JP5621749B2 - Radiation curable silicone composition for release paper - Google Patents

Description

  The present invention relates to a radiation curable silicone composition, and more particularly to a radiation curable silicone composition suitably used for forming release paper (including a release film).

  Conventionally, various means are known as a method for curing a silicone composition. In recent years, the curing method by radiation irradiation among them is energy-saving compared to the heat curing type, can be handled even if the installation space is small, and is also interested from the features such as the environment-friendly curing system It is also expected to be used in many fields. Among them, the curing method using cationic polymerization, in which an epoxy group is ring-opened using a photoacid generator, is less susceptible to curing by oxygen than conventional radical polymerization using an acrylic group, and is convenient and easy to operate. The use is expanding because of its excellent properties (see Patent Documents 1 and 2).

  In general, most of release papers and release films used for labels and production process papers are surface-treated with a silicone composition mainly composed of polyorganosiloxane. As quality control of these products, it is required that the coating state of the silicone composition on the base material is uniform and neatly treated, and that no silicone is detached.

  However, the conventional silicone composition is colorless and transparent, and usually the coating amount of the silicone composition relative to the substrate such as paper or film is extremely small. Since it was difficult to observe the coating state, it was difficult to check the drop-off of the silicone coating film, and quality control was difficult, for example, causing poor peelability when it was labeled.

  As a countermeasure against this problem, there is a method of coloring the silicone composition, whereby the silicone coating state can be visually confirmed.

  As a method of coloring the silicone composition, there is a method of adding a colorant such as a pigment to the silicone composition. However, since the pigment component is a curing inhibitor, it may cause curing failure or in the silicone composition. There is a problem that the coloring component settles with time. In addition, when the silicone composition is applied to a substrate such as paper or film, the silicone composition is often diluted with an organic solvent in order to apply the silicone composition thinly and uniformly. When the silicone composition to which the pigment has been added is diluted with an organic solvent, the dispersibility of the pigment may be significantly reduced.

  As a method for dispersing a pigment as a coloring component in a silicone composition, in Patent Document 3, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, which is a cationically polymerizable silane, silica having an average particle size of 5 to 10 μm, Although conductive fine particles are added, there is no particular description regarding the temporal dispersion stability of the fine particles. In Patent Document 4, the pigment dispersibility is good under the condition that the silicone composition is not diluted with a solvent or the like by adding a pigment having an average particle diameter of 1 to 1,000 nm to the cationic polymerizable polyorganosiloxane. There is no particular description regarding the pigment dispersibility in the diluted condition.

  As described above, for the above reason, the technique of coloring the silicone composition has not yet been put into practical use. In addition, as a method for coloring the release film or release paper, a method of using a colored base material has been proposed, but since the colored base material is expensive in addition to lack of flexibility such as color shading, even on the profit side Due to problems, it has not been put to practical use.

Japanese Patent No. 3384268 Japanese Patent No. 3993533 Japanese Patent No. 3207000 Japanese Patent Laid-Open No. 2001-226592

  The present invention has been made in view of the above-described problems in the prior art, and provides a radiation curable silicone composition capable of satisfactorily achieving both dispersibility and curability of a pigment for coloring a cured silicone product. With the goal.

  As a result of intensive studies to achieve the above object, the present inventor has found that a radiation-curable cationic polymerizable organopolysiloxane has a pigment for coloring a silicone cured product, and particularly an acrylic silicone polymer as a pigment dispersant. It has been found that it is possible to achieve both pigment dispersibility, particularly pigment dispersibility and curability under solvent dilution conditions, which has been difficult with conventional combinations of pigments and pigment dispersants. It was.

（式中、Ｒｆは水素原子の８０モル％以上がフッ素原子で置換された炭素数１〜８のアルキル基を表す。ｐはその個数を示し、１〜５の整数である。ｐ個のＲｆはそれぞれ同一であっても異なっていてもよい。）
<４> 前記成分（Ｂ）が、
Ｒ³ ₂Ｉ⁺Ｘ^-、Ｒ³ ₃Ｓ⁺Ｘ^-、Ｒ³ ₃Ｓｅ⁺Ｘ^-、Ｒ³ ₄Ｐ⁺Ｘ^-、又はＲ³ ₄Ｎ⁺Ｘ^-
（式中、Ｒ³は置換もしくは非置換のアリール基、置換もしくは非置換の複素環基、置換もしくは非置換のアリールオキシ基、置換もしくは非置換の複素環オキシ基である。Ｒ³は互いに結合してこれらが結合するＩ、Ｓ、Ｓｅ、Ｐ又はＮ原子と共に環構造を形成していてもよい。Ｘ^-はＳｂＦ₆ ^-、ＡｓＦ₆ ^-、ＰＦ₆ ^-、ＢＦ₄ ^-、ＨＳＯ₄ ^-、又はＣｌＯ₄ ^-である。）
で示されるジアリールヨードニウム塩、トリアリールスルホニウム塩、トリアリールセレノニウム塩、テトラアリールホスホニウム塩、又はアリールジアゾニウム塩であることを特徴とする<１>又は<２>記載の放射線硬化性シリコーン組成物。
<５> 前記成分（Ｂ）が、ジアリールヨードニウム又はトリアリールスルホニウムのヘキサフルオロアンチモン酸塩であることを特徴とする<４>記載の放射線硬化性シリコーン組成物。
<６> 前記成分（Ａ）中の全有機基Ｒ¹及びＲ²の１〜２５モル％が１価のエポキシ官能性有機基であることを特徴とする<１>〜<５>のいずれかに記載の放射線硬化性シリコーン組成物。 That is, the present invention provides the following radiation-curable silicone composition for release paper .
<1> (A) Cationic polymerizable organopolysiloxane having an epoxy group represented by the following average composition formula (1) and having a viscosity at 25 ° C. of 100 to 100,000 mPa · s : 100 parts by mass
R ¹ _m R ² _n SiO _{(4-mn) / 2} (1)
(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is an organic group containing an epoxy group, m> 0, n> 0, and further 0 <M + n ≦ 3.)
(B) a photoacid generator component that exhibits a catalytic action on the radiation curing reaction of the component (A): 0.05 to 20 parts by mass;
(C) radical copolymerizing a monomer raw material containing an organopolysiloxane compound (E) having one radical polymerizable group in one molecule and a radical polymerizable monomer (F) selected from acrylates and methacrylates. Acryl-silicone graft copolymer obtained: 0.05 to 25 parts by mass,
(D) a coloring pigment capable of cured silicone: Ri Na contain 1 to 25 parts by weight, 0.1% by mass Rukoto addition amount of the component (D) component (C) A radiation curable silicone composition for release paper .
<2> The mass ratio [E / F] of the organopolysiloxane (E) and the radical polymerizable monomer (F) in the acrylic-silicone graft copolymer (C) is 30/70 to 99/1. <1> The radiation curable silicone composition according to <1>.
<3> The radiation curable silicone composition according to <1> or <2>, wherein the component (B) is a fluorinated alkyl fluorophosphate represented by the following composition formula (2).

(In the formula, Rf represents an alkyl group having 1 to 8 carbon atoms in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. P represents the number and is an integer of 1 to 5. p Rf May be the same or different.)
<4> The component (B) is
R ³ ₂ I ⁺ X ⁻ , R ³ ₃ S ⁺ X ⁻ , R ³ ₃ Se ⁺ X ⁻ , R ³ ₄ P ⁺ X ⁻ , or R ³ ₄ N ⁺ X ⁻
(Wherein R ³ is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic oxy group. R ³ is bonded to each other. And may form a ring structure together with the I, S, Se, P or N atoms to which they are bonded, and X ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , HSO ₄ ⁻ , or ClO ₄ ^- a is).
The radiation curable silicone composition according to <1> or <2>, which is a diaryliodonium salt, triarylsulfonium salt, triarylselenonium salt, tetraarylphosphonium salt, or aryldiazonium salt represented by the formula:
<5> The radiation curable silicone composition according to <4>, wherein the component (B) is a hexafluoroantimonate of diaryliodonium or triarylsulfonium.
<6> Any one of <1> to <5>, wherein 1 to 25 mol% of all organic groups R ¹ and R ² in component (A) are monovalent epoxy-functional organic groups The radiation curable silicone composition described in 1.

  According to the radiation curable silicone composition of the present invention, a pigment as a silicone cured product colorant and a specific acrylic-silicone copolymer as a pigment dispersant for a cationically polymerizable organopolysiloxane having an epoxy group. The pigment dispersibility, particularly the pigment dispersibility when the component of the present invention is diluted with an organic solvent, is improved, and the cured silicone product can be colored. Moreover, the addition of the acrylic silicone copolymer makes it difficult for the inhibition of curing due to the addition of the pigment to occur than in the case of a conventional pigment dispersant, and good curability can be obtained.

  The radiation-curable silicone composition of the present invention is composed of components (A), (B), (C), and (D), which will be described in detail below.

[Component (A)]
Component (A) in the radiation curable silicone composition of the present invention is a cationically polymerizable organopolysiloxane, and is represented by the following average composition formula (1).
R ¹ _m R ² _n SiO _{(4-mn) / 2} (1)

Here, in the average composition formula (1), R ¹ is an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or these A hydroxypropyl group, a cyanoethyl group, a 1-chloropropyl group, 3,3,3-trimethyl, wherein a part or all of the hydrogen atoms bonded to the carbon atoms of the group are substituted with a hydroxy group, a cyano group, a halogen atom, or the like An unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms selected from a fluoropropyl group and the like, and R ² is a cationically polymerizable epoxy functional group. Further, 80 mol% or more of R ¹ is preferably an alkyl group, and more preferably a methyl group.

Further, the following structure is preferable as the cationic polymerizable epoxy functional group of R ² .

In the component (A), ¹ to 25 mol% of all organic groups (that is, the total of R ¹ and R ² ) is a monovalent epoxy functional organic group (that is, R ² ) from the viewpoint of curability. Cationic polymerizable organopolysiloxanes are preferred, and more preferred are cationic polymerizable organopolysiloxanes in which 1-20% of the total organic groups are epoxy functional organic groups. If the amount of this epoxy functional group is less than 1 mol%, the curing rate is slow, and there is a risk of poor curing.

  Further, the viscosity of the organopolysiloxane at room temperature (25 ° C.) is preferably 1,000,000 mPa · s or less, more preferably 100,000 mPa · s or less. In this case, 5 to 1 million mPa · s is preferable, and 100 to 100,000 mPa · s is more preferable. When the viscosity of the organopolysiloxane is higher than 1,000,000 mPa · s, the viscosity of the composition becomes high and handling may be difficult, and when it is lower than 5 mPa · s, the coating property may be deteriorated. The viscosity is measured using a rotational viscometer.

[Component (B)]
Component (B) of the radiation curable silicone composition of the present invention is a photoacid generator component that exhibits a catalytic action on the radiation curing reaction of component (A) (cationically polymerizable organopolysiloxane).
Examples of the component (B) include fluorinated alkyl fluorophosphates represented by the following composition formula (2).

Here, in the fluorinated alkylfluorophosphate anion represented by [(Rf) _p PF _6-p ] ⁻ in the composition formula (2), Rf represents an alkyl group substituted with a fluorine atom, and preferably has a carbon number. Are 1 to 8, more preferably 1 to 4 carbon atoms.

  Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl, branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl, and cyclopropyl, cyclobutyl and cyclopentyl. And cyclic alkyl groups such as cyclohexyl and the like. The proportion of alkyl group hydrogen atoms replaced by fluorine atoms is usually 80 mol% or more, preferably 90 mol% or more, and more preferably 100 mol%. When the substitution rate of fluorine atoms is less than 80 mol%, the cationic polymerization initiating ability of the onium salt of the present invention may be lowered.

Particularly preferred Rf is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%. Specific examples include CF ₃ , CF ₃ CF ₂ , ( _{CF 3) 2 CF, CF 3} CF 2 CF 2, CF 3 CF 2 CF 2 CF 2, (CF 3) 2 CFCF 2, CF 3 CF 2 (CF 3) CF, include (CF _{3) 3} C.

  In the composition formula (2), the number p of Rf is an integer of 1 to 5, preferably 2 to 4, particularly preferably 2 or 3. The p Rf's may be the same or different.

Specific examples of preferred fluorinated alkyl fluorophosphate anions include
[(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] _{^{-, [((CF 3)}} 2 CFCF 2) 3 PF 3] -, [(CF 3 CF 2 CF 2 CF 2) 2 PF 4] - and _{[(CF 3 CF 2 CF 2} CF 2) 3 PF 3] ^-. of _{these, [(CF 3 CF 2)} 3 PF 3] -, [(CF 3 CF 2 CF 2) 3 PF 3] -, [((CF 3) 2 CF) 3 PF 3] ^- , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ^- ,
_{[((CF 3) 2 CFCF} 2) 3 PF 3] - and _{[((CF 3) 2 CFCF} 2) 2 PF 4] - it is particularly preferred. )

  Examples of the component (B) further include diaryl iodonium salts, triaryl sulfonium salts, triaryl selenonium salts, tetraaryl phosphonium salts, aryl diazonium salts represented by the following general formula (3). Among them, diaryl iodonium and triarylsulfonium hexafluoroantimonate are preferable from the viewpoint of curing reactivity.

R ³ ₂ I ⁺ X ⁻ , R ³ ₃ S ⁺ X ⁻ , R ³ ₃ Se ⁺ X ⁻ , R ³ ₄ P ⁺ X ⁻ , or R ³ ₄ N ⁺ X ⁻ (3)
(Wherein R ³ is a substituted or unsubstituted aryl group such as a phenyl group, a tolyl group, a 4- (ethyl) phenyl group or the like, a substituted or unsubstituted aryl group such as a pyridyl group, an N-methylpyridyl group or an indolyl group) A substituted or unsubstituted aryloxy group such as a methoxyphenyl group, isopropoxyphenyl group, etc., or a substituted or unsubstituted heterocyclic oxy group such as a 4-methoxypyridyl group, etc. R ³ is bonded to each other. good I, S, Se, may form a ring structure with P or N atoms .X ^- is _{^{SbF 6 -, AsF 6 -,}} PF 6 -, BF 4 -, HSO 4 -, ClO 4 - , such as Anion.)

  Here, the addition amount of the component (B) is not particularly limited as long as it is an effective amount as an onium salt photoinitiator, that is, an amount effective for curing the silicone composition of the present invention by irradiation with ultraviolet rays. The component (A) may be 0.05 to 20 parts by mass, particularly 0.1 to 20 parts by mass with respect to 100 parts by mass.

[Component (C)]
The component (C) in the radiation curable silicone composition of the present invention is composed of an organopolysiloxane compound (E) having one radical polymerizable group in one molecule, radical polymerization selected from acrylates and methacrylates. An acrylic-silicone graft copolymer obtained by radical copolymerization of a monomer raw material containing the monomer (F).

  Here, the organopolysiloxane compound (E) having one radical polymerizable group in one molecule is preferably represented by the following general formula (4).

In the general formula (4), R ⁴ represents an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, or a carbon of these groups. Hydroxypropyl group, cyanoethyl group, 1-chloropropyl group, 3,3,3-trifluoropropyl group, etc. in which part or all of the hydrogen atoms bonded to the atom are substituted with hydroxy group, cyano group, halogen atom, etc. Is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and only one of the substituents R ⁴ is a substituent represented by the following general formula (5).

In the general formula (5), R ⁵ is a hydrogen atom or a methyl group, R ⁶ is a straight chain having 1 to 10 carbon atoms such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group or an isobutylene group, or A divalent saturated hydrocarbon group such as a branched alkylene group, and optionally one or two ether bonds may intervene.

  In the general formula (4), q is 2 or more, and r, s, and t are 0 or a positive number, but the number of silicon atoms in the component (E) is 2 to 500, especially 3 300 is preferable. As long as the component (E) has a structure satisfying the general formula (4), the effect of the present invention can be exhibited. However, q = 2, r = 1 to 300, s = 0 to 100, t = A range of 0 to 100 is preferable, and q = 2, r = 1 to 300, and s, t = 0 are particularly preferable.

  The radical polymerizable monomer (F) selected from acrylates and methacrylates is preferably a compound having one radical polymerizable unsaturated bond in the molecule. Examples of the acrylate and methacrylate used include methyl (meth) acrylate and ethyl. Hydroxyalkyl such as (meth) acrylate, alkyl (meth) acrylate such as n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate ( Examples include (meth) acrylates and perfluoroalkyl (meth) acrylates having 1 to 10 carbon chains.

  The mass ratio [(E) / (F)] of the organopolysiloxane compound (E) having one radical polymerizable group in one molecule and the radical polymerizable monomer (F) is 30/70 to 99 /. It is preferable to be within the range of 1. When the mass ratio [(E) / (F)] is less than 30/70, the silicone component decreases, so the solubility in the cationically polymerizable organopolysiloxane (component (A)) becomes poor and the pigment dispersibility is improved. In some cases, the pigment dispersibility may be deteriorated when the ratio exceeds 99/1. If necessary, other monomers can be copolymerized as long as the effects of the present invention are not hindered.

  Copolymerization of monomer raw materials containing an organopolysiloxane compound (E) having one radical polymerizable group in one molecule and a radical polymerizable monomer (F) is known as described in Japanese Patent No. 2704730. And is carried out in the presence of a normal radical polymerization initiator such as benzoyl peroxide, lauroyl peroxide, azobisisobutyronitrile, solution polymerization, emulsion polymerization, suspension polymerization, bulk Any of the polymerization methods can be applied.

  Component (C) is added in an amount of 0.05 to 25 parts by mass per 100 parts by mass of component (A). In this case, it is preferable to set it as 0.05-200 mass% with respect to the pigment which is the component (D) which describes a detail below, Most preferably, it is 0.1-100 mass%. If it is less than 0.05% by mass relative to the component (D), there is little influence on the improvement of pigment dispersibility, and even if it is added more than 200% by mass, improvement in pigment dispersibility cannot be expected.

  Examples of pigment dispersants other than component (C) generally include phosphate ester derivatives, quaternary ammonium compounds, and the like, but the use of such compounds improves the pigment dispersibility, but the present radiation curing. In cationic polymerization, which is a method for curing a functional silicone composition, curability is remarkably reduced, and a cured film cannot be formed efficiently. In addition, these compounds have a high possibility of trapping an important proton when the cationic polymerization proceeds, and the cationic polymerization is inhibited. On the other hand, the component (C) has a low possibility of trapping protons from the structure, and can improve the pigment dispersibility without inhibiting the curability.

[Component (D)]
The pigment which is the component (D) of the radiation curable silicone composition of the present invention is not particularly limited as long as it can color the cured silicone, and various known organic or inorganic pigments can be used. It is. Specific examples of the pigment (component (D)) include white pigments such as titanium white, zinc white, and antimony white, black pigments such as carbon black, graphite, and iron black, red pigments such as molybdenum red, brown, and pigment red. Examples thereof include yellow pigments such as yellow lead, yellow iron oxide, titanium yellow, and pigment yellow, and blue pigments such as copper phthalocyanine and cobalt blue. Among these, the radiation curable silicone composition used in the release paper application has a small coating amount on a substrate such as paper and film, and therefore when using pigment components such as red and blue, It is easy to visually check the silicone coating state after coating.

  The method for dispersing the pigment is not particularly limited, and a known method can be employed. Specific examples include a method of uniformly dispersing by using a three-roll, five-roll, paint shaker, ball mill, homogenizer and the like. Further, after preparing a master batch in which a pigment is dispersed at a high concentration, it may be diluted to a predetermined pigment concentration. In order to improve the operability of dispersion, a small amount of a solvent or the like may be added to the pigment and then dispersed.

  The addition amount of the pigment (component (D)) is 1 to 25 parts by mass, preferably 2 to 20 parts by mass with respect to 100 parts by mass of the component (A). If the addition amount of the component (D) is less than 1 part by mass, the coloring is thin and the purpose cannot be achieved. Moreover, when the addition amount of component (D) exceeds 25 parts by mass, the ultraviolet ray transmittance is deteriorated and the curability is remarkably lowered, and the viscosity of the silicone composition is increased, and the workability during coating is remarkably lowered. There is a risk.

  The radiation-curable silicone composition of the present invention contains an organic solvent, and can be used after diluted with an organic solvent. In this case, examples of the organic solvent include hydrocarbon compounds such as hexane, heptane, and octane, ketone compounds such as acetone, 2-butanone, and methyl isobutyl ketone, alcohol compounds such as methanol, ethanol, and i-propanol, toluene, xylene, and the like. Any of these compounds may be used as long as they can dissolve silicone.

The radiation curable silicone composition of the present invention is obtained by blending predetermined amounts of the above components, but in addition to the above components, as optional components, fillers, antistatic agents, flame retardants, antifoaming agents, Additives such as a flow modifier, a light stabilizer, a non-reactive resin, and a radical polymerizable compound can be blended.
The amount of the optional component added can be a normal amount as long as the effects of the present invention are not hindered.

Moreover, the radiation-curable silicone composition of the present invention can be cured by irradiation with radiation energy rays. Any radiation energy ray may be used as long as it has an energy that induces decomposition of the photoacid generator as component (B). Preferably, it is a high-pressure or ultrahigh-pressure mercury lamp, metal halide lamp, xenon lamp, carbon arc lamp. Energy beams in the ultraviolet to visible light region (about 100 to about 800 nm) obtained from fluorescent lamps, semiconductor solid lasers, argon lasers, He—Cd lasers, KrF excimer lasers, ArF excimer lasers, F ₂ lasers, and the like are used. It is recommended to use a radiation light source having a high light hardness, preferably at a wavelength of 200 to 400 nm, more preferably 300 to 400 nm. Furthermore, radiation having high energy such as electron beam and X-ray can be used. The irradiation time of radiation energy is usually about 0.1 to 10 seconds at room temperature. However, when the energy ray transmission is low or the film thickness of the curable composition is thick, the time is longer. It may be preferable to apply. If necessary, after irradiation with energy rays, it can be heated at room temperature to 150 ° C. for several seconds to several hours, and aftercured.

  Specific uses of the radiation curable silicone composition of the present invention include paints, coating agents, inks, positive resists, resist films, liquid resists, photosensitive materials, adhesives, release papers, molding materials, and casting materials. , Putty, glass fiber impregnating agent, sealing material, sealing material, sealing material, stereolithography material, and the like, which are particularly suitable for use as a release paper because they can be colored and have good curability.

When used for release paper, the radiation-curable silicone composition of the present invention is applied to a substrate such as paper or plastic film, and then cured by irradiation with radiation as described above. Is preferably 0.01 to 3.0 g / m ² , particularly preferably 0.05 to 2.5 g / m ² .

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by this. In the following examples, the physical properties in the tables are evaluated under the following conditions.

[Curability of radiation curable silicone composition]
After preparing the radiation curable silicone composition, it is applied to a polyethylene laminate fine paper by roll application so that the application amount is about 0.6 g / m ² , and then 100 mJ using two 80 W / cm high pressure mercury lamps. A cured film was formed by irradiating ultraviolet rays at an irradiation amount of / cm ² .
The obtained cured film was evaluated as follows.
○: When the entire composition is cured Δ: When the entire composition is being cured (during curing) ×: When the entire composition is uncured

[Pigment dispersibility of radiation curable silicone composition]
3 parts by weight of the radiation-curable silicone composition thus peeled is dissolved in 48.5 parts by weight of hexane and 48.5 parts by weight of methyl ethyl ketone, and the solution is stored in a cool and dark place. Evaluated.
○: When the pigment has not settled for more than one week Δ: When the pigment has settled within one week ×: When the pigment has settled within three days

  In the structural formula shown in Example 1, Me represents a methyl group, and Ep represents the following epoxy functional group.

成分（ｃ１）：
・下記方法で重合させて得たグラフトポリマー（アクリル−シリコーン系グラフト共重合体） １．４質量部 [Example 1]
The radiation-curable silicone composition of the present invention was prepared under the following conditions.
Component (a):
A cationically polymerizable organopolysiloxane that corresponds to the average composition formula (1) that is a component of the present invention, is represented by the following average composition formula (1 ′), and has a viscosity of 500 mPa · s at 25 ° C.
91.6 parts by mass

Component (c1):
-Graft polymer obtained by polymerizing by the following method (acryl-silicone graft copolymer) 1.4 parts by mass

成分（ｄ１）：
・銅フタロシアニン（東洋インキ製ＬＩＯＮＯＬ ＢＬＵＥ ＦＧ−７４００Ｇ（ｐｉｇｍｅｎｔ ｂｌｕｅ １５：４） ７質量部
まず、上記成分（ａ）、（ｃ１）、（ｄ１）を混合し、３本ロールにて均一分散させて、混合物を得た。
次いで、この混合物に、光酸発生剤である成分（ｂ１）として４−（イソプロピル）フェニル（ｐ−トリル）ヨードニウムトリス（ペンタフルオロエチル）トリフルオロホスフェートをトルエンに５０質量％で溶解した溶液を５．０質量部添加し、均一に混合させて、本発明の放射線硬化性シリコーン組成物であるシリコーン組成物１を得た。 [Synthesis of Component (c1)]
95 parts by weight of one-end methacrylate-substituted dimethylpolysiloxane (raw material component (e1)) represented by the following average composition formula (e1), 1 part by weight of methyl methacrylate (raw material component (f1)), 2-ethylhexyl acrylate (raw material component ( f2)) 4 parts by mass were polymerized with tert-butylperoxy 2-ethylhexanoate in a toluene solution to synthesize a graft polymer.

Component (d1):
・ Copper phthalocyanine (LIONOL BLUE FG-7400G (pigment blue 15: 4) 7 parts by mass manufactured by Toyo Ink Co., Ltd.) First, the above components (a), (c1) and (d1) are mixed and uniformly dispersed with three rolls A mixture was obtained.
Next, a solution of 4- (isopropyl) phenyl (p-tolyl) iodonium tris (pentafluoroethyl) trifluorophosphate dissolved in toluene at 50% by mass as component (b1) which is a photoacid generator was added to this mixture at 5% by mass. 0.0 part by mass was added and mixed uniformly to obtain a silicone composition 1 which is a radiation curable silicone composition of the present invention.

[Example 2]
In Example 1, instead of the component (c1) as an acrylic-silicone graft copolymer, the component (c2) (addition amount: 1.4 parts by mass) which is a graft polymer obtained by polymerization according to the following method was used. Except for the above, it was prepared under the same conditions as in Example 1 to obtain a silicone composition 2 which is a radiation curable silicone composition of the present invention.
[Synthesis of Component (c2)]
50 parts by weight of one-end methacrylate-substituted dimethylpolysiloxane (raw material component e2) represented by the following average composition formula (e2), 35 parts by weight of methyl methacrylate (raw material component f1), 8 parts by weight of 2-ethylhexyl acrylate (raw material component f2), A graft polymer (component (c2)) was synthesized by polymerizing 7.5 parts by mass of n-butyl methacrylate (raw material component f3) with tertiary butyl peroxy 2-ethylhexanate.

[Example 3]
In Example 1, instead of component (b1) as a photoacid generator, a solution in which bis- [4-nalkyl (C10-C13) phenyl] iodonium hexafluoroantimonate was dissolved in toluene at 50% by mass was used as a component ( b2) (addition amount 5.0 parts by mass), and the other conditions were the same as in Example 1 to obtain a silicone composition 3 which is a radiation curable silicone composition of the present invention.

[Example 4]
In Example 1, instead of component (d1) as a pigment, iron (III) red pigment (Sicotrans Red L 2715 D (Pigment Red 101) manufactured by BASF) was used as component (d2) (addition amount: 7 parts by mass). The others were prepared under the same conditions as in Example 1 to obtain a silicone composition 4 which is a radiation curable silicone composition of the present invention.

[Comparative Example 1]
In Example 1, the component (c1) was not added, and other than that was prepared on the same conditions as Example 1, and the silicone composition 5 was obtained.

[Comparative Example 2]
In Example 1, in place of the component (c1), a phosphate ester compound (DISPERBYK-145 manufactured by Big Chemie Japan) as a dispersant is used as the component (c3) (addition amount: 1.4 parts by mass), and the others Was prepared under the same conditions as in Example 1 to obtain a silicone composition 6.

[Comparative Example 3]
In Example 1, instead of the component (c1), a quaternary ammonium salt compound (BYK-9076, manufactured by BYK Japan) as a dispersant was used as the component (c4) (addition amount 1.4 parts by mass). Except for the above, it was prepared under the same conditions as in Example 1 to obtain a silicone composition 7.

  The silicone compositions 1 to 7 obtained above were evaluated for curability and dispersibility. The obtained results are shown in Table 1.

As a result of evaluation, in Examples 1 to 4, both curability and dispersibility were good.
On the other hand, in Comparative Example 1 in which no dispersant was added, the curability was good, but the dispersibility was poor. In Comparative Examples 2 and 3, the dispersibility was good, but the curability was poor.

Claims (6)

(A) Cationic polymerizable organopolysiloxane having an epoxy group represented by the following average composition formula (1) and having a viscosity at 25 ° C. of 100 to 100,000 mPa · s : 100 parts by mass
R ¹ _m R ² _n SiO _{(4-mn) / 2} (1)
(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ² is an organic group containing an epoxy group, m> 0, n> 0, and further 0 <M + n ≦ 3.)
(B) a photoacid generator component that exhibits a catalytic action on the radiation curing reaction of the component (A): 0.05 to 20 parts by mass;
(C) radical copolymerizing a monomer raw material containing an organopolysiloxane compound (E) having one radical polymerizable group in one molecule and a radical polymerizable monomer (F) selected from acrylates and methacrylates. Acryl-silicone graft copolymer obtained: 0.05 to 25 parts by mass,
(D) a coloring pigment capable of cured silicone: Ri Na contain 1 to 25 parts by weight, 0.1% by mass Rukoto addition amount of the component (D) component (C) A radiation curable silicone composition for release paper .   The mass ratio [E / F] of the organopolysiloxane (E) and the radical polymerizable monomer (F) in the acrylic-silicone graft copolymer (C) is 30/70 to 99/1. The radiation-curable silicone composition according to claim 1. The radiation-curable silicone composition according to claim 1 or 2, wherein the component (B) is a fluorinated alkyl fluorophosphate represented by the following composition formula (2).

(In the formula, Rf represents an alkyl group having 1 to 8 carbon atoms in which 80 mol% or more of hydrogen atoms are substituted with fluorine atoms. P represents the number and is an integer of 1 to 5. p Rf May be the same or different.) The component (B) is
R ³ ₂ I ⁺ X ⁻ , R ³ ₃ S ⁺ X ⁻ , R ³ ₃ Se ⁺ X ⁻ , R ³ ₄ P ⁺ X ⁻ , or R ³ ₄ N ⁺ X ⁻
(Wherein R ³ is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted aryloxy group, or a substituted or unsubstituted heterocyclic oxy group. R ³ is bonded to each other. And may form a ring structure together with the I, S, Se, P or N atoms to which they are bonded, and X ⁻ is SbF ₆ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , HSO ₄ ⁻ , or ClO ₄ ^- a is).
The radiation curable silicone composition according to claim 1 or 2, which is a diaryl iodonium salt, a triaryl sulfonium salt, a triaryl selenonium salt, a tetraaryl phosphonium salt, or an aryl diazonium salt represented by formula (1).   The radiation curable silicone composition according to claim 4, wherein the component (B) is a hexafluoroantimonate of diaryl iodonium or triaryl sulfonium. The radiation according to claim 1, wherein 1 to 25 mol% of all organic groups R ¹ and R ^{2 in} the component (A) is a monovalent epoxy-functional organic group. Curable silicone composition.