TWI742108B - Silicone composition, release paper and release film - Google Patents

Abstract

The present invention provides a silicone composition, which contains: (A) an organic polycarbonate having two or more alkenyl groups bonded to silicon atoms in one molecule, and one or more or no aryl groups in one molecule. Siloxane (B1) has 3 or more hydrogen atoms bonded to silicon atoms in a molecule, and the total number of aryl groups is relative to the hydrogen atoms bonded to silicon atoms and the groups bonded to silicon atoms. The ratio of the total number of aryl groups is at least 8% of the number of SiH groups in the organohydrogenpolysiloxane (B1) component containing aryl groups to the number of alkenyl groups in the component (A) It becomes an amount of 0.5-10, and [(B1) the ratio of the aryl group in the component]-[(A) the total number of aryl groups in the component relative to the total number of groups bonded to the silicon atom Ratio]≧8.

Description

Silicone composition, release paper and release film

The present invention relates to a silicone composition, particularly a solvent-free silicone composition, which provides the following cured material layer, and a release paper and a release film having a cured film of the composition, the cured material layer and the substrate , Especially the adhesion of plastic film substrates such as polyester film is excellent.

In the past, in order to provide the substrate with peeling characteristics relative to the adhesive material (for example, the property of completely peeling from the adhesive material), a film containing a cured silicone composition was formed on the surface of a sheet-like substrate such as paper or plastic. . As a method of forming a cured film of a silicone composition on the surface of a substrate, for example, Patent Document 1 describes a method in which an alkenyl group-containing organopolysiloxane and an organohydrogenpolysiloxane are formed on the surface of the substrate. The addition reaction proceeds in the presence of a platinum-based catalyst to form a peelable film.

As a silicone composition that is cured by an addition reaction to form a film, there are a type that dissolves the silicone composition in an organic solvent, a type that uses an emulsifier to disperse in water to make an emulsion, and a solvent-free type that does not contain a solvent. Type silicone composition. The solvent type has the disadvantage of being harmful to the human body or the environment, and the emulsion type requires high energy to remove water. Furthermore, there is a problem that a large amount of emulsifier remains, so the adhesion of the obtained cured film to the substrate is reduced, and if the adhesive material is attached to the release layer including the cured film and then peeled off, the adhesive The adhesive strength of the material (hereinafter referred to as residual adhesive strength) will decrease. Therefore, it is ideal as a solvent-free silicone composition.

However, although the conventional solvent-free silicone composition adheres well to the paper substrate, it has a problem that it lacks adhesion to plastic films such as polyester films or polypropylene films.

As a method of improving the adhesion of the solvent-free silicone composition to the film substrate, for example, there are a method of mixing a silane coupling agent in the silicone composition, applying easy adhesion treatment to the surface of the substrate on which the composition is coated, or The method of primer treatment. However, the solvent-free silicone composition prepared with the silane coupling agent has insufficient adhesion to the substrate. In addition, the method of performing the surface treatment of the substrate has the disadvantage of increasing the number of steps.

Patent Document 2 describes a method of adding a low-molecular-weight silicone containing alkenyl groups to a silicone composition, irradiating ultraviolet rays, and heating the composition to harden the composition, thereby improving the substrate without affecting the peeling characteristics Tightness. However, this method requires a heating dryer and an ultraviolet (Ultraviolet, UV) irradiation device.

Patent Document 3 describes a method of improving the adhesion to the substrate by using a small amount of additives, and adding an organopolysiloxane having an epoxy group to a silicone composition. However, in the examples of Patent Document 3, only the solvent-based silicone composition is described, and there is no mention of the residual adhesive strength after peeling the adhesive material from the peeling layer.

Patent Document 4 describes a _{solvent-free silicone composition containing a base polymer having RSiO 3/2} units and a branched structure, and describes that the silicone composition improves the adhesion of the obtained cured film to the substrate . However, there is the following problem: Although the adhesion to the Oriented Polypropylene (OPP) film (biaxially stretched polypropylene film) has been improved, the adhesion to the polyester film substrate is insufficient .

Patent Document 5 describes that a reaction product of a liquid polyorganosiloxane having an alkenyl group and a silanol group and a hydrolyzable silane having an epoxy group is added to a solvent-free silicone composition to improve the performance. Adhesion of the obtained cured film to the substrate. However, in the examples, _{the reaction product is only used in specific organopolysiloxanes containing Q units (SiO 4/2} ) and alkenyl groups, and there is no mention of the removal of the adhesive material from the peeling layer. Residual bonding strength. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 47-32072 [Patent Document 2] Japanese Patent Laid-Open No. 2011-252142 [Patent Document 3] Japanese Patent Laid-Open No. 2011-132532 [Patent Document 4] Japanese Patent Japanese Patent Application Publication No. 6-220327 [Patent Document 5] Japanese Patent Publication No. 2010-500462

[Problem to be Solved by the Invention] As described above, there is no solvent-free silicone composition that provides a cured film that has excellent adhesion to the film substrate and self-curing of the adhesive material After the film is peeled off, the adhesive material can retain high adhesive strength.

The present invention has been made in view of the above circumstances, and its object is to provide a solvent-free silicone composition that provides a cured film as follows, and to provide a release paper and a release film provided with the cured film, the cured film being opposed to a base The adhesive material, especially the plastic film base material, has excellent adhesion, and further, after peeling the adhesive material from the hardened film, the adhesive material can retain high adhesive strength. [Means to solve the problem]

The inventors of the present invention conducted diligent studies to achieve the above-mentioned object, and as a result, they found that an addition reaction type silicone composition containing an alkenyl group-containing organopolysiloxane and an organohydrogenpolysiloxane is The difference in the content of aryl groups between an alkane and an alkenyl group-containing organopolysiloxane is specifically defined, whereby the above-mentioned problem can be achieved, and the present invention has been completed. In addition, in the present invention, the aryl group refers to at least one of an aryl group bonded to a silicon atom and an aryl group of an aralkyl group bonded to a silicon atom. The aryl group possessed by the aralkyl group bonded to the silicon atom is, for example, a phenyl group possessed by a benzyl group (phenylmethyl) or a phenethyl group (phenylethyl).

That is, the present invention provides a silicone composition containing: (A) a molecule having two or more alkenyl groups bonded to silicon atoms, and having one or more or no aryl groups in one molecule Organopolysiloxane (B1) has 3 or more hydrogen atoms bonded to silicon atoms in a molecule, and the total number of aryl groups is relative to the hydrogen atoms bonded to silicon atoms and silicon atoms. The ratio (%) of the total number of groups (hereinafter referred to as the ratio of aryl groups) is at least 8% of the number of SiH groups in the organohydrogenpolysiloxane (B1) component containing aryl groups The ratio with respect to the number of alkenyl groups in the component (A) becomes an amount of 0.5-10, and the amount of (C) platinum group metal-based catalyst catalyst, and the ratio of the aryl group in the component [(B1) (%)]-[(A) Ratio of the total number of aryl groups in the component to the total number of groups bonded to the silicon atom (%)]≧8. In addition, the present invention provides a release paper or release film having a layer containing a cured product of the silicone composition. [Effects of the invention]

The silicone composition of the present invention is particularly a solvent-free type, and provides a cured film having excellent adhesion to a substrate, particularly a plastic film substrate. In addition, after the peeling layer including the cured film is attached to the adhesive material, the adhesive material is peeled from the peeling layer, and then the adhesive material can be left with high adhesive strength. That is, it is possible to provide a cured film excellent in non-adhesiveness.

Hereinafter, the present invention will be described in more detail. Furthermore, the “residual adhesion rate” in the present invention refers to the adhesive strength of the adhesive material remaining after peeling off the adhesive material from the peeling layer containing the cured film of the present invention, relative to the adhesive strength of the adhesive material before being attached to the peeling layer Then the ratio of intensity (%).

[(A) Organopolysiloxane having an alkenyl group] The component (A) is an organopolysiloxane having two or more alkenyl groups in one molecule and one or more or no aryl group. The aryl group refers to at least one of an aryl group bonded to a silicon atom and an aryl group of an aralkyl group bonded to a silicon atom as described above. The organopolysiloxane may be an alkenyl group-containing organopolysiloxane contained in a previously known addition reaction curable silicone composition.

The component (A) is preferably represented by the following general formula (3). The organopolysiloxane may be used singly, or two or more of them may be used in combination. The bonding sequence of each silicone unit shown in the parentheses is not limited to the following. [化1]

In the formula (3), R ^{3 is} independently a hydroxyl group, a substituted or unsubstituted monovalent hydrocarbon group that does not have an aliphatic unsaturated bond, or an alkenyl group having 2 to 12 carbons, or may have an oxygen atom The monovalent hydrocarbon group containing alkenyl groups. The organopolysiloxane has at least two alkenyl groups in one molecule.

As the monovalent hydrocarbon group not having an aliphatic unsaturated bond, those having 1 to 10 carbon atoms are preferred. For example, methyl, ethyl, propyl, and butyl are preferably alkyl groups having 1 to 6 carbon atoms, cyclohexyl and the like are preferably cycloalkyl groups having 5 to 8 carbon atoms, phenyl and tolyl groups, etc. It is preferably an aryl group having 6 to 10 carbons, and a benzyl group and the like are preferably an aralkyl group having 7 to 10 carbons, or part or all of the hydrogen atoms bonded to the carbon atoms of these groups are passed through a hydroxyl group or a cyano group. Substituents such as alkoxy groups, halogen atoms, alkoxysilyl groups, polyoxyalkylene groups, epoxy groups, and carboxyl groups. From the standpoint of self-peelability, an alkyl group and an aryl group are particularly preferred. More preferred are methyl, ethyl, propyl and phenyl.

In the case where the organopolysiloxane has at least one of an aryl group bonded to a silicon atom or an aralkyl group bonded to a silicon atom, the aryl group (including the aryl group of the aralkyl group) Content, the number of the aryl group (including the aryl group of the aralkyl group) relative to the group bonded to the silicon atom (more specifically, the group represented by ^{R 3 in the formula (3))} The ratio (%) of the total number of is preferably 0.5% to 50%, more preferably 0.5% to 40%. If the ratio of the aryl group exceeds the upper limit, the curability of the obtained composition may decrease.

Examples of alkenyl groups include alkenyl groups such as vinyl, allyl, hexenyl, and octenyl, and cycloalkenylalkyl groups such as cyclohexenylethyl. As the alkenyl-containing monovalent hydrocarbon group which may have an oxygen atom, for example, acryloylalkyl groups such as acryloyl propyl, acryloylmethyl, and methacryloyl propyl groups and methacryloyl alkyl groups can be cited. base. In addition, an ether bond may be included in the methylene chain, and examples thereof include -(CH ₂ ) ₂ -O-CH ₂ -CH=CH ₂ and -(CH ₂ ) ₃ -O-CH ₂ -CH=CH ₂ . Among them, vinyl is preferred from an industrial point of view.

(A) Organopolysiloxane has two or more alkenyl groups in one molecule. Preferably, the organopolysiloxane has 2 to 500 alkenyl groups in one molecule, more preferably 2 to 400 alkenyl groups. If the number of alkenyl groups is less than 2, there is a high possibility that uncrosslinked molecules will remain after curing the composition and the curability will decrease. If the number of alkenyl groups is more than 500, heavy peeling may occur and the residual adhesion rate may decrease. Case.

In the formula (3), f is 2 or more, preferably an integer of 2 to 300; g is 1 or more, preferably an integer of 30 to 20,000; h is 0 or more, preferably an integer of 0 to 100; k is 0 or more, preferably an integer of 0-100; 30≦f+g+h+k≦20,000, preferably 50≦f+g+h+k≦15,000. If f+g+h+k is less than the lower limit, the coating property of the obtained composition is reduced. In addition, if the upper limit is exceeded, mist may be generated in the coating roller portion of the coating machine when the composition is applied to the surface of the substrate at a high speed.

In addition, the component (A) preferably has a viscosity at 25°C of 50 mPa·s to 10,000 mPa·s, particularly 50 mPa·s to 5,000 mPa·s. Furthermore, if necessary, an organopolysiloxane having a viscosity of 50,000 mPa·s in a toluene solution of 10,000 mPa·s to 30% may be used in combination. When multiple organopolysiloxanes are used in combination, it is preferable that the total viscosity of the component (A) does not exceed 10,000 mPa·s. If the value exceeds this value, the coating properties of the composition are reduced, which is unsatisfactory. Furthermore, in the present invention, the viscosity can be measured by a rotary viscometer (the same applies below).

（30≦z1≦2,500） [化3]

（30≦z2≦10,000） [化4]

（30≦z3≦19,000，2≦z4≦500） [化5]

（30≦z5≦19,000，1≦z6≦498） [化6]

（1≦z7≦19,000，1≦z8≦500，1≦z9≦498） [化7]

（0≦z10≦1,000，0≦z11≦1,000，0≦z12≦1000，1≦z13≦100） [化8]

（0≦z14≦500，0≦z15≦500，0≦z16≦500，0≦z17≦100，0≦z18≦500，0≦z19≦500，1≦z20≦100）As (A) organopolysiloxane, the following can be mentioned, for example, but it is not limited to these. In addition, in the following formulae, Me, Vi, and Ph represent a methyl group, a vinyl group, and a phenyl group, respectively. The bonding sequence of each silicone unit shown in the parentheses is not limited to the following. [化2]

(30≦z1≦2,500) [Change 3]

(30≦z2≦10,000) [Chemical 4]

(30≦z3≦19,000, 2≦z4≦500) [Chemical 5]

(30≦z5≦19,000, 1≦z6≦498) [化6]

(1≦z7≦19,000, 1≦z8≦500, 1≦z9≦498) [化7]

(0≦z10≦1,000, 0≦z11≦1,000, 0≦z12≦1000, 1≦z13≦100) [Chemical 8]

(0≦z14≦500, 0≦z15≦500, 0≦z16≦500, 0≦z17≦100, 0≦z18≦500, 0≦z19≦500, 1≦z20≦100)

[(B) Organohydrogenpolysiloxane] The component (B) is an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to silicon atoms in one molecule. The silicone composition of the present invention is characterized in that it contains (B1) an organohydrogen polysiloxane having at least three silicon atoms bonded to silicon atoms in a molecule and a specific amount of an organohydrogen polysiloxane having an aryl group as the (B) component . The aryl group refers to at least one of an aryl group bonded to a silicon atom and an aryl group of an aralkyl group bonded to a silicon atom as described above. In addition, the silicone composition of the present invention may be used in combination with the (B1) component to contain (B2) an organohydrogen poly which has at least three hydrogen atoms bonded to silicon atoms in one molecule and does not have an aryl group. Siloxane. When the component (B2) is contained, the blending amount is 1 part by mass to 80 parts by mass relative to the total of 100 parts by mass of the (B1) and (B2) components, preferably 1 part by mass to 70 parts by mass The amount of is more preferably 1 part by mass to 50 parts by mass, still more preferably 1 part by mass to 30 parts by mass, and still more preferably 1 part by mass to 20 parts by mass.

(B) The SiH group present in the organohydrogenpolysiloxane and the alkenyl group present in the component (A) undergo an addition reaction and harden to form a film. (B) The compounding amount of the component is that the ratio of the number of SiH groups in the component (B) to the number of alkenyl groups in the component (A) is 0.5-10, preferably 1-8, and more preferably 1.5 ~6. It is particularly preferably an amount of 1.8-6, and further an amount of 2.0 or more to 5. If the number ratio is less than the lower limit, the adhesion to the base material will decrease. In addition, if it exceeds the upper limit, the obtained cured film will be re-peeled (that is, a strong force is required to peel the adhesive material from the cured film), and the adhesive strength of the adhesive material after peeling will decrease. When the component (B2) is contained, the ratio of the total number of SiH groups in the component (B1) and (B2) to the number of alkenyl groups in the component (A) is preferably 0.5-10 It is 1-8, more preferably 1.5-6, even in this case, the ratio of the total number of SiH groups in component (B1) to the number of alkenyl groups in component (A) It is preferably 1.5 or more, particularly preferably 1.8 or more, and more preferably more than 2.0.

(B1) For the component, the ratio (%) of the number of aryl groups to the total number of groups bonded to silicon atoms and hydrogen atoms bonded to silicon atoms (hereinafter referred to as the ratio of aryl groups) must be at least 8 % Contains aryl groups. It is preferably 9% to 60%, and more preferably 10% to 50%. If the ratio of the aryl group is less than the lower limit, the obtained cured film cannot be provided with good adhesion to the substrate. The number of the aryl group is as described above, and also includes the number of the aryl group of the aralkyl group. The group bonded to a silicon atom includes, for example, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an alkyl group substituted with a halogen atom, and the like. In more detail, the group represented by ^{R 1} mentioned later can be mentioned.

The composition of the present invention is characterized by the ratio (%) of the total number of aryl groups in the component (A) to the total number of groups bonded to the silicon atom (%), and the aromatic content in the component (B1) The proportion of base (%) is more than 8% larger. That is, [(B1) the ratio of the aryl groups in the component (%)]-[(A) the ratio of the total number of aryl groups in the component to the total number of groups bonded to the silicon atom (% )]≧8. Preferably, the difference is 8.5 or more, more preferably 9 or more, most preferably 10 or more. The upper limit of the difference is not particularly limited, but is preferably 50 or less, more preferably 40 or less, more preferably 30 or less, and most preferably 25 or less. The adhesiveness of the cured film obtained by this to the base material is improved. It is believed that the reason is that: component (B1) has more aryl groups than component (A) in the above range, so that the compatibility of component (B1) and component (A) is reduced, and component (B1) is cross-linked It reacts and locally exists in the vicinity of the substrate. In particular, by using an excessive amount of the (B1) component, more of the (B1) component can be gathered near the substrate, thereby improving the adhesion to the substrate. In this case, it is considered that the SiH group in the component (B1) interacts with the functional group present on the surface of the substrate. Especially when the substrate is a plastic film, the aryl group in the component (B1) interacts with the π electrons of the aromatic ring in the plastic, and the stacking effect improves the adhesion.

(B1) The organohydrogenpolysiloxane is represented by the following average composition formula (1), for example. R ¹ _a H _b SiO _{( 4-ab ) /2} (1) (In the formula, R ^{1 is} independently a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group without aliphatic unsaturated bond, relative to The total number of R ^{1 and} the number of hydrogen atoms bonded to silicon atoms are 8% or more. R ¹ is an aryl group, a and b are real numbers greater than zero, a+b≦3)

Examples of monovalent hydrocarbon groups include methyl, ethyl, propyl, butyl, etc., preferably alkyl having 1 to 6 carbons, cyclohexyl, etc., preferably cycloalkyl having 5 to 8 carbons, and phenyl. , Tolyl and the like are preferably aryl groups with 6 to 10 carbons, and benzyl and the like are preferably aralkyl groups with 7 to 10 carbons, or part or all of the hydrogen atoms bonded to the carbon atoms of these groups A monovalent hydrocarbon group with 1 to 10 carbons substituted by a hydroxyl group, a cyano group, a halogen atom, an alkoxysilyl group, a polyoxyalkylene group, an epoxy group, a carboxyl group, etc. At least one of R ¹ is an aryl group or an aralkyl group, preferably an aryl group. Among them, R ^{1 is} preferably an alkyl group or an aryl group, and more preferably a methyl group, an ethyl group, a propyl group, or a phenyl group.

a is preferably a real number of 0.1 to 2, and b is a real number of 0.1 to 3, particularly a number that satisfies 0.5<a+b≦2.9.

As the organohydrogenpolysiloxane represented by the above formula (1), for example ^{, at least one of R 1} HSiO _2/2 units, HSiO _3/2 units, and R ¹ ₂ HSiO _1/2 units can be exemplified, as the case may be. Furthermore, a polymer or copolymer containing at least one of ^{R 1} ₂ SiO _2/2 units, R ¹ SiO _3/2 units, and R ¹ ₃ SiO _{1/2 units.} R ¹ is as described above. It is preferable to have at least three, preferably at least five R ¹ HSiO _2/2 units or R ¹ ₂ HSiO _1/2 units in total in one molecule. In addition, SiO _4/2 units may be contained, and the amount may be in a range that does not impair the effects of the present invention.

Furthermore, regarding the content of SiH groups, there are 3 to 1,000, more preferably 5 to 800 per molecule of organohydrogenpolysiloxane. If the number of SiH groups is less than 3 or exceeds 1,000, the hardenability may decrease or the adhesion may decrease.

（式中，R¹ 為如上所述，c為0或1，d為1以上的整數，e為0以上的整數，2c+d≧3，以及1≦d+e≦1,000。括號內所示的各矽氧烷單元的鍵結順序不受限制）(B1) The shape of the organohydrogenpolysiloxane may be any of linear, branched, and cyclic, and may also be a mixture of these. The organohydrogenpolysiloxane is preferably represented by the following formula (2). [化9]

(In the formula, R ¹ is as described above, c is 0 or 1, d is an integer of 1 or more, e is an integer of 0 or more, 2c+d≧3, and 1≦d+e≦1,000. As shown in parentheses The bonding sequence of each siloxane unit is not limited)

d is preferably an integer of 5 to 1000, e is preferably an integer of 0 to 1000, and c, d, and e are preferably numbers satisfying 5≦2c+d≦1000 and 5≦d+e≦1000.

(B1) The viscosity of the component at 25°C is preferably 0.001 Pa·s to 10 Pa·s, particularly 0.005 Pa·s to 5 Pa·s. If the viscosity is too low, the curability may decrease, and if it is too high, the handleability may decrease.

（5≦z21≦1000，1≦z22≦500，6≦z21+z22≦1000） [化11]

（1≦z23≦998、1≦z24≦500、2≦z23+z24≦1000） [化12]

（3≦z25≦1000，1≦z26≦400，1≦z27≦400，5≦z25+z26+z27≦1000） [化13]

（3≦z28≦1000，2≦z29≦800，5≦z28+z29≦1000） [化14]

（0≦z30≦100，0≦z31≦100，0≦z32≦100，0≦z33≦100，0≦z34≦100，0≦z35≦100，0≦z36≦100） [化15]

（0≦z37≦100，0≦z38≦100，0≦z39≦100，0≦z40≦100，0≦z41≦100，0≦z42≦100，0≦z43≦100，0≦z44≦100，0≦z45≦100，0≦z46≦100，0≦z47≦100，0≦z48≦100）As (B1) component, the following are mentioned, for example, but it is not limited to these. In addition, Me and Ph in the following formula represent a methyl group and a phenyl group, respectively. The bonding sequence of each silicone unit shown in the parentheses is not limited to the following. [化10]

(5≦z21≦1000, 1≦z22≦500, 6≦z21+z22≦1000) [化11]

(1≦z23≦998, 1≦z24≦500, 2≦z23+z24≦1000) [化12]

(3≦z25≦1000, 1≦z26≦400, 1≦z27≦400, 5≦z25+z26+z27≦1000) [Chemical 13]

(3≦z28≦1000, 2≦z29≦800, 5≦z28+z29≦1000) [Chemical 14]

(0≦z30≦100, 0≦z31≦100, 0≦z32≦100, 0≦z33≦100, 0≦z34≦100, 0≦z35≦100, 0≦z36≦100) [化15]

(0≦z37≦100, 0≦z38≦100, 0≦z39≦100, 0≦z40≦100, 0≦z41≦100, 0≦z42≦100, 0≦z43≦100, 0≦z44≦100, 0 ≦z45≦100, 0≦z46≦100, 0≦z47≦100, 0≦z48≦100)

(B2) The component is an organohydrogenpolysiloxane containing 3 or more hydrogen atoms bonded to silicon atoms in one molecule and does not have an aryl group. For example, it is represented by the following average composition formula (4). R ⁴ _j H _k SiO _{( 4-jk ) /2} (4)

In the above formula (4), R ^{4 is} independently a substituted or unsubstituted monovalent hydrocarbon group without an aliphatic unsaturated bond, or a hydroxyl group, but is not an aryl group or an aralkyl group. Examples of the monovalent hydrocarbon group include methyl, ethyl, propyl, butyl, etc., preferably alkyl having 1 to 6 carbons, cyclohexyl, etc., preferably cycloalkyl having 5 to 8 carbons, or a bond A part or all of the hydrogen atoms bound to the carbon atoms of these groups are substituted with hydroxyl, cyano, halogen, alkoxysilyl, polyoxyalkylene, epoxy, carboxyl, etc. The carbon number is 1 ~10 monovalent hydrocarbon group. Among them, an alkyl group is preferred, and from the viewpoint of increasing the addition reaction rate, a methyl group is more preferred.

In the formula (4), j is j>0, preferably a real number of 0.1 to 2.0; k is k>0, preferably a real number of 0.1 to 3; satisfies 0<j+k≦3, especially satisfies 0.5<j+k≦2.9.

(B2) The organohydrogenpolysiloxane may be linear, branched, or cyclic, and may also be a mixture of these. As the organohydrogenpolysiloxane, for example, it has ^{at least one of R 4} HSiO _2/2 units, HSiO _3/2 units, and R ⁴ ₂ HSiO _1/2 units, and optionally further includes R ⁴ ₂ SiO _{2 /} A polymer or copolymer of at least one of ₂ units, R ⁴ SiO _3/2 units, and R ⁴ ₃ SiO _{1/2 units.} R ⁴ is as described above. Preferably, there are at least three, preferably 5 to 300 R ⁴ HSiO _2/2 units or R ⁴ ₂ HSiO _1/2 units in total in one molecule. In addition, SiO _4/2 units may be contained, and the amount may be in a range that does not impair the effects of the present invention.

The organohydrogenpolysiloxane has 3 to 300 SiH groups in one molecule, more preferably 5 to 200 SiH groups. If the number of SiH groups is less than 3 or exceeds 300, the curability may decrease, or the adhesion between the base material and the cured film may decrease.

(B2) The component preferably has a viscosity at 25°C of 0.001 Pa·s to 10 Pa·s, particularly 0.005 Pa·s to 5 Pa·s. If the viscosity is too low, the curability may decrease, and if it is too high, the handleability may decrease.

（3≦z49≦300） [化17]

（3≦z50≦300，1≦z51≦500） [化18]

（1≦z52≦298，1≦z53≦500） [化19]

（0≦z54≦100，0≦z55≦100，0≦z56≦100，1≦z57≦49） [化20]

（0≦z58≦100，0≦z59≦100，0≦z60≦100，0≦z61≦50，0≦z62≦100，0≦z63≦100，1≦z64≦50）As (B2) component, the following compounds can be mentioned, for example, but it is not limited to these. In addition, Me in the following formula represents a methyl group. The bonding sequence of each silicone unit shown in the parentheses is not limited to the following. [化16]

(3≦z49≦300) [化17]

(3≦z50≦300, 1≦z51≦500) [Chemical 18]

(1≦z52≦298, 1≦z53≦500) [Chemical 19]

(0≦z54≦100, 0≦z55≦100, 0≦z56≦100, 1≦z57≦49) [化20]

(0≦z58≦100, 0≦z59≦100, 0≦z60≦100, 0≦z61≦50, 0≦z62≦100, 0≦z63≦100, 1≦z64≦50)

[(C) Platinum group metal-based catalyst] The component (C) is a catalyst for accelerating the addition reaction of the component (A) and the component (B). As long as it is a catalyst that promotes the so-called hydrosilation reaction, a known catalyst can be used. Examples of platinum group metal-based catalysts include platinum-based, palladium-based, rhodium-based, and ruthenium-based catalysts. Among these, platinum-based catalysts are particularly preferably used. Examples of the platinum-based catalyst include chloroplatinic acid, an alcohol solution or aldehyde solution of chloroplatinic acid, and complexes of chloroplatinic acid with various olefins or vinylsiloxanes.

(C) The compounding amount of the component may be the amount of the catalyst. The amount of the catalyst refers to an amount that promotes the addition reaction of the (A) component and the (B) component (that is, the (B1) component and any (B2) component). In order to obtain a good cured film, it is preferable to set it to 1 ppm to 5,000 ppm, especially 20 ppm to 1,000 ppm in terms of the mass of platinum group metals relative to the total mass of (A) component and (B) component Scope.

[Other optional components] The silicone composition of the present invention can be obtained by blending the above-mentioned (A) component to (C) component in the above-mentioned amount. In addition to (A) component-(C) component, other components may be added as needed within the range which does not impair the effect of this invention. This other component should just be what is usually used in a silicone release agent composition, and a well-known other component can be added in a normal compounding amount. For example, as pot life extenders, various organic nitrogen compounds, organic phosphorus compounds, acetylene compounds, oxime compounds, and organic chlorine compounds can be cited.

In more detail, for example, 3-methyl-1-butyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-pentene- Acetylene-based alcohols such as 3-alcohol and phenylbutynol; acetylene-based compounds such as 3-methyl-3-1-pentene-1-yne and 3,5-dimethyl-1-hexyne-3-yne , The reactants of these acetylene compounds with alkoxysilanes or siloxanes or hydrogen silanes, vinyl siloxanes such as tetramethylvinylsiloxane cyclics, organic nitrogen compounds such as benzotriazoles, and others Organophosphorus compounds, oxime compounds, and organic chromium compounds, etc. The compounding amount of these compounds should just be an amount that can obtain a good pot life. Generally, it is preferably 0.01 parts by mass to 10 parts by mass, and more preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B).

Furthermore, within a range that does not hinder the effects of the present invention, well-known antioxidants, pigments, stabilizers, antistatic agents, defoamers, adhesion promoters, tackifiers, solvents, and inorganic materials such as silica can be blended as needed. Filler.

The preparation method of the silicone composition is not particularly limited. In terms of pot life, it is ideal to mix the (A) component, (B) component, and optional components uniformly in advance, and then add the (C) component immediately before use.

By applying the silicone composition of the present invention to the surface of a substrate and curing it, a cured film is formed on the surface of the substrate. This imparts peelability to the substrate (the property that the substrate can be completely peeled from the adhesive material). If the base material having the release layer including the cured product of the silicone composition of the present invention is bonded to the adhesive material, the adhesive material can be peeled from the release layer without reducing the residual adhesion rate of the adhesive material. The step of applying the silicone composition on the surface of the substrate may be carried out in accordance with a previously known method. For example, it can be used: by a comma coater, a lip coater, a roll coater, a die coater, a knife coater ( knife coater, blade coater, rod coater, kiss coater, gravure coater, wire bar coater Coating methods such as coating, screen coating, dip coating, and casting coating. By this method, a silicone composition is coated on one or both sides of a sheet-like substrate such as paper and film. The thickness of the applied silicone composition is usually 0.01 g/m ² to 100 g/m ² . The curing conditions may be in accordance with a previously known method, and are usually cured at 50°C to 200°C for 1 second to 120 seconds. When a release layer is formed on both sides of the base material, it is preferable to form a hardened film on each side of the base material.

As the substrate, various coated papers such as polyethylene laminated paper, cellophane, forest paper, kraft paper, and kaolin coated paper, synthetic papers such as YUPO, polyethylene film, cast polypropylene (cast polypropylene, CPP) or OPP and other polypropylene films, polyethylene terephthalate film (PET (polyethylene terephthalate) film) and other polyester films, polyamide film, polyimide film, polylactic acid film, polyphenol Film, and polycarbonate film, etc. In addition, in order to improve the adhesion between these base materials and the cured film, corona treatment, etching treatment, or plasma treatment may be performed on the surface of the base material in advance. [Example]

Hereinafter, examples and comparative examples are shown to describe the present invention in more detail, but the present invention is not limited to the following examples. In addition, in the following examples, parts represent parts by mass.

芳基比例：0% （A-2） [化22]

芳基比例：0% （A-3） [化23]

芳基比例：5.2% （A-4） [化24]

芳基比例：10.9% （A-5） [化25]

芳基比例：29.0%The components used in the examples and comparative examples are as follows. Hereinafter, the proportion of aryl groups (%) refers to the number of aryl groups (hereinafter referred to as Ph groups) relative to the hydrogen atoms bonded to silicon atoms and the groups bonded to silicon atoms (hereinafter referred to as Vi groups, Me groups, and Ph groups). Base) the proportion of the total number. In addition, the bonding order of the siloxane units shown in parentheses is not limited to the following. (A) Ingredient (A-1) [Chemical 21]

Aryl ratio: 0% (A-2) [Chemical 22]

Aryl ratio: 0% (A-3) [Chemical 23]

The proportion of aryl groups: 5.2% (A-4) [Chemical 24]

The proportion of aryl groups: 10.9% (A-5) [化25]

Aryl ratio: 29.0%

芳基比例：9.8% （B1-2） [化27]

芳基比例：19.8% （B1-3） [化28]

芳基比例：18.2% （B1-4） [化29]

芳基比例：29.3% （B1-5） [化30]

芳基比例：4.9% （B2-1） [化31]

芳基比例：0%(B) Ingredient (B1-1) [化26]

The proportion of aryl groups: 9.8% (B1-2) [Chemical 27]

The proportion of aryl groups: 19.8% (B1-3) [Chemical 28]

The proportion of aryl groups: 18.2% (B1-4) [化29]

The proportion of aryl groups: 29.3% (B1-5) [Chemical 30]

The proportion of aryl groups: 4.9% (B2-1) [化31]

Aryl ratio: 0%

(C) Catalyst: platinum-vinylsiloxane complex

（Ep¹ 為2-(3,4-環氧環己基)乙基，Me為甲基）[Component adhesion promoter for comparative examples] (D-1) Organopolysiloxane represented by the following formula [Chem. 32]

(Ep ¹ is 2-(3,4-epoxycyclohexyl) ethyl, Me is methyl)

(D-2) Epoxy-containing organopolysiloxane is made of 43% by mass of organopolysiloxane and 57% by mass of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane in silanol In the presence of potassium (Potassium Siliconate), the reaction was carried out at 100°C for 1 hour to obtain an epoxy-containing organopolysiloxane containing (CH ₃ ) ₂ (OH)SiO _1/2 silicon terminal 20 mole% siloxane unit Si alcohol, a methyl _{(CH 3) (CH 2 =} CH) SiO 2/2 siloxane represented by a vinyl silicone unit 40 mole%, and a (CH _{3) 2} The _{dimethylsiloxane unit represented by SiO 2/2} is 40 mol%, and has a viscosity of 20 mm ² /s at 25°C. The organopolysiloxane has a viscosity of 0.6 Pa·s at 25°C, an alkenyl content of 0.20 mol/100 g, and an average degree of polymerization of 20. Relative to the number of all siloxane units, it has an epoxy ring The ratio of the number of hexyl siloxane units is 20%.

(D-3) Epoxy group-containing silicone oligomer: 99.98% by mass of 3-glycidoxypropyltriethoxysilane and 0.02% by mass of water are used in the presence of hydrochloric acid at 100°C for 5 hours. Hydrolysis and condensation to obtain epoxy-containing silicone oligomers. The viscosity of this silicone oligomer at 25°C was 0.01 Pa·s, and the average degree of polymerization was 3.

(E) Pot life extender: ethynyl cyclohexanol

<Example 1 to Example 10, Comparative Example 1 to Comparative Example 13> The (A) component, (B) component, and (D) component were taken into the flask in accordance with the blending ratios described in Table 1 to Table 3 below In addition, 0.3 part of (E) component is further added, and it stirs and melt|dissolves. The (C) catalyst is added to the obtained mixture so that the total of (A) component and (B) component becomes 100 ppm in terms of platinum mass, and the mixture is stirred and mixed to obtain a silicone composition . Using this silicone composition, a coating product (release film) was produced by the method described below, and evaluated.

<Evaluation> [Peeling force] The obtained composition was ^{applied to a PET film with a thickness of 38 μm at a solid content of 0.5 g/m 2} using a bar coater, and then applied in a hot-air dryer at 120°C for 40 seconds Heat and harden to form a peeling layer. According to the FINAT law, the peeling layer was evaluated in the following order. Adhesive tape (Tesa 7475 tape, a trade name manufactured by Tesa Tape. Inc) with a width of 25 mm is pasted on the surface of the release agent layer, and 20 g/ A load of cm ² is used for heating treatment for 20 hours. After air cooling for about 30 minutes, the Tesa 7475 tape was stretched using a tensile testing machine at an angle of 180° and a peeling speed of 0.3 m/min, and the force required to peel it off (gf/25 mm) was measured. The results are shown in Tables 1 to 3.

[Residual Adhesion Rate] The Tesa 7475 tape after the peel test was attached to a stainless steel (SUS) plate, and a 2 kg tape roller was used for one round-trip crimping, and then a tensile testing machine was used The peeling was performed at an angle of 180° at 0.3 m/min, and the force F (N/25 mm) required for peeling was measured. As a comparison, an unused Tesa 7475 tape was attached to a SUS board, and the force F _O (N/25 mm) required for peeling off was measured by the same operation as described above. Using the formula: F/F _O ×100, calculate how many% of the remaining adhesive strength between the Tesa 7475 tape and the unused Tesa 7475 tape after the peeling layer is peeled off. )). The results are shown in Tables 1 to 3.

[Adhesiveness] A release layer was formed on a PET film having a thickness of 38 μm by the same operation as described above, and it was stored at 25° C. and 50% RH. After storage for 1 day, 5 days, and 30 days, the peeling layer was wiped 10 times with a finger by visual observation, and whether the peeling layer fell off was evaluated by the following criteria. The results are shown in Tables 1 to 3. A: No peeling was seen after 30 days B: No peeling was seen after 1 day, but peeling after 5 days C: The peeling layer fell off as soon as it was formed

[Table 1]

[Table 2]

[table 3]

As described in Table 2 and Table 3, in the silicone compositions of Comparative Examples 1 to 9, the ratio of the aryl group of the organohydrogenpolysiloxane and the ratio of the aryl group of the alkenyl group-containing organopolysiloxane The difference does not meet the scope of the present invention. The cured film obtained from this silicone composition has poor adhesion to the plastic substrate. In addition, the silicone compositions of Comparative Examples 11 to 13 contained the conventional adhesion promoter, but there was no difference in the ratio of aryl groups, so the adhesion to the plastic substrate was poor. In contrast, as shown in Table 1 above, the cured film obtained from the silicone composition of the present invention has excellent adhesion to the plastic film substrate. In addition, when the adhesive material is peeled from the peeling layer containing the cured film, the adhesive material can be peeled in a state where high adhesive strength remains. [Industrial availability]

The silicone composition of the present invention preferably functions as a solvent-free release agent. By forming a cured film containing the silicone composition on the surface of a substrate such as a paper substrate and a plastic substrate, it is in good contact with these substrates, and a release paper and a release film are provided.

without

without

Claims (8)

A silicone composition containing: (A) Organopolysiloxanes having more than two alkenyl groups bonded to silicon atoms in one molecule, and having more than one or no aryl groups in one molecule (B1) There are 3 or more hydrogen atoms bonded to silicon atoms in one molecule, and the proportion of aryl groups is at least 8%, containing aryl groups, organohydrogen polysiloxanes, in which, The ratio of aryl groups is the ratio of the total number of aryl groups to the total number of hydrogen atoms bonded to silicon atoms and the total number of groups bonded to silicon atoms, and the number of SiH groups in component (B1) is relative to (A) An amount such that the ratio of the number of alkenyl groups in the component becomes 0.5-10; and (C) The amount of platinum group metal-based catalyst catalyst, the amount of catalyst refers to an amount that promotes an addition reaction, and is relatively Compared with the ratio (%) of the total number of aryl groups in the component (A) to the total number of groups bonded to silicon atoms, the ratio (%) of the aryl groups in the component (B1) is 8 %above. The silicone composition as described in claim 1 further contains (B2) in an amount of 1 part by mass to 80 parts by mass relative to 100 parts by mass of the total of the components (B1) and (B2) For organohydrogen polysiloxanes that have 3 or more hydrogen atoms bonded to silicon atoms and do not have aryl groups in a molecule, the total number of SiH groups in the (B1) component and (B2) component is relative to (A ) The ratio of the number of alkenyl groups in the component is 0.5-10. The silicone composition as described in item 1 or item 2 of the scope of patent application, wherein the component (B1) is represented by the following average composition formula (1), R ¹ _a H _b SiO _(4-ab)/2 (1 ) In the formula, R ^{1 is} independently a hydroxyl group, or a substituted or unsubstituted monovalent hydrocarbon group without aliphatic unsaturated bond, relative to ^{the total number of R 1} and the hydrogen atom bonded to the silicon atom ^{R 1} whose total number is 8% or more is an aryl group or an aralkyl group, a and b are real numbers greater than zero, and a+b≦3. The silicone composition described in item 3 of the scope of patent application, wherein the component (B1) is represented by the following formula (2),

In the formula, R ¹ is as described in formula (1) in item 3 of the scope of patent application, c is 0 or 1, d is an integer of 1 or more, e is an integer of 0 or more, 2c+d≧3, and 1 ≦d+e≦1,000. The silicone composition described in item 1 or item 2 of the scope of patent application, wherein the ratio of the number of SiH groups in component (B1) to the number of alkenyl groups in component (A), or (B2) In the case of a component, the ratio of the total number of SiH groups in the component (B1) and the component (B2) to the number of alkenyl groups in the component (A) is 1.5-6. For example, the silicone composition described in item 1 or item 2 of the scope of patent application does not contain a solvent. A release film comprising: a film substrate; and a layer containing the cured product of the silicone composition according to any one of items 1 to 6 of the scope of the patent application on at least one side of the film substrate. A release paper comprising: a paper substrate; and a layer containing a cured product of the silicone composition according to any one of items 1 to 6 of the scope of the patent application on at least one side of the paper substrate.