
Under an atmosphere of 0 ppm or less, line speed 30 m/m
After electron beam irradiation with an irradiation dose of 3 Mrad, samples were prepared by heat-treating the rolls in a gear oven at 280° C. for 3 days, and used for each measurement. (Example 26) LD-D/EP/EPDM-1=60/30/10(%
) Example 2 except that 5% of dimethylpolysiloxane with a viscosity of 60,000 cs at 25°C and capped with trimethylsilyl groups at both ends was used in the mixture melt-mixed at the ratio of
Samples were prepared in the same manner as in 5, and each measurement was performed. (Example 27) LD-E/EP/EPDM-1=60/30/10(%
), 5% dimethylpolysiloxane with a viscosity of 1oo00cs at 25°C and capped with trimethylsilyl groups at both ends, 2% TMPTMA, and pentaerythrityltetrakis (3-(3,5-di-t
-butyl-4-hydroxyphenyl)propionate)
A sample was prepared in the same manner as in Example 25, except that the resin composition mixed with 0.1% was extruded and laminated on the polyethylene surface of kraft paper laminated with polyethylene at a resin temperature of 270 ° C. and lamination f'420 u. Then, each measurement was performed. (Example 28) LL-A/EP/EPDM-1=60/30/10(
%), 5% dimethylpolysiloxane with a viscosity of 100,000 cs at 25°C and capped with trimethylsilyl groups at both ends, 2% TAIC and octadecyl-3-(3,5-di-t-butyl-4). Samples were prepared in the same manner as in Example 26, except that a resin composition containing 0.15% of -hydroxyphenyl)propionate was used, and each measurement was performed. (Comparative Example 23) A sample was prepared in the same manner as in Example 25 except that TAIC was not added, and each measurement was performed. (Comparative Example 24) Example 25 except that the electron beam irradiation was not performed in Example 11.
Samples were prepared in the same manner as above, and each measurement was performed. Examples 25 to 28 above. The measurement results of Comparative Examples 23 and 24 are collectively shown in Table 4. (Margin below) Table (Note) Comparative Example 24: Poor peelability (base laminate film and paper peeled off, making measurement impossible)

【Effect of the invention】

The present invention uses chemically stable dimethylpolysiloxane, which is difficult to cure even when heated alone, and polyolefin-based thermoplastic resin or low-density polyethylene and monoolefin instead of conventional organopolysiloxane compounds that impart release properties. We have developed a resin composition for radiation-curable release materials that is made by blending a mixture with copolymer rubber, a polyfunctional compound, and an antioxidant, and we have developed a resin composition for use in radiation-curable release materials that does not require complicated processes. In addition, we have developed a method for producing a releasable material that does not require large equipment, which has been a problem in the past, and also requires the use of organic solvents.

Claims (5)

[Claims] (1) It is characterized by consisting of (a) a polyolefin thermoplastic resin or a mixture of low density polyethylene and monoolefin copolymer rubber, (b) dimethylpolysiloxane, (c) a polyfunctional compound, and (d) an antioxidant. A resin composition for radiation-curable releasable materials. (2) Based on a resin composition consisting of (a) a polyolefin thermoplastic resin or a mixture of low density polyethylene and monoolefin copolymer rubber, (b) dimethylpolysiloxane, (c) a polyfunctional compound, and (d) an antioxidant. A removable material that is laminated onto a material and then cured by radiation. (3) A removable material characterized in that the removable material according to claim 2 is treated at a temperature below the melting point of the resin component (a). (4) A resin composition consisting of (a) a polyolefin thermoplastic resin or a mixture of low density polyethylene and monoolefin copolymer rubber (b) dimethylpolysiloxane (c) a polyfunctional compound (d) an antioxidant is applied to paper. Alternatively, a method for producing a removable material, which comprises laminating a polyolefin resin onto paper and then irradiating it with radiation. (5) A method for producing a releasable material, which comprises treating the releasable material obtained according to claim 4 at a temperature below the melting point of the resin component (a).