KR101661941B1 - Curable organopolysiloxane composition and Sheet-form article having a cured layer obtained therefrom - Google Patents

Abstract

(A) at least one organopolysiloxane having a viscosity of 20 to 500 mPa · s and a content of a higher alkenyl group of 1.0 to 5.0 mass%, (B) at least one organopolysiloxane having a viscosity of 1,000,000 mPa · s or more, (C) an organohydrogenpolysiloxane, and (D) a platinum-type catalyst, wherein the content of the organopolysiloxane is in the range of 0.005 to 0.1 mass%. Even when the substrate is thickly coated, the cured layer exhibits an inhibitory effect on the increase in kinetic friction coefficient.

Description

[0001] The present invention relates to a curable organopolysiloxane composition and a sheet-form article having a cured layer obtained therefrom having a curable organopolysiloxane composition and a cured layer composed of the composition,

The present invention relates to a curable organopolysiloxane composition capable of forming a cured layer which is capable of forming a cured layer which is characterized in that an increase in kinetic friction coefficient of a cured layer is suppressed and a kinetic friction coefficient rate dependency is small, ≪ / RTI > More specifically, the present invention relates to a curable organopolysiloxane composition which is easy to handle, forms a cured layer on the surface of a substrate, and is capable of imparting good releasability to a pressure-sensitive adhesive and a sticky material and smoothness of a cured layer, To a laminate comprising a sheet-shaped substrate, in particular a surface-protective film and the sheet-shaped substrate, with a cured layer formed by curing the composition. The present invention also relates to such a sheet-shaped substrate and a method for producing the surface protective sheet.

Methods of imparting releasability to a pressure-sensitive adhesive or a sticky material by forming a cured layer of an organopolysiloxane composition on the surface of a substrate such as various types of paper, laminated paper, synthetic film, and metal foil are well known. In this case, as a method of forming a peelable cured coating, an addition reaction type organopolysiloxane composition for addition reaction of an organopolysiloxane having an unsaturated hydrocarbon group with an organohydrogenpolysiloxane in the presence of a hydrosilylation reaction catalyst (for example, 1) has been widely used, and recently, an organopolysiloxane composition capable of forming a peelable cured film of a non-solvent in consideration of safety and environment has been required for a wide range of uses.

However, the conventional solvent-free curable peelable coating-forming organopolysiloxane composition uses an organopolysiloxane base component having a viscosity of about 50 to 1000 cS and a viscosity of about 50 to 1000 cS, does not contain a high viscosity organopolysiloxane, On the other hand, the cured coating formed has poor slidability and has a disadvantage that its application is limited. In order to solve such a problem, a composition prepared by adding a reactive organopolysiloxane having a low viscosity to a cured coating-forming composition (see Patent Document 2-4) is known. Further, the present inventors have found that (A) an alkenyl-functional organopolysiloxane having a silicon atom-bonded phenyl group and (B) an organopolysiloxane having a viscosity of 100,000 mPa · s or more (Refer to Patent Document 5). In addition, the present invention provides a solvent-free releasable cured coating-forming organopolysiloxane composition.

On the other hand, it is known that organopolysiloxanes containing, for example, higher alkenyl groups such as hexenyl groups can be used as a base component of organopolysiloxane compositions which are cured by addition reaction, for example, It is known that it is possible to improve the peeling property and the like (see Patent Document 6-9). Patent Document 10 discloses a curable coating composition comprising 0.1 to 20% by weight of a higher alkenyl group organopolysiloxane gum. When the gum is introduced, it is possible to quickly cure the coating with a low coefficient of friction and stable release properties over a long period of time Compositions can be provided.

However, this reference discloses a curable organopolysiloxane composition having a low viscosity organopolysiloxane in which the content of a higher alkenyl group as a base component is in the range of 1.0 to 5.0 mass%, a high viscosity organopolysiloxane, And does not disclose a curable organopolysiloxane composition further containing an organopolysiloxane gum having a vinyl group only at the chain terminal. Also, this document does not disclose or suggest the use of two or more organopolysiloxanes having a low viscosity and a different content of higher alkenyl groups.

[Patent Document 1] JP 47-32072 A

[Patent Document 2] JP 61-159480 A

[Patent Document 3] JP 2006-206884 A

[Patent Document 4] JP 2008-169322 A

[Patent Document 5] WO 2006/070947

[Patent Document 6] JP 02-145650 A

[Patent Document 7] JP 04-020570 A

[Patent Document 8] JP 05-171047 A

[Patent Document 9] JP 06-049413 A

[Patent Document 10] JP 09-507523 A

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and an object of the present invention is to provide a pressure-sensitive adhesive and a pressure-sensitive adhesive which are easy to handle and which form a cured layer on the surface of a substrate and which can give good releasability and smooth sliding properties of the cured layer, To provide a composition.

The inventors have also found new technical problems to be solved by the present invention. The cured layer of the known curable organopolysiloxane composition can be appropriately selected according to the use of the sheet-like base material having the above-mentioned cured layer, and can be used not only when the base is thinly coated in an amount less than 1.0 g / m ² , g / m < ² > to form a cured layer. However, as the thickness of the cured layer increases, the coefficient of dynamic friction of the cured layer increases and the slidability of the cured layer is impaired. This problem is very important in applications where both the peeling property and the adhesion property of the cured layer are important, such as an optical display and a glass surface protective film. Further, the inventors have found that when a thick cured layer is formed on the substrate, the peeling force tends to increase more particularly when peeling at a high speed of 100 mm / min or more than when peeling at a low speed.

Therefore, the present invention is characterized in that even when the substrate is coated thickly, the increase in kinetic friction coefficient of the cured layer is suppressed and the kinetic friction coefficient rate dependency is small, compared with the case of coating thinly, Thereby providing an organopolysiloxane composition. The present invention also provides a sheet-like substrate with a cured layer of the composition cured, in particular a laminate comprising the sheet-like article, and to provide a surface protective film. The present invention also provides a method for producing such a sheet-like article and a method for producing a surface protective sheet.

The above-

(A) 100 parts by weight of at least one organopolysiloxane having a viscosity at 25 占 폚 of 20 to 500 mPa 占 퐏 and a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 1.0 to 5.0%

(B) 0.5 to 15 parts by mass of an organopolysiloxane having a viscosity of from 1,000 to 1,000,000 mPa · s at 25 ° C in a gum state or a liquid state and having an alkenyl group content of from 2 to 12 carbon atoms in an amount of from 0.005 to 0.100%

(C) a silicon-bonded hydrogen atom (Si-H) in each molecule and the molar ratio of the SiH group in the component (C) to the alkenyl group in the component (A) The amount of the organohydrogenpolysiloxane,

(D) a catalytic amount of a platinum-type catalyst,

Is achieved by a curable organopolysiloxane composition.

That is, the above object is achieved by the following [1] to [14]:

(A) 100 parts by mass of at least one organopolysiloxane having a viscosity at 25 ° C of 20 to 500 mPa · s and a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 1.0 to 5.0% by mass ,

(B) 0.5 to 15 parts by mass of an organopolysiloxane having a viscosity at 25 ° C of not less than 1,000,000 mPa · s or a liquid state and having an alkenyl group content of from 2 to 12 carbon atoms in an amount of from 0.005 to 0.100% by mass,

(C) a silicon-bonded hydrogen atom (Si-H) in each molecule and the molar ratio of the SiH group in the component (C) to the alkenyl group in the component (A) And the content of the organohydrogenpolysiloxane, and

(D) a catalytic amount of a platinum-type catalyst.

[2] The composition according to [1], wherein the component (A)

(A1) an organopolysiloxane having a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 0.5 to 2.0% by mass, and

(A2) a mixture of two or more organopolysiloxanes obtained by mixing an organopolysiloxane having a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 2.5 to 5.0 mass% in a mass ratio of 1/4 to 4/1 , And the curable organopolysiloxane composition according to [1].

[3] The curable organopolysiloxane composition according to [1] or [2], wherein the higher alkenyl group in the component (A) is a hexenyl group.

[4] The curable organopolysiloxane composition according to [1], wherein the component (B) is a dimethylpolysiloxane end-blocked with dimethylvinylsiloxy groups at both ends of the molecular chain.

[5] The curable organopolysiloxane composition according to any one of [1] to [4], wherein the composition is solvent-free and the viscosity of the entire composition at 25 ° C is 100 to 5,000 mPa · s.

[6] The curable organopolysiloxane dynamic friction coefficient in the cured layer provided by coating the composition of 0.6g / m ² and 1.6g / m ² on a sheet-like substrate, and then cured by heating to 130 ℃ for 30 seconds in each case, the Measured at a displacement speed of 10 mm / min under the measurement conditions according to Japanese Industrial Standard P8147,

Growth (Δ)% of the dynamic friction coefficient = [{(1.6g / m coefficient of dynamic friction of the cured coating layer of ²⁾ - (coefficient of dynamic friction of the cured coating layer to ^{0.6g / m 2)} / 0.6g} / m ² Coefficient of kinetic friction of the cured layer] × 100

The curable organopolysiloxane composition according to any one of [1] to [5], wherein the rate of increase (Δ) of the kinetic friction coefficient measured according to the following formula is 10% or less.

[7] A sheet-like article having a cured layer provided by heat-curing the curable organopolysiloxane composition according to any one of [1] to [6].

[8] The cured layer is obtained by coating the sheet-like base material with the curable organopolysiloxane composition described in any one of [1] to [6] at a coating rate of 1.0 to 10.0 g / m ² and applying heat to cure the composition The sheet-like article according to [7], wherein the sheet is a cured layer.

[9] A sheet-like article according to [7] or [8], wherein the substrate is a polyethylene laminate paper or a plastic film.

[10] A surface protective sheet comprising the sheet-like article according to any one of [7] to [9].

[11] A curable organopolysiloxane composition as described in any one of [1] to [6], wherein 1.0 to 10.0 g / m ² of the curable organopolysiloxane composition is coated on a sheet-like substrate; The method for producing a sheet-like article according to [7] or [8], wherein the cured layer is formed by heat curing.

[12] A curable organopolysiloxane composition according to any one of [1] to [6], wherein the substantially transparent sheet-like substrate is coated with 1.0 to 10.0 g / m ² ; Wherein the cured layer is formed by heat curing.

[13] A sheet-like base material comprising a sheet-like base material having a cured layer provided on at least one side of the sheet-like base material by heating and curing the curable organopolysiloxane composition according to any one of [1] to [6] Sensitive adhesive sheet (SA) comprising a pressure-sensitive adhesive layer provided on at least one side of the sheet-like base material (S1), wherein the pressure-sensitive adhesive layer And a layer of cured material.

[14] A sheet-like base material (S1) comprising a sheet-like base material having a cured layer provided on at least one side of the sheet-like base material by heating and curing the curable organopolysiloxane composition according to any one of [1] to [6] And a release sheet (SR) comprising a release layer provided on at least one side of the sheet-like base material, wherein the release layer is in contact with the above-mentioned cured layer when the application is performed.

The curable organopolysiloxane composition of the present invention can form a cured layer characterized in that even when the substrate is coated thickly, the increase in kinetic friction coefficient is suppressed and the rate dependency thereof is small, compared with the case of thin coating. The cured layer exhibits excellent peelability and smooth activity for a pressure-sensitive adhesive or a sticky material. It is also possible to provide a sheet-like article, in particular a surface protective film, and a laminate composed of the sheet-like article having a cured layer exhibiting the above technical effect by curing the composition, Can be provided.

The curable organopolysiloxane composition according to the present invention is a curable organopolysiloxane composition comprising (A) at least one (meth) acrylate having a viscosity at 25 DEG C of 20 to 500 mPa.s and a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 1.0 to 5.0% (B) an organopolysiloxane having a viscosity of from 1,000,000 mPa.s or more at 25 DEG C to a gelled state or a liquid state and having an alkenyl group content of from 0.005 to 0.100% by weight, the content of an alkenyl group having from 2 to 12 carbon atoms, (C) An organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (Si-H) in the molecule, and (D) a platinum type catalyst. Hereinafter, each component of the curable organopolysiloxane composition, the sheet-like article formed using the composition, and the laminate will be described in detail.

(A) is at least one organopolysiloxane having a viscosity of 20 to 500 mPa · s at 25 ° C. and a content of a higher alkenyl group having 4 to 12 carbon atoms in the range of 1.0 to 5.0 mass%. A cured layer having a high crosslinking density can be formed on the surface of the substrate by using the above component (A) having a high viscosity and a high content of a higher alkenyl group such as hexenyl, and the content of the alkenyl group is 0.005 to 0.100 mass% To effectively promote the bleed-out of the component (B) having a low reactivity from the inside of the cured layer to the surface. Therefore, even when the curable organopolysiloxane composition of the present invention is coated thickly on the substrate, the increase in kinetic friction coefficient and the rate dependence are suppressed depending on the thickness of the cured layer, and the excellent peelability and smooth activity for the pressure- . When the content of the higher alkenyl group is less than the lower limit, the thickness of the cured layer increases, the coefficient of dynamic friction increases and the coefficient of kinetic friction of the cured layer exhibits speed dependence, so that the object of the present invention can not be achieved. On the other hand, if the content of the higher alkenyl group exceeds the above limit, bleeding out of the component (B) is inhibited on the surface of the cured layer, and the technical effect of excellent peelability and smooth slippery property can be lost.

In view of the technical effect of the present invention, the component (A) preferably has a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 1.5 to 4.0% by mass, and a higher alkenyl group having 4 to 12 carbon atoms It is particularly preferable that the cyanyl group is an organopolysiloxane having the same molecular chain terminal ends and side chain hexenyl groups represented by the following structural formulas. The component (A) preferably contains (A1) a content of a higher alkenyl group having 4 to 12 carbon atoms in the range of 0.5 to 2.0% by mass, (A2) an organopolysiloxane having a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 2.5 to 5.0% by mass, preferably in a mass ratio of 1/4 to 4/1, A mixture of two or more organopolysiloxanes mixed at a mass ratio of 1/2 to 2/1, and the content of the higher alkenyl group in the mixture is preferably in the range of 1.5 to 4.0 mass%, more preferably 2.0 to 3.5 Particularly preferably in the range of 0.1 to 5% by mass.

[Chemical Formula 1]

Wherein m and n are each a positive number; m is a number which gives a content of a hexenyl group (- (CH ₂ ) ₄ CH = CH ₂ ) in the range of 1.0 to 5.0 mass%; Also, m + n is a number providing a viscosity at 25 캜 in the range of 20 to 500 mPa 占 퐏.

Also, in the case of high-speed measurement, when the technical effect of suppressing or inhibiting the increase of the surface friction coefficient of the substrate-cured layer (rate dependence) is particularly important, the component (A) preferably has a content of higher alkenyl groups of 2.0 to 5.0 mass% %, More preferably 2.0 to 3.5 mass%, or a content of a higher alkenyl group in the range of 2.0 to 5.0 mass%, more preferably 2.0 to 3.5 mass%, based on the total amount of the organopolysiloxane Is a mixture of two or more kinds of organopolysiloxanes.

(B) is an additive for imparting slipperiness to the surface of the cured layer, and more particularly, to a cured product obtained by effectively bleeding out the surface of the cured layer provided by the high crosslinking density curing achieved by using the component (A) bleed out, thereby imparting an appropriate kinetic friction coefficient to the surface of the cured layer and imparting excellent releasability and smooth sliding property to the pressure-sensitive adhesive or the sticky material.

The component (B) is an organopolysiloxane having a viscosity at 25 ° C of 1,000,000 mPa · s or more and a gelled state or a liquid state, wherein the content of an alkenyl group having 2 to 12 carbon atoms is 0.005 to 0.100% by mass. Examples of the non-alkenyl silicon-bonded organic group include alkyl groups such as methyl, ethyl, and propyl groups; An aryl group such as phenyl group; A haloalkyl group such as a 3,3,3-trifluoropropyl group and a nonafluorohexyl group; And a silanol group.

In order to achieve the object of the present invention, the component (B) is a low-reacting organopolysiloxane having an alkenyl group content of 2 to 12 carbon atoms in the range of 0.005 to 0.100 mass%, preferably 0.010 to 0.050 mass% , More preferably at least 90%, more preferably all of the alkylalkoxy-bonded organic groups are non-reactive alkyl or aryl groups. When the content of the alkenyl group in the component (B) is less than the above lower limit value, problems such as an increase in silicon migration to the substrate and a decrease in the residual adhesion rate may occur. When the content of the alkenyl group exceeds the upper limit, the component (B) is included in the cured layer by an addition reaction, and the effect of imparting slipperiness to the surface of the cured layer may be insufficient.

The component (B) may be a gum or liquid having a viscosity at 25 ° C of 1,000,000 mPa · s or more, and in the case of a liquid, the viscosity is preferably 10,000,000 mPa · s or more. When the component (B) takes a gum shape, the plasticity is preferably in the range of 0.5 to 10.0 mm, particularly preferably in the range of 0.9 to 3.0 mm. This plasticity is a plasticity measured by a plasticizer according to the method specified in Japanese Industrial Standard 6249. It is measured when a load of 1 kgf is applied to a spherical sample of 4.2 g at 25 ° C for 3 minutes.

The component (B) specifically includes polydimethylsiloxane end-blocked with the same or different groups selected from the group consisting of an alkyl group, an alkenyl group, an aryl group, a haloalkyl group or a silanol group bonded to the silicon at the molecular chain terminal in each case, dimethyl Siloxane-phenylmethylsiloxane copolymer, and dimethylsiloxane-diphenylsiloxane copolymer. The component (B) is particularly preferably a straight-chain or branched dimethylpolysiloxane end-blocked with the same or different groups selected from the group consisting of a trimethylsiloxy group, a silanol group or a vinyl group at the molecular chain terminal. Mixtures of polydimethylsiloxanes having different degrees of polymerization can also be used.

Particularly preferably, the component (B) is a polydimethylsiloxane end-blocked with dimethylvinylsiloxy groups at both ends of the molecular chain, and it is particularly preferable to use polydimethylsiloxane gum.

The curable organopolysiloxane composition of the present invention contains 0.5 to 15 parts by mass of the component (B) per 100 parts by mass of the above component (A), particularly preferably 1.0 to 5.0 parts by mass of the component (B) per 100 parts by mass of the component (A) By mass. When the content of the component (B) is lower than the above lower limit value, the slidability of the surface of the cured layer is insufficient. If the upper limit is exceeded, the viscosity of the organopolysiloxane composition becomes excessively high. In particular, when it is used as a solvent-free type, it may interfere with actual operations such as coating and manufacturing.

(C) is an organohydrogenpolysiloxane having at least two silicon-bonded hydrogen atoms (Si-H) in each molecule, and is a crosslinking agent. The component (C) preferably has at least three silicon-bonded hydrogen atoms in each molecule, and its bonding position is not particularly limited. The content of silicon-bonded hydrogen atoms is preferably from 0.1 to 2.0% by mass of the total organopolysiloxane composition, more preferably from 0.5 to 1.8% by mass of the total organopolysiloxane composition. Examples of the organic group bonded to the silicon in component (C) in addition to the hydrogen atom include alkyl groups such as methyl group, ethyl group, propyl group, butyl group and octyl group, and methyl group is preferable. The molecular structure of the component (C) is exemplified by linear, branched and branched cyclic structures.

The viscosity of the component (C) at 25 占 폚 is 1 to 1000 mPa 占 퐏, preferably 5 to 500 mPa 占 퐏. The reason for this is as follows: If the viscosity at 25 ° C is less than 1 mPa · s, the component (C) is easily volatilized from the organopolysiloxane composition, and if it exceeds 1,000 mPa · s, the curing time of the organopolysiloxane composition becomes long . Examples of the component (C) include a dimethylsiloxane · methylhydrogensiloxane copolymer in which both terminals are terminally blocked by a trimethylsiloxy group, dimethylsiloxane · methylhydrogensiloxane in which both terminals are terminally blocked by a dimethylhydrogensiloxy group, Copolymer, a methylhydrogenpolysiloxane having both terminals terminated with a trimethylsiloxy group, cyclic methylhydrogenpolysiloxane, and cyclic methylhydrogensiloxane-dimethylsiloxane copolymer. As component (C), two or more organohydrogenpolysiloxanes may be blended together.

More preferably, the component (C) is at least one organohydrogenpolysiloxane represented by the following formula (2), and the silicon-bonded alkenyl group contained in the component (A) and the component (B) (Hydrosilylation reaction) to form a cured layer.

(2)

Wherein R < ¹ > is substituted or unsubstituted, An unsubstituted monovalent saturated hydrocarbon group, and the same groups as mentioned above are exemplified. p is a positive integer, q is an integer of 2 or more, and p and q satisfy the relationship 10? (p + q)? 200. (p + q) is less than the above lower limit value, it is volatile in accordance with the curing condition, and there is a possibility that the curing is not sufficiently performed. In addition, when the upper limit is exceeded, there is a possibility of generating a gel while the bath standing time is increased. It is also preferable that p and q satisfy a relation of 0.3? Q / (p + q)? 1. When q / (p + q) is not more than the lower limit value, the curing of the curable organopolysiloxane composition according to the present invention may be insufficient.

The compounding amount of the component (C) is such that the molar ratio of the SiH group of the component (C) to the alkenyl group of the component (A) and the component (B) is 0.5 to 5, preferably 1 to 5. If the molar ratio is lower than the lower limit value, the curability is lowered, and if the molar ratio is higher than the upper limit value, the peeling resistance becomes larger and substantial peelability can not be obtained.

The component (D) is a platinum catalyst and promotes the addition reaction (hydrosilylation reaction) between silicon-bonded alkenyl groups present in the system and silicon-bonded hydrogen atoms. Preferred examples of the platinum-type catalyst include platinum chloride, alcohol-modified platinum chloride, olefin complexes of chloroplatinic acid, complexes of platinum chloride and ketones, complexes of platinum chloride with vinylsiloxane, platinum tetrachloride, fine platinum powder, alumina or Platinum black, an olefin complex of platinum, a platinum alkenylsiloxane complex, a carbonyl complex of platinum, a thermoplastic organic resin powder such as methyl methacrylate resin, polycarbonate Platinum-type catalysts including resins, polystyrene resins, silicone resins, and the like. Particularly, a complex of platinum chloride and divinyltetramethyldisiloxane, a complex of platinum chloride with tetramethyltetravinylcyclotetrasiloxane, a platinum / divinyltetramethyldisiloxane complex, a platinum / tetramethyltetravinylcyclotetrasiloxane complex and the like The same platinum / alkenylsiloxane complexes can be preferably used.

The component (D) is added in a catalytic amount. Generally, the amount of the platinum-based metal contained in the component (D) is 1 to 1,000 ppm, preferably 5 to 500 ppm based on the total mass of the curable organopolysiloxane composition of the present invention Lt; / RTI >

In addition to the above components, the curable organopolysiloxane composition of the present invention comprises (E) a hydrosilylation inhibitor for inhibiting gelation and curing at room temperature and providing curing under heating to improve storage stability at room temperature . A hydrosilylation reaction inhibitor, acetylenic compounds, ene-phosphorus compounds, organic nitrogen compounds, may be mentioned organic phosphorus compounds, oxime compounds. In particular, 2-methyl-3-butyne-2-ol, 3,5-dimethyl-1-hexyn- Alkyne alcohol such as 1-ethynyl-1-cyclohexanol (ETCH); 3-methyl-3-trimethylsiloxy-1-butyne; 3-methyl-3-trimethylsiloxy-1-pentyne; 3,5-dimethyl-3-trimethylsiloxy-1-sexine; 3-pentene-1-yne, 3,5-dimethyl-3-hexene-1-yne and the like; 1-ethynyl-1-trimethylsiloxycyclohexane; Bis (2,2-dimethyl-2-butynoxy) dimethylsilane; And alkenylsiloxanes such as 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7- Tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane, and the like. The addition amount of the (E) hydrosilylation reaction inhibitor generally ranges from 0.001 to 5 parts by mass per 100 parts by mass of the component (A), but the kind of the component (E), the performance and content of the hydrosilylation reaction catalyst, ), The amount of silicon atom-bonded hydrogen atoms in component (C), the desired pot life, and the working environment.

The composition of the present invention comprises a component (A), a component (B), a component (C), a component (D) and an optional component (E). Particularly suitable is the use of a solventless curable organopolysiloxane composition. The composition of the present invention may further comprise an alkenyl group-containing organopolysiloxane resin in order to lower the peeling force of the cured layer to the pressure-sensitive adhesive or the sticky material. In order to increase the viscosity of the coating liquid, a thickener such as a fine silica powder may be further added. Particularly, when the composition of the present invention is used in the form of solvent-free form, the composition of the present invention has a viscosity in the range of 50 to 10,000 mPa · s at 25 ° C in consideration of the possibility of coating the sheet- More preferably 100 to 5,000 mPa · s as the total viscosity of the composition.

On the other hand, the composition of the present invention may be dispersed in a known organic solvent for the purpose of thin coating or the like. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, octane and isoparaffin, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and isobutyl acetate, Ether solvents such as diisopropyl ether and 1,4-dioxane, cyclic polysiloxanes having a degree of polymerization of 3 to 6 such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, trichlorethylene, perchloro And halogenated hydrocarbons such as ethylene, trifluoromethylbenzene, 1,3-bis (trifluoromethyl) benzene and methylpentafluorobenzene. When thinly coated on a sheet-like substrate having low heat resistance, the use of an ether solvent is preferable based on the problem of hardening and swelling. The technical effect of the present invention in which the increase in kinetic friction coefficient is suppressed when the substrate is coated thickly compared with the case where the substrate is thinly coated and the speed dependence due to the coefficient of dynamic friction is small when the substrate is coated thickly, It may not be sufficiently satisfactory in the case of < / RTI >

Any component other than the above components may be added to the curable organopolysiloxane composition according to the present invention. An adhesion promoter comprising an alkoxysilane compound such as, for example, 3-glycidoxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and the like; Antioxidants such as phenol type, quinone type, amine type, phosphorus type, phosphite type, sulfur type, thioether type and the like; Light stabilizers such as triazole, benzophenone and the like; Flame retardants such as phosphoric ester, halogen, phosphorus, and antimony; At least one antistatic agent including a cationic surfactant, an anionic surfactant, a nonionic surfactant, and the like; Antioxidants, heat-resistant agents, dyes, pigments, and the like.

Particularly, the sheet-like article having the cured layer provided by the composition according to the present invention can be used as an optical component such as a liquid crystal panel, a plasma display, a polarizing plate and a retarder or a surface of an electric / electronic component such as a printed wiring board, IC, When used as a surface protective film for protecting, the addition of an antistatic agent is preferable.

The composition of the present invention can be prepared by simply and uniformly mixing the components (A) to (D), the component (E) and all other components. Although the order of addition of the respective components is not particularly limited, when the components (A), (B) and (C) are mixed and the component (D) is separately stored, . Further, in the composition containing the component (A) to the component (D), and further the component (E), it is also preferable to control the amount of the component (E) to be crosslinked at room temperature.

When the curable organopolysiloxane composition of the present invention as described above is uniformly coated on the sheet-like substrate and the components (A) and (C) are heated under conditions sufficient for hydrosilylation reaction-mediated crosslinking, , A sheet-like article having transparency and a cured layer excellent in adhesion to a sheet-like base material can be produced. Further, the cured layer obtained by curing the composition of the present invention is excellent in flexibility and air permeability, and has an advantage of being less inclusive of air bubbles even when attached to an object other than a flat surface. Therefore, it can be suitably used in applications where both the peeling property of the cured layer such as the optical display and the glass surface protective film and the adhesion property of the cured layer to the object to be protected are all important.

In particular, the curable organopolysiloxane compositions of the present invention can be applied on sheet-like substrates, such as sheet-like substrates such as polyethylene-laminated paper and polyethylene terephthalate films, with different coating ratios, especially 0.6 g / m ² (= m ² (= thick cured layer) and heating each of them at a temperature of 130 ° C for 30 seconds to form a sheet-like article having an increase rate of the coefficient of dynamic friction (Δ) of 10% or less with respect to the cured cured layer And a cured layer characterized in that an increase in kinetic friction coefficient is suppressed or inhibited with respect to a change in the coating rate. Further, according to the present invention, a sheet-like article having an increase rate of the kinetic friction coefficient of 5% or less can be obtained, and a sheet-like article having an increase rate of the coefficient of dynamic friction of -15% to 3% can also be obtained.

Here, the " kinetic friction coefficient for the cured layer "in the " rate of increase (%) of kinetic friction coefficient" indicates the coefficient of dynamic friction of the front and back surfaces of the sheet- The kinetic friction coefficient was measured using a measuring device such as a Tensilon tensile tester under the conditions of a load of 1,000 g, a moving speed of 10 mm / min, a temperature of 23 ° C and a humidity of 65% in accordance with an industrial standard P8147 standard Is a determined value.

In addition, the rate of increase (Δ)% of the coefficient of dynamic friction is composed of a sheet-like substrate having a cured layer obtained by the sample-and-coating rate of 1.6g / m ² composed of a sheet-like substrate having a cured layer obtained from a coating rate of 0.6g / m ² The values of the respective kinetic friction coefficients are measured on the sample in the manner described above and the increase rate of the kinetic friction coefficient of the cured layer is calculated according to the following equation.

Δ (%) = {(1.6g / m coefficient of dynamic friction of the cured coating layer with ² - 0.6g / m coefficient of dynamic friction of the cured coating layer to ²⁾ / 0.6g / m ² of the cured coating layer to movement Friction coefficient} x 100

A substrate, a substrate, a substrate, a substrate, a substrate, a substrate, a substrate, a substrate, a substrate, a substrate, a substrate, ), Glass fibers, and various sheet-like substrates of these materials

As synthetic resin films, synthetic resin films such as polyester, polytetrafluoroethylene, polyimide, polyphenylene sulfide, polyamide, polycarbonate, polystyrene, polypropylene, polyethylene, polyvinyl chloride, polyethylene terephthalate, have. Since the cured layer of the present invention is substantially transparent, it is useful to select a sheet-like base material having high transparency composed of such a synthetic resin film serving as a substantially transparent sheet-like base material in that a protective film excellent in transparency can be obtained.

Examples of paper include Japanese paper, synthetic paper, polyolefin laminate paper (particularly polyethylene laminate paper), corrugated paper, and clay coated paper.

The thickness of the sheet-like substrate exemplified above is not particularly limited, but is usually about 5 to 300 mu m. Further, a primer treatment, a corona treatment, an etching treatment or a plasma-treated auxiliary film may be used to improve the adhesion between the sheet-like substrate and the cured layer. The primer composition used in this connection is a condensation type silicone primer composition comprising a polyorganosiloxane having a SiOH group at the terminal, a SiH group-containing polysiloxane and / or an alkoxy group-containing polysiloxane and a condensation reaction catalyst, and an alkenyl (for example, Vinyl) -containing polydiorganosiloxanes, SiH group-containing polysiloxanes, and addition reaction catalysts.

The surface opposite to the sheet-like substrate from the cured layer may be subjected to surface treatment such as for example, a damage prevention treatment, a stain prevention treatment, a fingerprint adhesion prevention treatment, an anti-glare treatment, an antireflection treatment, and an antistatic treatment. Such a surface treatment may be performed after coating the curable organopolysiloxane composition of the present invention on the sheet-like substrate, or after the surface treatment is performed, the composition may be applied.

The damage prevention treatment (hard coat treatment) can be exemplified by treatment with an acrylate-based, silicone-based, oxetane-based, inorganic or organic / inorganic hybrid hard coating agent.

The anti-stain treatment may be, for example, treatment with a fluorine-based, silicone-based, ceramic-based or photocatalyst-containing antifouling agent.

Examples of the antireflection treatment include a wet treatment based on a fluorine-based or silicone antireflective coating, and a dry treatment by vapor deposition or sputtering. Examples of the antistatic treatment include a treatment using a surfactant system, a silicon system, an organic boron system, a conductive polymer system, a metal oxide system, or a deposition metal antistatic agent.

The temperature for curing the curable organopolysiloxane composition of the present invention in a sheet-like base material is generally in the range of 50 to 200 ° C, but may be 200 ° C or more if the heat resistance of the sheet-like base material is favorable. The heating method is not particularly limited, and examples include heating in a hot-air circulating oven, passing through a long heating furnace, and infrared radiation by an infrared lamp and a halogen lamp. It may also be cured by using both heating and ultraviolet irradiation. (D) is a platinum / alkenylsiloxane complex catalyst, even when the content of the catalyst is in the range of 80 to 200 ppm based on the total amount of the composition, at 100 to 150 ° C in a short time of 1 to 40 seconds A cured layer excellent in slidability, transparency and adhesion to a sheet-like base material can be easily obtained.

On the other hand, in the case of a sheet-like base material such as polyolefin having a low heat resistance, after the curable organopolysiloxane composition of the present invention is coated on the sheet-like base material such as polyolefin, the temperature is preferably from 50 캜 to 100 캜, It is preferable to heat at a low temperature of 50 캜 to 80 캜. In this case, the effective curing time is from 30 seconds to several minutes, such as from 1 to 10 minutes.

Immersion by a method of coating the curable organopolysiloxane composition of the present invention on a sheet-like substrate surface; spray; Gravure coating; Offset coating, offset gravure coating; Roll coating using an offset transfer roll coater or the like; Reverse roll coating; Air knife coating; For example curtain coating with a curtain flow coater; Comma coating; Known methods used for forming Mayer bar coatings and other hardened layers can be used without limitation.

The coating rate is set depending on the application, but is generally from 0.1 to 200.0 g / m ² in the case of a sheet type substrate, and may be selected from 0.1 to 1.0 g / m ² for the purpose of thinly coating the curable organopolysiloxane of the present invention with the release layer And it is possible to select 1.0 to 10.0 g / m < ² > for the purpose of thick coating, and for applications requiring both peelability and adhesive property like protective film applications. The curable organopolysiloxane of the present invention is preferably coated at 1.0 to 10.0 g / m ² , particularly preferably at 1.0 to 5.0 g / m ² , because it is excellent in slipperiness especially when thickly coated.

The cured layer of the curable organopolysiloxane composition of the present invention functions as a peelable cured layer. On the other hand, there is an advantage that the composition can be used as a micro-tacky adhesive layer having a superior peeling property equivalent to that of a thin coating of the composition. The use of the composition of the present invention, taking advantage of these characteristics, will be described as follows.

The composition of the present invention is useful for forming a hardened layer having excellent surface slipperiness and excellent releasability to a pressure-sensitive adhesive and a sticky material, and more particularly to a process paper, an asphalt papermaking paper, Can be suitably used as a forming agent.

Particularly, since the cured layer made of the composition of the present invention is excellent in peeling properties with respect to other pressure-sensitive adhesive layers or adhesive layers, it is possible to use a process paper such as a laminate including a pressure-sensitive adhesive layer or a viscous material, Lt; RTI ID = 0.0 > laminate. ≪ / RTI > Specifically, using the curable organopolysiloxane composition of the present invention, (S1) a cured layer (a parting layer or a release layer) obtained by heat-curing the curable organopolysiloxane composition of the present invention on at least one side of a sheet- (SA) a laminate composed of an adhesive sheet having a pressure-sensitive adhesive (or adhesive layer) on at least one side of the sheet-shaped substrate and the pressure-sensitive adhesive layer contacting the cured layer can be obtained.

The pressure-sensitive adhesive or sticky material applied to the laminate may be any of various pressure-sensitive adhesives, various adhesives, and the like, and may be an acrylic resin-based pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, Acrylic resin adhesives, synthetic rubber adhesives, silicone adhesives, epoxy resin adhesives, and polyurethane adhesives. In addition, sticky foods such as asphalt and rice cake, pastes, glues, starch, and new catches can be mentioned.

On the other hand, the cured layer composed of the composition of the present invention can be used as a fine-tacky adhesive layer with excellent peeling property equivalent to that of thinly coated, especially when the composition is coated thickly, And can be used as an adhesive layer of an adhesive sheet or the like. Such an adhesive layer maintains adhesion for a long period of time after adhering to a subject and has a merit of being excellent in peelability after adhesion for a long period of time without causing a phenomenon that the adhesion position is deviated or peeled off. Also, re-application is easily performed, and when the protective sheet is used for a long period of time, there is an advantage that it can withstand deformation of the cured layer, whitening, generation of residual adhesive, and the like.

The protective sheet or the re-peelable adhesive sheet having the cured layer composed of the composition of the present invention can be used as a sheet for a metal sheet, a coated metal sheet, an aluminum sash, a resin sheet or a plate, a decorating steel sheet or plate, a polyvinyl chloride - Can be used to attach or protect surfaces such as laminated steel sheets or plates, glass sheets or plates. It is also very suitable for use as a protective sheet used for manufacturing various liquid crystal display panels (also referred to as a monitor or a display), a process of circulating a polarizing plate, a process of manufacturing and distributing resin members of various machines such as automobiles, .

Likewise, a protective sheet with an adhesive layer made of the cured layer of the present invention is easy to re-apply, and such a protective sheet is suitable as a protective sheet for a variety of displays such as the following. The protective sheet of the present invention is used for the purpose of preventing damage to the surface, preventing stains, preventing fingerprints, preventing static electricity, preventing reflection, and anti-peeking in the manufacture, distribution and use of such a display.

The laminate composed of such a surface-protective sheet can be produced by using a curable organopolysiloxane composition of the present invention to cure a cured layer (a release layer and an adhesive layer) obtained by thermally curing the curable organopolysiloxane composition of the present invention on at least one side of a sheet- By bringing the release layer into contact with the cured layer with a release sheet SR including a release layer on at least one side of the sheet-like base material, on the sheet-like base material S1 containing the release layer.

[Example]

Hereinafter, the present invention will be described in detail by way of examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, all parts are parts by mass, Hex is a hexenyl group, and Me is a methyl group. Viscosity and plasticity are values measured at 25 ° C. The slipperiness of the cured layer made of the curable organopolysiloxane composition was evaluated by measuring the kinetic friction coefficient by the following method.

[Formation of hardened layer]

The curable organopolysiloxane composition was coated on the substrate surface in an amount of 0.6, 1.0 or 1.6 g / m < ² > as siloxane using a printing tester (Seiko Co., Ltd., RI-2) Respectively. After coating, the substrate was heat-treated at 130 캜 for 30 seconds in a hot-air circulating oven to form a cured layer on the surface of each substrate.

[Measurement of kinetic friction coefficient of polyethylene laminate paper (Examples 1 to 3 and Comparative Examples 1 to 3)]

Using a polyethylene-laminated paper having a cured layer obtained by the method described above on the surface thereof, a measurement sample was produced one day after curing, and this cured layer was coated on the untreated back side of the polyethylene-laminated paper The front / back kinematic friction coefficient of a polyethylene-laminated paper prepared by superimposing a cured layer (surface, cured silicone layer) and having a cured layer obtained as described above was measured using a tensile tensile tester (trade name: Tensilon RTC-1210, Orientec Co., Ltd.). Each individual moving speed was measured under the conditions of load: 1000 g, moving speed: 10, 30, 100 mm / min, temperature 23 캜 and humidity 65%.

[Measurement of kinetic friction coefficient of polyethylene terephthalate film (Examples 4 to 6)]

Using a polyethylene terephthalate (PET) film (thickness 50 탆) having a cured layer obtained by the above-described method on its surface, a measurement sample was produced one day after curing, and this cured layer was treated with a polyethylene terephthalate film The front / rear dynamic friction coefficient of the PET film having the cured layer obtained by superimposing the back side (PET substrate side) and the cured layer (surface silicone hardened layer) which had not been obtained as described above was measured using a tensile tensile tester Tensilon RTC-1210, Orientec Co., Ltd.). Each moving speed was measured under the conditions of load: 1000 g, moving speed: 10, 30, 100 mm / min, temperature of 23 캜 and humidity of 65%.

[Increase rate (?)% Of kinetic friction coefficient]

0.6g / m ² and according to the method described for the sample having a coating ratio of 1.6g / m ² was measured dynamic friction coefficient (the value measured in the movement speed of 10 mm), rate of increase in dynamic friction coefficient of the cured layer (?)% Was determined according to the following equation. Also, the increase rate of the kinetic friction coefficient was calculated as a reference value at the moving speed of 30 and 100 mm / min (Table 1 and Table 3).

Δ (%) = {(1.6g / m coefficient of dynamic friction of the cured coating layer with ² - 0.6g / m coefficient of dynamic friction of the cured coating layer to ²⁾ / 0.6g / m ² of the cured coating layer to movement Friction coefficient} x 100

[Velocity dependence of kinetic friction coefficient of hardened layer: (? S)%]

The kinematic friction coefficient was measured by the method described above at a displacement rate of 10 mm / min and a velocity of 100 mm / min for the cured layer having the same coating rate, and the change in the coefficient of dynamic friction (δS) Respectively.

δS (%) = {(kinetic friction coefficient of the cured layer measured at a moving speed of 100 mm / min - kinetic friction coefficient of the cured layer measured at a moving speed of 10 mm / min) / moving speed of 10 mm / Coefficient of kinetic friction of layer} × 100

[Example 1]

(A1) 93.6 parts of polydimethylsiloxane (viscosity 220 mPa s, hexenyl group content 1.15 mass%) having hexenyl groups at both terminals and side chains of the molecular chain;

(B1) 3.0 parts of a dimethylsiloxane rubber having a plasticity of 1.4 mm and end-blocked with a vinyl group at the molecular chain terminal;

(C1) 3.2 parts of a methylhydrogenpolysiloxane (silicon-bonded hydrogen atom content: 1.6% by mass) end-blocked with a molecular chain end trimethylsiloxy group having a viscosity of 25 mPa · s; And

(E) 1-ethynyl-1-cyclohexanol (ETCH) were uniformly mixed. To this mixture, a chloroplatinic acid · 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content: 0.6 mass%) (D) was blended so as to have a platinum metal amount of 100 ppm, and a viscosity of 800 mPa Gt; s < / RTI > solvent-free curable organopolysiloxane composition was obtained as Composition 1. The molar ratio of the silicon-bonded hydrogen atoms (Si-) H / Hex of the composition was 1.27. The resulting organopolysiloxane composition was coated on the polyethylene laminate paper in the amounts of 0.6, 1.0, and 1.6 g / m ² by the above method and cured, and the coefficient of dynamic friction of each of the cured layers was measured. The results are shown in Table 1.

[Example 2]

(A1) 46.8 parts of polydimethylsiloxane (viscosity 220 mPa s, hexenyl group content 1.15 mass%) having hexenyl groups at both terminals and side chains of the molecular chain;

(A2) 44.5 parts of polydimethylsiloxane (viscosity 100 mPa s, hexenyl group content 3.00 mass%) having hexenyl groups at both terminals and side chains of the molecular chain;

(B1) 3.0 parts of a dimethylsiloxane rubber having a plasticity of 1.4 mm and having a molecular chain terminal end-blocked with a vinyl group;

(C1) 7.8 parts of a methylhydrogenpolysiloxane (silicon-bonded hydrogen atom content: 1.6% by mass) end-blocked with a trimethylsiloxy group at both ends of a molecular chain having a viscosity of 25 mPa · s;

(E) 1-ethynyl-1-cyclohexanol (ETCH) 0.2 parts were homogeneously mixed. (D) platinum chloride · 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content: 0.6% by mass) was blended so as to have a platinum metal amount of 100 ppm to obtain a mixture having a viscosity of 600 mPa · s of a solvent-free curable organopolysiloxane composition was obtained as Composition 2. The molar ratio of the silicon-bonded hydrogen atoms (Si-) H / Hex of the composition was 1.25. The resulting organopolysiloxane composition was coated on the polyethylene laminate paper in the amounts of 0.6, 1.0, and 1.6 g / m ² by the above method and cured, and the coefficient of dynamic friction of each of the cured layers was measured. The results are shown in Table 1.

[Example 3]

(A2) 89.0 parts of polydimethylsiloxane (viscosity 100 mPa s, hexenyl group content 3.00 mass%) having hexenyl groups at both terminals and side chains of the molecular chain;

(B1) 3.0 parts of a dimethylsiloxane rubber having a plasticity of 1.4 mm and having a molecular chain terminal end-blocked with a vinyl group;

(C1) 7.8 parts of a methylhydrogenpolysiloxane (silicon-bonded hydrogen atom content: 1.6% by mass) end-blocked with a trimethylsiloxy group at both ends of the molecular chain having a viscosity of 25 mPa · s;

(E) 1-ethynyl-1-cyclohexanol (ETCH) 0.2 parts were homogeneously mixed. (D) platinum chloride · 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (platinum metal content: 0.6% by mass) was blended so as to have a platinum metal content of 100 ppm, and a viscosity of 300 mPa · s of a solvent-free curable organopolysiloxane composition was obtained as Composition 3. The molar ratio of the silicon-bonded hydrogen atoms (Si-) H / Hex of the composition was 1.25. The resulting organopolysiloxane composition was coated on polyethylene laminating paper in the amounts of 0.6, 1.0, and 1.6 g / m < ² > according to the above method and cured to measure the kinetic friction coefficient of each cured layer. The results are shown in Table 1.

[Comparative Example 1]

(CA1) 91.3 parts of polydimethylsiloxane (viscosity 60 mPa,, vinyl group content 1.60% by mass) having vinyl groups at both ends of the molecular chain and side chain instead of the component (A1) and the component (A2) Similarly to Example 2, a solvent-free curable organopolysiloxane composition was obtained as Comparative Composition 1. The resulting organopolysiloxane composition was coated on the polyethylene laminate paper in the amounts of 0.6, 1.0, and 1.6 g / m ² by the above method and cured, and the coefficient of dynamic friction of each of the cured layers was measured. The results are shown in Table 1.

[Comparative Example 2]

Except that the component (A1) and the component (A2) were replaced by 3 parts of polydimethylsiloxane (viscosity: 350 mPa · s, hexenyl group content: 0.70% by mass) having 3 parts at both terminals of the molecular chain and a hexenyl group at the side chain Similarly to Example 2, a solvent-free curable organopolysiloxane composition was obtained as Comparative Composition 2. The resulting organopolysiloxane composition was coated on the polyethylene laminate paper in the amounts of 0.6, 1.0, and 1.6 g / m ² by the above method and cured, and the coefficient of dynamic friction of each of the cured layers was measured. The results are shown in Table 1.

[Comparative Example 3]

Except that 91.3 parts of polydimethylsiloxane (viscosity 100 mPa · s, hexenyl group content: 8.00 mass%) having hexenyl groups at both ends of the molecular chain and at both ends of the chain (CA3) was used instead of the component (A1) Similarly to Example 2, a solvent-free curable organopolysiloxane composition was obtained as Comparative Composition 3. The resulting organopolysiloxane composition was coated on polyethylene laminate paper in the amounts described above by the methods described above in amounts of 0.6, 1.0, and 1.6 g / m < ² >, and cured to determine the coefficient of kinetic friction of each of the cured layers. The results are shown in Table 1.

The peel resistance values of the respective cured layers of Example 2 and Comparative Examples 1 to 3 were measured in the following manner. The measurement results are shown in Table 2.

[Peel resistance value]

On the surface of the cured layer formed by the above method, an acrylic solvent-type pressure-sensitive adhesive (Toyo Ink Mfg. Co., Ltd., product name: ORIVINE BPS-5127) was uniformly coated using a coater to give a solid of 30 g / m ² and heated at 70 캜 for 2 minutes. High quality paper (areal weight = 64 g / m ² ) was pasted on the surface of the acrylic pressure-sensitive adhesive, and the resultant adhesive paper was cut to a width of 5 cm to prepare a specimen. A load of 20 g / cm < ² > was applied to the specimen, and the specimen was left in the air at a temperature of 25 DEG C and a humidity of 60% for 24 hours. Thereafter, the adhered paper was peeled off under the condition of an angle of 180 degrees and a peeling speed of 0.3 m / min using a tensile tester (Tensilon universal testing machine of A & D Co., Ltd.), and the force (mN / 50 mm) was measured.

[Example 4]

The kinetic friction coefficient of each cured layer was measured in the same manner as in Example 1, except that a polyethylene terephthalate (PET) film was used in place of the polyethylene laminated paper. The results are shown in Table 2.

[Example 5]

The kinetic friction coefficient of each cured layer was measured in the same manner as in Example 2, except that a polyethylene terephthalate (PET) film was used in place of the polyethylene laminate paper, and the results are shown in Table 2.

[Example 6]

Others using a polyethylene terephthalate (PET) film instead of the polyethylene laminating paper measured the kinetic friction coefficient of each of the cured layers in the same manner as in Example 3. The results are shown in Table 2.

[Table 1]

* Increased kinetic friction coefficient

[Table 2]

[Table 3]

* Increased kinetic friction coefficient

When using a polyethylene laminated paper composition of the present invention as shown in Table 1, in particular the composition and the second composition is 3 to increase the dynamic friction coefficient of the cured layer, if different, such as the application thickness of 0.6, 1.0 and 1.6g / m ² And the kinetic friction coefficient rate dependence was suppressed even when the coating rate was 1.6 g / m ² (thick coating). Also, the composition 3 had a kinetic friction coefficient rate dependence of 20% or less even when the coating rate was 1.6 g / m ² (thick coating). On the other hand, each of the cured layers obtained in Comparative Examples 1 to 3, when peeled at a high speed of 30 mm / min or more, greatly changed in accordance with the thickness of the coating, because the coefficient of dynamic friction of the cured layer exceeded the upper limit of 20%. Similarly, in the case of the cured layer of Comparative Example 1 and Comparative Example 2, the coefficient of kinetic friction coefficient of the cured layer showed a very high dependency on the coating rate of 1.6 g / m ² (thick coating). Also, as shown in Table 2, the peeling resistance value of Comparative Example was relatively larger than that of Examples.

Increase in the dynamic friction coefficient of the cured layer in a variety of cases, such as polyethylene terephthalate case of using the film, the composition of the present invention as shown in Table 3, especially 2, and the composition is applied to the composition 3 having a thickness of 0.6, 1.0 and 1.6g / m ² Respectively.

Claims (14)

(A) 100 parts by weight of an organopolysiloxane having a viscosity at 25 ° C of 20 to 500 mPa · s and a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 1.0 to 5.0 mass%
(B) 0.5 to 15 parts by mass of an organopolysiloxane having a viscosity of from 1,000 to 1,000,000 mPa · s at 25 ° C in a gum state or a liquid state and having an alkenyl group content of from 2 to 12 carbon atoms in an amount of from 0.005 to 0.100%
(C) a silicon-bonded hydrogen atom (Si-H) in each molecule and the molar ratio of the SiH group in the component (C) to the alkenyl group in the component (A) And the content of the organohydrogenpolysiloxane, and
(D) a catalytic amount of a platinum-type catalyst,
Wherein the component (A)
(A1) an organopolysiloxane having a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 0.5 to 2.0% by mass, and
(A2) a mixture of two or more organopolysiloxanes obtained by mixing an organopolysiloxane having a content of a higher alkenyl group having 4 to 12 carbon atoms in a range of 2.5 to 5.0 mass% in a mass ratio of 1/4 to 4/1 , A curable organopolysiloxane composition. delete Claim 3 has been abandoned due to the setting registration fee. The curable organopolysiloxane composition of claim 1, wherein the higher alkenyl group in the component (A) is a hexenyl group. Claim 4 has been abandoned due to the setting registration fee. The curable organopolysiloxane composition of claim 1, wherein component (B) is dimethylpolysiloxane wherein both ends of the molecular chain are terminally blocked by a dimethylvinylsiloxy group. Claim 5 has been abandoned due to the setting registration fee. The curable organopolysiloxane composition according to any one of claims 1, 3 and 4, wherein the composition is solvent-free and the viscosity of the entire composition at 25 占 폚 is from 100 to 5,000 mPa 占 퐏 . Claim 6 has been abandoned due to the setting registration fee. The method of any one of claims 1, 3, and 4, wherein the curable organopolysiloxane composition is coated on the sheet-like substrate at 0.6 g / m ² and 1.6 g / m ² , The coefficient of kinetic friction on the cured layer provided by heating and curing is measured at a displacement rate of 10 mm / min under the measurement conditions according to Japanese Industrial Standard P8147,
Growth (Δ)% of the dynamic friction coefficient = [{(1.6g / m coefficient of dynamic friction of the cured coating layer of ²⁾ - (coefficient of dynamic friction of the cured coating layer to ^{0.6g / m 2)} / 0.6g} / m ² Coefficient of kinetic friction of the cured layer] × 100
% Of the kinetic friction coefficient measured according to formula (I) is less than or equal to 10%. ≪ RTI ID = 0.0 > 11. < / RTI > A sheet-like article having a cured layer provided by heat-curing the curable organopolysiloxane composition according to any one of claims 1, 3 and 4. Claim 8 has been abandoned due to the setting registration fee. A curable organopolysiloxane composition according to any one of claims 1, 3 and 4 is applied to a sheet-like substrate at a rate of 1.0 to 10.0 g / m < ² > and cured by heating to form a cured layer . Claim 9 has been abandoned due to the setting registration fee. The sheet-like article according to claim 8, wherein the substrate is a polyethylene-laminated paper or a plastic film. Claim 10 has been abandoned due to the setting registration fee. A surface protective sheet comprising the sheet-like article according to claim 7. A method of producing a sheet-like article,
Coating the sheet-like substrate with the curable organopolysiloxane composition according to any one of claims 1, 3 and 4 in an amount of from 1.0 to 10.0 g / m ² ; Wherein the cured layer is formed by applying heat to form a cured layer. Claim 12 is abandoned in setting registration fee. A method for producing a surface protective sheet,
Coating a curable organopolysiloxane composition according to any one of claims 1, 3 and 4 to 1.0 to 10.0 g / m ² on a transparent sheet-like substrate; Wherein the cured layer is formed by applying heat to form a cured layer. A curable organopolysiloxane composition according to any one of claims 1 to 3, which is obtained by thermally curing the curable organopolysiloxane composition, is applied to a sheet-like base material (S1) comprising a sheet-like base material having at least one surface of the sheet- And a pressure-sensitive adhesive sheet (SA) comprising a pressure-sensitive adhesive layer provided on at least one side of the sheet-like base material, wherein the pressure-sensitive adhesive layer is in contact with the cured layer mentioned above when the application is performed . A sheet-like base material (S1) comprising a sheet-like base material having a cured layer provided on at least one side of a sheet-like base material by heat-curing the curable organopolysiloxane composition according to any one of claims 1, 3 and 4 And a release sheet (SR) comprising a release layer provided on at least one side of the sheet-like base material, wherein the release layer is in contact with the above-mentioned cured layer when the application is performed.