KR20070054122A - Solvent-free silicone composition for release paper - Google Patents

Abstract

The present invention is a silicone composition exhibiting heavy peeling property at the time of low-speed peeling, and having a large difference between the peeling force at the time of low-speed peeling and the peeling force at the high-speed peeling, that is, the peeling force having a positive correlation with respect to the peeling rate. To provide.

The silicone composition of the present invention comprises MQ resin (A) having an alkenyl group amount of 0.06 to 0.10 mol / 100 g in the molecule, MQ resin (B) having an alkenyl group amount of 0.4 to 0.7 mol / 100 g in the molecule, and both ends The organopolysiloxane (C) which has an alkenyl group only is mix | blended in fixed amount, and has organohydrogenpolysiloxane (D) as a main component as a crosslinking agent.

Solvent-free release paper silicone composition, organopolysiloxane, organohydrogenpolysiloxane

Description

Solvent free release silicone composition {SOLVENT-FREE SILICONE COMPOSITION FOR RELEASE PAPER}

[Patent Document 1] Japanese Unexamined Patent Publication No. 49-47426

[Patent Document 2] Japanese Unexamined Patent Publication No. 50-141591

[Patent Document 3] Japanese Patent Application Laid-Open No. 52-39791

[Patent Document 4] Japanese Unexamined Patent Publication No. 57-77395

This invention relates to the silicone composition for non-solvent type release paper in which peeling force has a positive correlation with respect to peeling speed.

Conventionally, various kinds of silicone compositions for release paper used to prevent adhesion or sticking between substrates such as paper and plastic and adhesive materials are known, and among them, the solvent-type silicone compositions have relatively low surface selectivity and relatively low substrate selectivity. It has been widely used in this regard. However, in recent years, the demand for a solvent-free silicone composition is increasing in terms of safety and hygiene. Various types of this solvent-free silicone composition are known (Japanese Patent Laid-Open No. 49-47426, Japanese Patent Laid-Open No. 50-141591, Japanese Patent Laid-Open No. 52-39791 and Japanese Patent) See Publication (S) 57-77395).

Generally, the silicone composition for release paper is required to have various peeling forces depending on the purpose. In particular, in the silicone composition used for the release paper for double-sided tape, the silicone composition for forming a hard peelable film (called mirror surface) and a heavy peelable film (called heavy surface) on both adhesion layers is calculated | required. . There must be a clear difference in this peeling force between the mirror and the middle surface, and the difference must be maintained even at a high peel rate. If the peeling force of the mirror surface and the middle surface is reversed when the peeling speed is high, a problem arises that the release paper on the side of the surface is peeled off first when the mirror surface is to be peeled off due to this difference.

For this reason, the silicone composition from which peeling force differs is used for a mirror surface and a middle surface, and in order to obtain such a cured film, the method of using the peelable composition whose crosslinking degree is lower than a middle surface for mirror surface is proposed. However, when this method is used for non-solvent type silicone, there existed a problem that peeling force of the mirror surface and the middle surface was reversed when peeling speed becomes high, and peeling force of the middle surface becomes small at high speed.

In view of this, a silicone composition exhibiting heavy peeling property at low peeling and having a large difference in peeling force at low peeling and peeling at high peeling, ie, a silicone for a non-solvent type release paper having a positive correlation with peeling force with respect to peeling speed, It is required.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, as a result, MQ resin (A) whose amount of alkenyl groups is 0.06-0.10 mol / 100 g in a molecule | numerator, and 0.4-0.7 mol / 100 g of alkenyl groups in a molecule | numerator When a fixed amount of phosphorus MQ resin (B) and an organopolysiloxane (C) having an alkenyl group at both ends is blended, a cured film obtained from a silicone composition containing organohydrogenpolysiloxane (D) as a main component as a crosslinking agent may have a slow peeling rate. When it shows heavy peeling property, it discovered that peeling force has a positive correlation with respect to peeling rate, and came to complete this invention.

That is, (A) 10-30 mass parts of organopolysiloxane represented by following formula (1), (B) 10-30 mass parts of organopolysiloxane represented by following formula (2), (C) organopolysiloxane represented by following formula (3) 40 to 80 parts by mass, (D) the number of moles of hydrogen atoms bonded to the silicon atom represented by the following formula (4), the organopolysiloxane of the component (A), the organopolysiloxane of the component (B), and the Organopolysiloxane which is a mass part equivalent to 1.0-4.0 times mole with respect to the total number of alkenyl groups of the sum total of the organopolysiloxane, and (E) catalyst group platinum group metal type compound

It is a silicone composition for use in a non-solvent type release paper having a viscosity of 1000 mPa · s or less, wherein the film after curing of the composition exhibits heavy peeling property at the time of low-speed peeling, and it is confirmed that the peeling force has a positive correlation with the peeling rate. The invention has been completed.

In the formula, R ¹ is an unsubstituted or substituted C1-C10 monovalent hydrocarbon group having no aliphatic unsaturated bond, and R ² is-(CH ₂ ) _p -CH = CH ₂ (p is an integer of 0 to 6). ) Is an alkenyl group, the amount of alkenyl groups in the molecule is 0.06 to 0.10 mol / 100 g, a, b and c are positive numbers 1≤a≤100, 5≤b≤200, 5≤c≤300, (a + b) /c=0.5 to 1.0.

In formula, R <^1> and R <^2> are the same as the above, and the amount of alkenyl groups is 0.4-0.7 mol / 100g in a molecule | numerator. D, e, and f are 1 ≦ d ≦ 75, 0 ≦ e ≦ 20, 1 ≦ f ≦ 50, (d + e) /f=0.6 to 1.5, and d, e and f are organo It is the number which makes the viscosity in 25 degreeC of polysiloxane into 5-100 mPa * s.

In formula, R <^1> and R <^2> is the same as the above, g is the number whose viscosity of the organopolysiloxane containing an alkenyl group only at the terminal is 800-2000 mPa * s.

In formula, R <^1> is the same as the above and R <^3> is a hydrogen atom or R <^1> . J is an integer of 8 ≦ j ≦ 20.

Best Mode for Carrying Out the Invention

The silicone composition of this invention has components (A)-(D) as a main component, and each component is demonstrated in detail below. The organopolysiloxane of (A) component is represented by following formula (1).

<Formula 1>

^{_{R 2 R 1 2 SiO 1/}} 2 units, R _{¹ 3} SiO _^1/2, and an organopolysiloxane containing units and SiO _4/2 units, R ¹ is C 1 -C 10 unsubstituted or substituted, aliphatic unsaturation It is a monovalent hydrocarbon group which does not have, and specifically, is bonded to an alkyl group such as methyl group, ethyl group, propyl group and butyl group, cycloalkyl group such as cyclohexyl group, aryl group such as phenyl group and tolyl group or carbon atom of these groups Selected from hydroxypropyl group, cyanoethyl group, 1-chloropropyl group, 3,3,3-trifluoropropyl group, etc. in which some or all of the hydrogen atoms are substituted with hydroxyl groups, cyano groups, halogen atoms, etc. do. Preferably, it is an alkyl group and an aryl group from the point of curability and peelability. In particular, it is a methyl group.

R ² is an alkenyl group represented by — (CH ₂ ) _c —CH═CH ₂ (c is an integer of 0 to 6). Moreover, the amount of alkenyl groups of this organopolysiloxane is 0.06-0.10 mol / 100 g, Preferably it is 0.07-0.08 mol / 100g. In addition, a, b and c are positive numbers of 1 ≦ a ≦ 100, 5 ≦ b ≦ 200, and 5 ≦ c ≦ 300, and may be in a range of (a + b) /c=0.5 to 1.0, preferably It may range from 0.6 to 0.9.

Moreover, although the compounding quantity of this organopolysiloxane (A) is 10-30 mass parts, Preferably it is 15-25 mass parts. If the blending amount of the organopolysiloxane does not meet 10 parts by mass, it will not exhibit sufficient heavy peeling property when the peeling rate is slow, and if it is more than 30 parts by mass, the viscosity characteristic will change, and the coating property as the silicone composition will be impractical. not.

The organopolysiloxane of component (B) is represented by following formula (2).

<Formula 2>

In formula, R <^1> and R <^2> are the same as the above, Alkenyl group amount is 0.4-0.7 mol / 100g in a molecule | numerator, Preferably it is 0.5-0.6 mol / 100g. Further, d, e and f are positive numbers of 1 ≦ d ≦ 75, 0 ≦ e ≦ 20, 1 ≦ f ≦ 50, and (d + e) /f=0.6 to 1.5, preferably in the range of 0.8 to 1.2 to be. Since this value is less than 0.6 when R ² SiO _3/2, the ratio of the components becomes high, the synthesis of the organopolysiloxane becomes difficult. Moreover, when it exceeds 1.5, the correlation of the amount of peeling force with respect to peeling rate will fall. d, e and f may be a number of the organopolysiloxane having a viscosity at 25 ° C. of 5 to 100 mPa · s, and if the viscosity at 25 ° C. of this organopolysiloxane is less than 5 mPa · s, the curability deteriorates. When it exceeds 100 mPa * s, since the viscosity as this composition becomes high too much, it is not practical.

Moreover, although the compounding quantity of this organopolysiloxane (B) is 10-30 mass parts, Preferably it is 10-20 mass parts. When the compounding quantity of this organopolysiloxane does not satisfy 10 mass parts, sufficient heavy peeling property will not be exhibited when a peeling rate is slow, and when more than 30 mass parts, the correlation of the amount of peeling force with respect to a peeling rate will fall.

This organopolysiloxane (B), for example, co-hydrolyzes the trialkoxymethylsilane and dialkyl tetramethyldisiloxane or hexamethyldisiloxane in an alcohol solvent by using an acid catalyst, and neutralizes to remove by-product alcohol. And water washing and unreacted material removal process.

The organopolysiloxane of component (C) is represented by following formula (3).

<Formula 3>

Wherein R ¹ and R ² are the same as above, and g is a number such that the viscosity of the organopolysiloxane containing an alkenyl group only at the terminal becomes 800 to 2000 mPa · s, preferably 1000 to 1500 mPa · s. It is a number.

When the viscosity of the organopolysiloxane is less than 800 mPa · s, the correlation of the peeling force with respect to the peeling rate is lowered. When the viscosity of the organopolysiloxane is larger than 2000 mPa · s, the viscosity as the silicone composition of the present invention becomes too high and the coating property is deteriorated. Is not

Moreover, although the compounding quantity of this organopolysiloxane (C) is 40-80 mass parts, Preferably it is 50-70 mass parts. When the compounding quantity of this organopolysiloxane does not satisfy 40 mass parts, the correlation of the quantity of peeling force with respect to peeling rate falls. When more than 80 mass parts, when the peeling rate is slow, it will not show sufficient heavy peeling property.

The organohydrogenpolysiloxane of component (D) is represented by following formula (4).

<Formula 4>

In formula, R <^1> is monovalent hydrocarbon group which does not have the same aliphatic unsaturated bond as mentioned above. J may also be in the range 8 ≦ j ≦ 20, preferably 10 ≦ j ≦ 15. When j is smaller than 8, when heat-hardening the silicone composition of this invention, this organohydrogenpolysiloxane (D) volatilizes and sufficient hardening or a characteristic cannot be obtained. Also, if j is larger than 20, it is not practical because silicon transition increases. The organohydrogenpolysiloxane may be a mixture of two or more kinds.

The compounding quantity of this organohydrogenpolysiloxane is 1.0-4.0 with respect to the total number of alkenyl groups in the organopolysiloxane (A), organopolysiloxane (B), and organopolysiloxane (C) component of the number-of-moles of the hydrogen atom couple | bonded with the silicon atom. The mass part equivalent to a double penetration can be made. Preferably it may be a mass part equivalent to 1.2-2.5 times mole. Hardening becomes inadequate when a compounding quantity is 1.0 times mole or less, and when it exceeds 4 times mole, the change of peeling force with time progresses large.

Component (E) is a catalytic amount of a platinum group metal compound, and a well-known addition reaction catalyst can be used as this platinum group metal compound. Examples of such platinum group metal catalysts include catalysts such as platinum-based, palladium-based, rhodium-based and ruthenium-based catalysts. Among these, platinum-based catalysts are particularly preferably used. Examples of the platinum catalyst include complexes of chloroplatinic acid, alcoholic or aldehyde solutions of chloroplatinic acid, various olefins of chloroplatinic acid, or vinylsiloxanes. Although the addition amount of these platinum group metal catalysts is a catalyst amount, in consideration of economics, the range of 10-1000 ppm is preferable as a platinum-based metal amount with respect to the organopolysiloxane total amount of components (A)-(D), and 50-200 It is more preferable to set it as ppm.

Although the silicone composition of this invention is obtained by mix | blending the predetermined amount of the said component, as an arbitrary component other than each said component, for example, various organic nitrogen compounds as (F) component for the purpose of controlling the catalyst activity of a platinum group metal type catalyst, Reaction control agents such as organophosphorus compounds, acetylene compounds, oxime compounds and organic chloro compounds. The addition amount of an arbitrary component can be made into the normal amount in the range which does not impair the effect of this invention.

As a control agent of the said reaction, a well-known thing can be used. Acetylene alcohols such as 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-penten-3-ol and phenylbutynol, Acetylene compounds such as 3-methyl-3-1-pentene-1-yne and 3,5-dimethyl-1-hexyn-3-yne, reactants of these acetylene compounds with alkoxysilanes or siloxanes, hydrogensilanes or siloxanes And organic nitrogen compounds such as vinylsiloxanes such as tetramethylvinylsiloxane cyclic bodies and benzotriazoles, and other organic phosphorus compounds, oxime compounds and organic chromium compounds.

The compounding quantity of (F) component can be the quantity from which favorable process bath stability is obtained, and can be generally made into 0.01-10 mass% with respect to the total amount of (A)-(E) component, Preferably 0.05-5 mass% is Used.

Other optional components can be added to the silicone composition of this invention as needed. For example, stabilizers, heat resistance improvers, fillers, pigments, leveling agents, adhesion promoters to substrates, antistatic agents, antifoaming agents, nonreactive organopolysiloxanes, and the like can be added.

As a base material which apply | coats the composition of this invention and forms a cured film, it is paper base materials, such as glassine paper, kraft paper, and clay coated paper, laminated papers, such as polyethylene laminated fine paper and polyethylene laminated kraft paper, polyester, polypropylene, polyethylene And metal foils such as aluminum, such as plastic films and sheets obtained from synthetic resins such as polyvinyl chloride, polytetrafluoroethylene and polyimide.

In order to apply | coat the composition of this invention to the said base material, well-known methods, such as roll coating, gravure application | coating, wire doctor application | coating, air knife application, and immersion application | coating, can be used. The coating amount may be 0.01 to 100 g / m 2, and the thickness of the coating film is about 0.1 to 10 μm, and is partially applied to the entire surface of the substrate or a part where peelability is required. Moreover, it is preferable to perform hardening of the said silicone composition at 50-200 degreeC, and in this case, it is more preferable to make heating time into 1 second-5 minutes.

<Example>

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by this. In addition, the physical property in a table in the following example is measured by the following test method.

[Method of Curing Silicone Composition]

Immediately after the production of the silicone composition, the silicone composition was applied onto the polyethylene laminate paper substrate so as to be 0.6 to 0.8 g / m 2, and heated in a hot air dryer at 120 ° C. for 60 seconds, and the resultant was used as the silicone separator (paper) for the following measurements.

[Low speed peel force]

After the silicone separator obtained by the curing method of the silicone composition was stored at 50 ° C. for 3 days, the Nitto double-coated tape No.502 tape was adhered to the silicon separator, cut into 5 cm × 23 cm, and the sample was placed on a glass plate. Samples were stored at a weight of 70 g / cm 2 and 70 ° C. for 20 hours, and the adhesive surface was peeled at a peel rate of 0.3 m / min at an angle of 180 ° using a tensile tester, and the force required to peel was measured. It was set as the low speed peeling force (N).

[High speed peeling force]

After the silicone separator obtained by the curing method of the silicone composition was stored at 50 ° C. for 3 days, the Nitto double-coated tape No.502 tape was adhered to the silicon separator, cut into 5 cm × 23 cm, and the sample was placed on a glass plate. Samples were stored at a weight of 70 g / cm 2 and stored at 70 ° C. for 20 hours, and the adhesive surface was peeled off at an angle of 180 ° using a tensile tester, and the force required to peel was measured. It was set as the high speed peeling force (N).

[Peel rate]

The degree of positive correlation was calculated | required using the said low speed peeling force and high speed peeling force by the following formula (1), and it was made into this peeling force ratio.

[Peeling force ratio] = [High speed peeling force] / [Low speed peeling force]

The larger the peeling force ratio, the greater the correlation of the amount of peeling force with respect to the peeling rate, which is consistent with the object of the present invention.

[Residual Adhesion Rate]

A polyester tape Nitto-31B (trade name, manufactured by Nitto Denko Co., Ltd.) was adhered to the surface of the silicon separator obtained by the curing method of the silicone composition described above, and was heated at 70 ° C. for 20 hours under a load of 1976 Pa. After that, the tape was peeled off and adhered to the stainless plate, and the force required for peeling the treated tape from the stainless plate using a tensile tester was measured in the same manner as the initial peel force test to obtain the adhesive force (I). It was. Similarly, the polyester tape Nitto-31B tape was adhered to a Teflon (registered trademark, manufactured by Dupont), heated at 70 ° C. for 20 hours with a load of 1976 Pa, and then peeled off and taped to a stainless plate. The force required for peeling off the treated tape from the stainless plate by using a tensile tester was measured in the same manner as in the initial peel force test, so that the blank adhesive force (II) was not in contact with the silicon cured surface. Residual adhesion rate (%) was calculated | required by following formula (2).

Residual Adhesion Rate = Adhesion (I) / Blank Adhesion (II) × 100

Example 1

20 parts by mass of organopolysiloxane A-1 having an amount of alkenyl groups corresponding to the component (A) of the present invention represented by the following formula (5) of 0.08 mol / 100 g, and a component (B) of the present invention represented by the following formula (6) 10 mass parts of organopolysiloxane B-1 whose amount of alkenyl groups to make is 0.58 mol / 100 g, and the viscosity in 25 degreeC corresponding to the component (C) of this invention represented by following General formula (7) is 1500 mPa * s, 70 parts by mass of organopolysiloxane C-1 having a kenyl group amount of 0.01 mol / 100 g, 9.1 parts by mass of methylhydrogenpolysiloxane D-1 corresponding to component (D) of the present invention represented by the following formula (8) and ethynylcyclohexane 0.3 mass part of all the mixture was mixed uniformly and the silicone mixture 1 was obtained. The viscosity of this silicone mixture 1 was 680 mPa * s. 2 mass parts (100 ppm of platinum conversion) of the complex salt of chloroplatinic acid and vinylsiloxane were added to 100 mass parts of this mixture 1, and it mixed sufficiently, and obtained the silicone composition 1. This silicone composition 1 was hardened by the said method, and peeling force, transferability, and residual adhesiveness were measured. The results are shown in Table 1.

However, m ≒ 250

Example 2

20 parts by mass of organopolysiloxane A-1 of Example 1, 20 parts by mass of organopolysiloxane B-1, 60 parts by mass of organopolysiloxane C-1, 15.5 parts by mass of methylhydrogenpolysiloxane D-1, 0.3 mass part of thynyl cyclohexanol was mixed uniformly, and the silicone mixture 2 was obtained. The viscosity of this silicone mixture 2 was 410 mPa * s. 2 mass parts (100 ppm of platinum conversion) of the complex salt of chloroplatinic acid and a vinylsiloxane was added to 100 mass parts of this mixture 2, and it mixed sufficiently, and obtained the silicone composition 2. This silicone composition 2 was hardened by the said method, and peeling force, transferability, and residual adhesiveness were measured. The results are shown in Table 1.

Example 3

A silicone mixture 3 was obtained in the same manner as in Example 2, except that 19.95 parts by mass of methylhydrogenpolysiloxane D-1 of Example 2 was used. The viscosity of this silicone mixture 3 was 360 mPa * s. 2 mass parts (100 ppm of platinum conversion) of the complex salt of chloroplatinic acid and a vinylsiloxane was added to 100 mass parts of this mixture 3, and it mixed sufficiently, and obtained the silicone composition 3. This silicone composition 3 was hardened by the said method, and peeling force, transferability, and residual adhesiveness were measured. The results are shown in Table 1.

Comparative Example 1

40 parts by mass of the organopolysiloxane A-1 of Example 1, 60 parts by mass of the organopolysiloxane C-1, 5.5 parts by mass of methylhydrogenpolysiloxane D-1 and 0.3 parts by mass of ethynylcyclohexanol were uniformly mixed. Silicone Mixture 4 was obtained. The viscosity of this silicone mixture 4 was 1050 mPa * s. 2 mass parts (100 ppm of platinum conversion) of the complex salt of chloroplatinic acid and vinylsiloxane were added to 100 mass parts of this mixture 4, and it mixed sufficiently, and obtained the silicone composition 4. This silicone composition 4 was hardened by the said method, and peeling force, transferability, and residual adhesiveness were measured. The results are shown in Table 1.

Comparative Example 2

30 parts by mass of the organopolysiloxane B-1 of Example 1, 70 parts by mass of the organopolysiloxane C-1, 26.0 parts by mass of methylhydrogenpolysiloxane D-1, and 0.3 parts by mass of ethynylcyclohexanol were uniformly mixed. Silicone Mixture 5 was obtained. The viscosity of this silicone mixture 5 was 200 mPa * s. 2 mass parts (100 ppm of platinum conversion) of the complex salt of chloroplatinic acid and a vinylsiloxane was added to 100 mass parts of this mixture 5, and it mixed sufficiently, and obtained the silicone composition 5. This silicone composition 5 was hardened by the said method, and peeling force, transferability, and residual adhesiveness were measured. The results are shown in Table 1.

Comparative Example 3

100 mass parts of organopolysiloxane C-1 of Example 1, 1.5 mass parts of methylhydrogenpolysiloxane D-1, and 0.3 mass part of ethynyl cyclohexanol were mixed uniformly, and the silicon mixture 6 was obtained. The viscosity of this silicone mixture 6 was 1300 mPa * s. 2 mass parts (100 ppm of platinum conversion) of the complex salt of chloroplatinic acid and a vinylsiloxane was added to 100 mass parts of this mixture 6, and it mixed sufficiently, and obtained the silicone composition 6. This silicone composition 6 was hardened by the said method, and peeling force, transferability, and residual adhesiveness were measured. The results are shown in Table 1.

[Comparative Example 4]

Except having used 60 mass parts of organopolysiloxane C-2 whose viscosity at 25 degreeC is 600 mPa * s and the amount of alkenyl groups are 0.015 mol / 100 g instead of the organopolysiloxane C-1 of Example 1, In the same manner as 3, a silicon mixture 7 was obtained. The viscosity of this silicone mixture 7 was 210 mPa * s. 2 mass parts (100 ppm of platinum conversion) of the complex salt of chloroplatinic acid and a vinylsiloxane was added to 100 mass parts of this mixture 7, and it mixed sufficiently, and obtained the silicone composition 7. This silicone composition 7 was hardened by the said method, and peeling force, transferability, and residual adhesiveness were measured. The results are shown in Table 1.

[Comparative Example 5]

A silicone mixture 8 was obtained in the same manner as in Example 3, except that 20.3 parts by mass of methylhydrogenpolysiloxane D-2 represented by the following formula (9) was used instead of the methylhydrogenpolysiloxane D-1 of Example 1. The viscosity of this silicone mixture 8 was 480 mPa * s. 2 mass parts (100 ppm of platinum conversion) of the complex salt of chloroplatinic acid and vinylsiloxane were added to 100 mass parts of this mixture 8, and it mixed sufficiently, and obtained the silicone composition 8. This silicone composition 8 was hardened by the said method, and peeling force, transferability, and residual adhesiveness were measured. The results are shown in Table 1.

Component (D) *: ratio of the number of moles (H) of hydrogen atoms bonded to silicon atoms to the total number of moles (V) of alkenyl groups of components (A), (B) and (C) (H / V)

When the silicone composition of the present invention is used as a silicone for a non-solvent type release paper, a cured film having a positive correlation with the peeling force with respect to the peeling speed of the cured film is obtained (when the peeling speed is increased, the peeling force also increases accordingly).

Claims (6)

(A) organopolysiloxane represented by the following general formula (1), (B) organopolysiloxane represented by the following general formula (2), (C) an organopolysiloxane represented by the following general formula (3), and having an alkenyl group only at the terminal, (D) Organopolysiloxane represented by the formula (4) and (E) includes a catalytic amount of platinum group metal compound, To the total mass of components (A), (B) and (C), component (A) is 10 to 30 mass%, component (B) is 10 to 30 mass%, and component (C) is 40 to 80 mass% Included as, Component (D) is contained in an amount such that the number of moles of hydrogen atoms bonded to silicon atoms in component (D) is 1.0 to 4.0 times relative to the total molar amount of the alkenyl groups of components (A), (B) and (C). , Silicone composition for solvent-free release paper. <Formula 1>

Wherein R ¹ is an unsubstituted or substituted C1-C10 monovalent hydrocarbon group having no aliphatic unsaturated bonds, and R ² is-(CH ₂ ) _p -CH = CH ₂ (p is 0-6) Integer), the amount of alkenyl group is 0.06 to 0.10 mol per 100 g of the organopolysiloxane, a, b and c are 0.05 to 0.2, a / c is 0.5 to 1.0, ( a + b) / c is a number from 0.5 to 1.0. <Formula 2>

In formula, R <^1> and R <^2> is the same as the above, Alkenyl group amount is 0.4-0.7 mol / 100g, d / e and f are 0.8-1.5 in d / f, 0-0.5 in e / f, ( d + e) / f is 0.6-1.5, and is a number which makes the viscosity in 25 degreeC of this organopolysiloxane into 5-100 mPa * s. <Formula 3>

In formula, R <^1> and R <^2> are the same as the above, g is a number which makes the viscosity of this organopolysiloxane 800-2000 mPa * s. <Formula 4>

In formula, R <^1> is the same as the above, R <^3> is a hydrogen atom or R <^1> , j is an integer of 8 <j <20. The silicone composition for a solventless release paper according to claim 1, wherein component (A) has an alkenyl group of 0.07 to 0.09 mol / 100 g, and component (B) has an alkenyl group of 0.5 to 0.6 mol / 100 g. The silicone composition for a non-solvent type release paper according to claim 1 or 2, wherein the component (C) has a viscosity of 1000 to 1700 mPa · s. The molar number of hydrogen atoms bonded to the silicon atom is 1.2 to 2.5 times as high as the component (D) according to the total molar amount of the alkenyl groups of the components (A), (B) and (C). Included in an amount that is, j in formula 4 is an integer of 8 to 15, the solvent-free release silicone composition. The silicone composition for a non-solvent type release paper according to claim 1 or 2, wherein the viscosity is 50 to 1000 mPa · s. The precursor composition of the silicone composition for non-solvent type release paper of Claim 1 or 2 containing component (A), (B), (C) and (D).