TWI479003B - Solvent-free polyfluorene stripper composition for film and release film using the same - Google Patents

Description

Solvent-free polyfluorene stripper composition for film and release film using the same

The present invention relates to a solvent-free curable polydecane oxygen stripper composition exhibiting excellent adhesion to a plastic film, and a release film using the same. The release film formed on the surface of the substrate film in the form of a cured film of the composition can be advantageously used as a film pressure-sensitive adhesive label or a film pressure-sensitive adhesive tape.

Conventionally, in order to prevent adhesion or bonding between a substrate such as a plastic film or paper and a pressure-sensitive adhesive material, a cured film of a polysiloxane composition has been applied to a surface of a substrate to impart releasability to the substrate.

In this case, a method widely used to form a polyfluorene oxide film on the surface of a substrate is to use a platinum-based compound as a catalyst to achieve an alkenyl group-containing organopolyoxane and an organic hydrogen polyoxyalkylene. The addition reaction, thereby forming a peelable film (for example, see Patent Reference 1).

In recent years, solvent-based polyoxynitride strippers containing an organic solvent such as toluene or xylene have been replaced with a solventless stripper containing no organic solvent for reasons including safety and hygiene.

A variety of solvent-free polyfluorene oxide compositions are known (for example, see Patent References 2 and 3). However, although these compositions exhibit favorable adhesion to the paper substrate, their adhesion to the plastic substrate is not good.

In order to solve the above problems, the invention disclosed in Patent References 4 and 5 uses an organic polyoxyalkylene having a branched structure and a high alkenyl content. However, in these inventions, although the adhesion to the plastic film substrate is specifically modified Good, but since the amount of the organohydrogenpolyoxyalkylene crosslinking agent also increases, there is a problem that the peeling resistance tends to increase.

[Patent Reference 1] JP 47-32072 A

[Patent Reference 2] JP 50-141591A

[Patent Reference 3] JP 52-39791 A

[Patent Reference 4] JP 06-293881 A

[Patent Reference 5] JP 2005-231355 A

The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a solvent-free curable polysulfide stripper composition exhibiting favorable adhesion to a plastic film substrate and good peelability, and a release film comprising the cured film of the composition.

In order to achieve the above object, the inventors of the present invention conducted various studies relating to an alkenyl group-containing organopolyoxane used as a main component of the composition, and thus made the following findings. That is, when only a so-called MQ resin (a siloxane resin having a branched or three-dimensional molecular structure) is mixed with a generally used alkenyl-containing linear diorganopolyoxyalkylene oxide, the resulting cured film is usually exhibited with a film substrate. Reduce the degree of adhesion. However, the inventors have found that a product obtained by reacting an alkenyl group-containing organopolyoxane with an MQ resin under heating using a basic catalyst exhibits a markedly improved adhesion to a film substrate. This finding is believed to be due to the fact that the MQ resin is incorporated into the alkenyl group-containing organopolyoxane, thereby increasing the strength of the cured film, and in the MQ resin. The condensation of the stanol groups in the group reduces the amount of residual stanol groups. Further, the present inventors have found that in this method, since the alkenyl content does not need to be significantly increased, the blending amount of the organohydrogenpolysiloxane used as the crosslinking agent can be suppressed, so that any deterioration of the peeling performance can be prevented.

In other words, the present invention provides a solventless curable polyoxynitride stripper composition for a plastic film having a viscosity in the range of 100 to 1,500 mPa‧s at 25 ° C, and comprising: (A) by A basic catalyst is used under heating to carry out a reaction between the component (A1) and the component (A2) described below to obtain 100 parts by mass of the product: (A1) 97 to 80 parts by mass of the diorganopolyoxyl An alkane containing at least two alkenyl groups bonded to a ruthenium atom in each molecule, wherein the amount of the alkenyl group is in the range of 0.01 to 0.05 mol/100 g, and the viscosity at 25 ° C is 100 to 1,500 mPa ‧ In the range of s, (A2) 3 to 20 parts by mass of R ₃ SiO _1/2 units (wherein R represents the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms which does not contain an aliphatic unsaturated bond, or a hydroxyl group) and a polyorganosiloxane of the SiO _4/2 unit, wherein the molar ratio between the R ₃ SiO _1/2 unit and the SiO _4/2 unit is in the range of 0.6 to 1.5 (wherein the component (A1) and the component) (A2) is a combined amount of 100 parts by mass), (B) 0.5 to 10 parts by mass of an organohydrogenpolysiloxane having at least three hydrogen atoms bonded to a ruthenium atom in each molecule, and 25 Under the Department of viscosity in the range of 5 to 1,000 mPa‧s, an effective amount of (C) an addition reaction retarder, and an effective amount of (D) of platinum group metal based catalyst.

The present invention also provides a release film comprising a plastic film substrate and a cured film of the solvent-free curable polyoxynitride stripper composition formed on at least one surface of the plastic film substrate.

When cured, the solventless curable polyoxynitride stripper composition of the present invention produces a film that exhibits a high level of strength, excellent adhesion to the film substrate, and superior peelability.

Best mode for carrying out the invention

A more detailed description of the invention is provided below.

The organopolysiloxane used to prepare the component (A1) used as the component (A) of the main component of the present invention is a diorganopolysiloxane which is used for improving the curability and releasability of the composition. The diorganopolysiloxane has at least two alkenyl groups bonded to the ruthenium atom in each molecule, and has an alkenyl group content of 0.01 to 0.05 mol/100 g [component (A1)], and has a temperature at 25 ° C Viscosity of 100 to 1,500 mPa‧s. Examples of the diorganopolysiloxane include a compound represented by the following formula (1) which contains at least two alkenyl groups bonded to a ruthenium atom in each molecule, which is represented by R ² in the formula Said. Linear diorganopolyoxyalkylene is preferred.

(R ² R ¹ ₂ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _a (R ² R ¹ SiO _2/2 ) _b (1)

(wherein R ² is an alkenyl group represented by -(CH ₂ ) _c -CH=CH ₂ (wherein c is an integer of 0 to 8), and R ¹ represents the same or different and has 1 to 10 carbon atoms and is free of aliphatic A monovalent hydrocarbon group of an unsaturated bond, and a and b are each an integer satisfying 60≦a≦280 and 0≦b≦10).

Examples of the alkenyl group R ² include a vinyl group, an allyl group, a propenyl group, a hexenyl group, an octenyl group or a nonenyl group. Vinyl is preferred from the standpoint of cost and efficacy.

Examples of the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms which does not contain an aliphatic unsaturated bond (represented by R ¹ in the formula) include an alkyl group such as a methyl group, an ethyl group or a propyl group such as a phenyl group. Or a tolyl aryl group. In terms of improving curability and peelability, 80 mol% or more of the R ¹ group is preferably a methyl group.

Further, the amount of the alkenyl group bonded to the ruthenium atom in the component (A1) bis organopolyoxane is an important factor, and can be ensured by the amount of 0.01 to 0.05 mol per 100 g of the component (Al). In order to achieve the desired adhesion and peeling performance. If the amount exceeds 0.05 mols, the cured film becomes brittle and the adhesion is deteriorated. In order to ensure that the amount is within this range, the b value in the structural formula (1) should be adjusted so as to satisfy 0 ≦ b ≦ 10, and preferably 0 ≦ b ≦ 5.

In addition, in order to achieve a viscosity at 25 ° C in the range of 100 to 1,500 mPa ‧ s (this represents the ideal viscosity range from the viewpoint of coating properties), the value of a in the structural formula (1) should satisfy 60 ≦ a ≦ 280, and preferably 70 ≦ a ≦ 250. The component (A1) may be used singly or in combination of two or more different compounds.

Component (A2) is agglomerates comprising R ₃ SiO _1/2 units (wherein R represents the same or different monovalent hydrocarbon groups having 1 to 10 carbon atoms which do not contain an aliphatic unsaturated bond, or a hydroxyl group) and SiO _4/2 units An organic siloxane (having a branched or three-dimensional molecular structure, also known as an MQ resin) wherein the molar ratio between the R ₃ SiO _1/2 unit and the SiO _4/2 unit is in the range of 0.6 to 1.5. If the molar ratio between the R ₃ SiO _1/2 unit and the SiO _4/2 unit is less than 0.6, it is likely to become gelled during heating under reaction with the component (A1) in the presence of a basic catalyst. If the molar ratio exceeds 1.5, the adhesion between the cured film and the film substrate is not improved. Examples of the same or different monovalent hydrocarbon groups (represented by R) having 1 to 10 carbon atoms which do not contain an aliphatic unsaturated bond include an alkyl group such as a methyl group, an ethyl group or a propyl group, and a aryl group such as a phenyl group or a tolyl group. Base, although methyl is preferred.

The component (A2) may include an OH group bonded to a ruthenium atom, although the OH group content is usually less than 0.2 mol/100 g [component (A2)], and preferably 0 to 0.15 mol/100 g [component (A2)) ] within the scope. If the OH group content exceeds 0.2 mol/100 g, it may be difficult to achieve the desired degree of adhesion. The component (A2) may be used singly or in combination with two or more different compounds.

The target product (A) can be obtained by reacting a mixture of the component (A1) and the component (A2) with a basic catalyst under heating.

Examples of the basic catalyst include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal alkoxides such as sodium methoxide and potassium butoxide, organic alkali metals such as butyllithium, and rings. A dimethyl carbonate polyoxane and a basic metal hydroxide are previously reacted together with a siliconate. The potassium hydroxide of potassium hydroxide is particularly preferred from the viewpoint of solubility in the polyorganosiloxane. The amount of the basic catalyst to be used is preferably in the range of 0.001 to 2.0 parts by mass, and even more preferably 0.002 to 1.0 part by mass per 100 parts by mass of the combination of the components (A1) and (A2).

The temperature or time of the reaction between the component (A1) and the component (A2) is not particularly limited, although in the case of using an organic solvent such as toluene or xylene, the reaction can be carried out at the reflux temperature of the organic solvent. . Further, it is preferred to remove the condensation water produced by the reaction from the reaction system. Examples of specific reaction conditions include a reaction temperature in the range of 80 to 180 ° C, and preferably 100 to 160 ° C. The reaction should be carried out for a sufficient period of time to ensure that the reaction proceeds sufficiently, and if the reaction temperature is in the range of from 80 to 180 ° C, the reaction time is usually in the range of from 0.5 to 20 hours, and if the reaction temperature is in the range of from 100 to 160 ° C, the reaction is carried out. The time is usually 1 to 12 hours. The blending amount of the component (A1) and the component (A2) must be in the range of 97 to 80 parts by mass (A1) and 3 with respect to 100 parts by mass of the combined mass components (A1) and (A2). It is within the range of 20 parts by mass of component (A2). If the blending amount is outside these ranges, it is difficult to achieve adhesion to the film substrate. The blending amount is preferably 95 to 82 parts by mass of the component (A1) and 5 to 18 parts by mass of the component (A2) with respect to 100 parts by mass of the combined mass components (A1) and (A2).

After the reaction, it is preferred to add a neutralizing agent such as 2-chloroethanol, hydrochloric acid, carbon dioxide gas or trimethylchloromethane to 0.003 to 3.0 in a combination of 100 parts by mass of components (A1) and (A2). The amount of the reaction mixture in the range of parts by mass is neutralized, and the neutralization is carried out at a temperature of 40 to 160 ° C for 0.5 to 20 hours. In the case where they use an organic solvent, the organic solvent can be removed by heating under reduced pressure using a conventional method. If necessary, purification-filtration can be performed to remove the neutral salt.

The organohydrogenpolyoxane of component (B) contains 3 or more (generally from 3 to 200), preferably 4 or more (for example 4 to 4) in each molecule. 150), and even more preferably 4 to about 100 hydrogen atoms bonded to the ruthenium atom (i.e., SiH group). These SiH groups undergo an addition reaction with an alkenyl group in the product of component (A), thereby forming a cured film. The organohydrogenpolyoxyalkylene of component (B) may be a linear, branched, cyclic or three-dimensional resinous structure, and the constraint is that the viscosity at 25 ° C is in the range of 5 to 1,000 mPa ‧ s.

The number of germanium atoms (or degree of polymerization) in each molecule of the organohydrogenpolyoxyalkylene is usually in the range of 3 to 300, more preferably 3 to 200, and most preferably 4 to about 100.

Specific examples of this type of organohydrogenpolyoxyalkylene include 1,3,5,7-tetramethylcyclotetraoxane, tris(hydrodimethyldecyloxy)methyldecane, and tris(hydrogendimethyl) a cyclic copolymer of decyloxy)phenylnonane, methylhydrocyclopolyoxyalkylene, methylhydroquinoxane and dimethyloxane, having two ends blocked by trimethyldecyloxy Methylhydrogen polyoxyalkylene, a copolymer of two dimethyl methoxyoxanes with a terminal blocked by trimethyl decyloxy group and methyl hydrooxane, having two dimethyl hydrocin a copolymer of dimethyl oxoxane and methylhydroquinoxane at the end of the oxy block, two methyl hydrazines having a terminal blocked by trimethyl decyloxy group and diphenyl hydrazine a copolymer of oxyalkylene, a copolymer of two methylhydropolysiloxanes having a terminal blocked by trimethylnonyloxyl, a mixture of diphenylphosphorane and dimethyloxane, having two a copolymer of methylhydrogenpolyoxane, methylphenyloxane and dimethyloxane at the end of the trimethyldecyloxy block, with two blocked with dimethylhydroquinoloxy Methyl hydrogen polyoxyalkylene at the end, two a copolymer of a base oxane and a diphenyl sulfoxane, a methyl hydrogen polyoxyalkylene having two ends blocked by a dimethylhydroquinoloxy group, a dimethyl methoxy alkane and a methylphenyl group. a copolymer of decane, a copolymer composed of (CH ₃ ) ₂ HSiO _1/2 units, (CH ₃ ) ₃ HSiO _1/2 units, and SiO _4/2 units, from (CH ₃ ) ₂ HSiO _1/2 a copolymer composed of a unit and an SiO _4/2 unit, a copolymer composed of a (CH ₃ ) ₂ HSiO _1/2 unit, a SiO _4/2 unit, and a (C ₆ H ₅ ) ₃ SiO _1/2 unit, and each of the above compounds A compound in which a part or all of a methyl group is substituted with another alkyl group or a phenyl group such as an ethyl group or a propyl group, and a compound represented by the structural formula (3) shown below, although this is a non-exhaustive list.

(R ³ R ¹ ₂ SiO _1/2 ) ₂ (HR ¹ SiO) _r (R ¹ ₂ SiO) _s (3)

(wherein H represents a hydrogen atom, and R ¹ represents the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms which does not contain an aliphatic unsaturated bond, R ^{3 is the} same as H or R ¹ , and r and s are 1 ≦r≦ An integer of 250 and 0 ≦ s ≦ 250, the constraint is 8 ≦ r + s ≦ 250, although if R ³ is a R ¹ group, r must be 3 or more). Examples of R ¹ include an alkyl group such as a methyl group, an ethyl group or a propyl group, and an aryl group such as a phenyl group or a tolyl group, however, a methyl group is preferred from the viewpoint of a modified addition reaction rate. Component (B) may be used alone or in combination with two or more different compounds.

The blending amount of the component (B) is usually in the range of 0.5 to 10.0 parts by mass per 100 parts by mass of the component (A), and preferably 1.0 to 8.0 parts by mass. Further, the SiH group in the component (B) is preferably in the range of from 1.0 to 5.0 with respect to the molar of the alkenyl group bonded to the ruthenium atom in the component (A). If the molar ratio is too small, a favorable cured film cannot be formed, and if the ratio is too large, the peeling resistance is increased, which is also undesirable. The blending amount of the components is even more preferably adjusted so that the molar ratio is in the range of 1.3 to 4.0.

Component (C) Addition reaction retarder is the so-called lifetime delay The agent, which delays the catalytic activity of the platinum group metal-based catalyst of the component (D) under normal temperature conditions, thereby prolonging the usable life time of the composition of the present invention. Examples of the addition reaction retarder include conventional compounds such as various organic nitrogen compounds, organophosphorus compounds, acetylene-based compounds, hydrazine compounds, and organochlorine compounds, which may be used alone or in combination of two or more. The compounds are used in combination. Deuterated products of acetylene alcohol and acetylene alcohol are especially preferred.

The blending amount of the component (C) is only required to be an effective amount, and in order to achieve a favorable balance between the curability and the service life of the composition of the present invention, the blending amount is usually in the component (A) per 100 parts by mass. It is in the range of 0.01 to 10 parts by mass, and preferably 0.05 to 5 parts by mass.

The platinum group metal-based catalyst of the component (D) is an addition reaction of an alkenyl group bonded to a ruthenium atom in the component (A) and a hydrogen atom bonded to a ruthenium atom in the component (B). An accelerated catalyst, and a platinum group metal-based compound known as an addition reaction catalyst can be used. Examples of such platinum group-based catalysts include platinum-based, palladium-based and rhodium-based catalysts, and platinum-based catalysts are particularly preferred. Examples of such platinum-based catalysts include chloroplatinic acid, an alcoholic or aldehyde solution of chloroplatinic acid, and a complex of chloroplatinic acid with any of a variety of olefins or vinyl siloxanes.

The amount of the platinum group metal-based catalyst added needs only to be an effective catalytic amount, and the weight of the platinum group metal relative to the weight of the component (A) from the viewpoint of realizing a favorable cured film and maintaining economic feasibility. The amount added is usually in the range of 1 to 1,000 ppm, and preferably 10 to 300 ppm.

The composition of the present invention can be obtained by blending a predetermined amount of the above components (A) to (D) together, however, in addition to the above components, the composition may also include 0 per 100 parts by mass of the product (A). Up to 30 parts by mass of the component (E) represented by the structural formula (2) shown below.

(where p and q are integers satisfying 0≦p≦20 and 0≦q≦20, respectively, and the constraint is 14≦p+q≦20).

Component (E) is a double-chain olefin or a so-called reactive diluent, and not only reduces the viscosity of the composition and improves the properties of the coating, but also improves the adhesion of the composition to the film substrate. The double-chain olefin exhibits a lower volatility than the equivalent α-olefin having the same number of carbon atoms during heat curing, and under the restriction condition of 14 ≦p + q ≦ 20, the white smog problem generated during heat curing can be prevented.

Since the component (E) is incorporated into the cured film by the addition reaction with the hydrogen atom bonded to the ruthenium atom in the component (B), the component (B) is used in the case where they are used in the component (E). The blending amount is preferably adjusted so that the molar ratio of the SiH group in the component (B) to the alkenyl group bonded to the ruthenium atom in the component (A) is in the range of 1.5 to 5.0.

The blending amount of the component (E) is preferably from 0 to 30 parts by mass, even more preferably from 0 to 25 parts by mass, and most preferably from 0.1 to 20 parts by mass per 100 parts by mass of the component (A). If the blending amount exceeds 30 parts by mass, the co-solubility of the components in the composition of the present invention tends to deteriorate.

The double-chain olefin represented by the structural formula (2) is commercially available, and an example is the product Linealene Dimer sold by Idemitsu Kosan Co., Ltd.

Other additives such as high viscosity dimethyl polyoxyalkylene and the like for imparting smoothness to the composition may also be added as an optional component as the case may be. A typical number of such optional components can be added without prejudice to the effects of the present invention.

In the preferred preparation of the polyxanthene composition of the present invention, the components (A) to (C) to which the component (E) and any other optional components are added are first uniformly mixed together, and then finally Add component (D). Each component can be a single material or a combination of two or more different materials. However, the viscosity of the overall composition at 25 ° C must be in the range of 100 to 1,500 mPa ‧ s. If the viscosity exceeds 1,500 mPa‧s, the properties of the coating are deteriorated, making the composition difficult to practically apply.

A description of an example of a method of manufacturing a release film according to a second aspect of the present invention is presented below. However, the release film of the present invention is not limited to the release film produced by the following method, and other conventional production methods may be used.

Examples of the plastic film used as the substrate to which the composition of the present invention is applied to form a cured film include films prepared from synthetic resins such as polyester, polypropylene, polyethylene, polyvinyl chloride, polytetrafluoroethylene, and polyimine. . The thickness of the substrate film is preferably from 10 μm to 150 μm, and even more preferably in the range of from 15 μm to 100 μm.

The composition of the present invention can be applied to the above substrate by a conventional method, including a three-roll method of indirect gravure-offset or a multi-step roll method containing 5 to 6 rolls. The amount of the composition applied to the substrate is usually in the range of 0.01 to 5.0 g/m ² , and preferably 0.1 to 2.0 g/m ² . The composition may be applied to the entire surface of the substrate or may be applied in a localized manner to locations where peeling properties are desired. After application to the substrate, the composition is cured by heating at a temperature of 60 to 200 ° C, and preferably 70 to 180 ° C for a period of 1 second to 5 minutes, thereby forming the release film of the present invention. The thickness of the cured film formed on the substrate film in this manner is preferably in the range of 0.01 μm to 5.0 μm, and even more preferably 0.1 μm to 2.0 μm.

[Examples]

The following is a description of the invention based on a series of examples and comparative examples, but the invention is not limited in any way to the examples presented below. In each of the examples, the number of parts means "parts by mass", and the viscosity value means a value measured at 25 °C.

Adhesion (initial and subsequent aging), stripping strength, and residual tack ratio of each polyoxymethylene composition were measured using the methods described below.

(adhesive: initial and subsequent aging)

A predetermined amount of the polyoxymethylene composition is applied to the surface of the film or sheet substrate, and then heated in a hot air drier set to a predetermined temperature for a predetermined period of time, thereby producing a cured film. Immediately after curing, the fingers were scratched back and forth 10 times across the surface of the cured film, and whether the film was separated to evaluate the initial adhesion, and was reported as follows.

Not separated: O

Separation: X

The cured film sample was stored under atmospheric pressure at 25 ° C and 60% humidity for 20 days, and then the film was scratched with a finger in the same manner as described above. Make The unseparated film was evaluated by the symbol O. For films that were separated under the above-mentioned type of finger scraping before the end of 20 days, the adhesion after aging was recorded as the number of days of separation.

(stripping strength)

A predetermined amount of the polyoxymethylene composition is applied onto the surface of the film substrate, and then heated in a hot air drier set to a predetermined temperature for a predetermined period of time, thereby producing a cured film. Subsequently, the cured film was aged in a separator at 25 ° C for 24 hours, and an acrylic solvent-based pressure-sensitive adhesive was used in a wet method to form a coating layer having a thickness of 130 μm (product name: BPS-5127) It was applied to the surface of the cured film by Toyo Ink Mfg. Co., Ltd., and then the structure was heat-treated at 100 ° C for 3 minutes. Subsequently, a surface sheet having the same material as the film-form substrate coated with the polyfluorene oxide composition was bonded to the treated surface, and aging was performed at 25 ° C for 20 hours. The obtained laminate was cut into strips having a width of 50 mm, and the surface sheet was gently peeled off from the release film at one edge of the strip-shaped sample, and a tensile tester (DSC-500 tester, manufactured by Shimadzu Corporation) was used. The two edges were gripped, and then the surface sheet was pulled away at an angle of 180 degrees and a stripping rate of 0.3 m/min and peeled off from the release film. Measure the minimum force (N) required to achieve this strip.

(residual adhesion ratio)

A release sheet having a cured film of a polysiloxane composition formed on the surface of the substrate was prepared in the same manner as the measurement of the peeling strength to make a pressure-sensitive adhesive tape of the polyester (product name: No. 31B, by Nitto Denko made) bonded to the surface of the release sheet, and then aging at 70 ° C Apply a load of 1.96 kPa at the same time for 20 hours. Subsequently, the pressure-sensitive adhesive tape was peeled off from the release sheet and bonded to the stainless steel sheet. One edge of the pressure-sensitive adhesive tape was then gently peeled off, and then the edge was gripped and peeled off at a stripping rate of 0.3 m/minute with respect to the direction of the 180-degree angle of the stainless steel sheet. Measure the minimum force A (N) required to achieve this strip. Further, as a blank, the polyester pressure-sensitive adhesive tape was also bonded to a Teflon (registered trademark) sheet, and then treated in the same manner as above, and the minimum force required for peeling the strip from the stainless steel sheet was measured. (N). The value of (A/B) × 100 (%) is described as the residual adhesion ratio.

[Synthesis Example 1: Preparation of Component (A)]

A four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel was charged with 900 g of a dimethylpolyoxane of the formula (1), wherein R ¹ represents a methyl group and R ² represents a vinyl group. a = 146, b = 0, the vinyl content is 0.018 mol / 100 g, and the viscosity is 400 mPa ‧ s, that is, as shown by the average composition formula (1-1) of the component (A1) Methyl polyoxane,

And 1.0 g of potassium citrate prepared in advance by reacting a cyclic dimethyl polysiloxane with 10% by mass of potassium hydroxide, and then raising the temperature to 120 ° C under a nitrogen atmosphere, thereby using citric acid Potassium is completely dissolved in the vinyl-containing dimethyl polyoxane. The resulting solution was cooled to 60 ° C, and then, as component (A2), an MQ resin containing R ₃ SiO _1/2 unit (wherein R represents a methyl group or a hydroxyl group) and a SiO _4/2 unit (active component: 100 g) was used. 143 g of a 70% toluene solution having a molar ratio of R ₃ SiO _1/2 unit/SiO _4/2 unit of 0.75 and an OH group content of 0.03 mol/100 g was added to the solution. The temperature of the resulting mixture was then raised again, and the reaction was allowed to proceed at 140 ° C for 6 hours while removing the resulting condensation water from the system. Subsequently, the temperature was cooled to 120 ° C, then 1.5 g of 2-chloroethanol was added to the cooled mixture, and after neutralizing at 120 ° C for 2 hours, stripping under reduced pressure to produce an organopolyoxane Ai . The organic polyoxyalkylene has a vinyl content of 0.016 mol/100 g (organopolyoxyalkylene Ai) and a viscosity of 440 mPa. s.

[Synthesis Example 2: Preparation of component (A)]

The flask was charged with 900 g of a vinyl group-containing dimethylpolysiloxane represented by the above average composition formula (1-1) as a component (A1) containing R ₃ SiO _1/2 unit (wherein R represents MQ resin having a methyl or hydroxy group and a SiO _4/2 unit and wherein the R ₃ SiO _1/2 unit/SiO _4/2 unit has a molar ratio of 1.15 and an OH group content of 0.06 mol/100 g (active component: 100 g) 143 g of a 70% toluene solution was used as the component (A2), and 1.0 g of potassium citrate used in Synthesis Example 1. The temperature of the resulting mixture was then raised under a nitrogen atmosphere, and the reaction was allowed to proceed at 140 ° C for 6 hours while removing the resulting condensation water from the system. The temperature of the reaction mixture thus obtained was cooled to 70 ° C, 0.5 g of trimethylchloromethane was added, and after neutralizing at 70 ° C for 2 hours, stripping was carried out under reduced pressure to produce an organopolyoxane A. -ii. The organic polydecane has a vinyl content of 0.016 mol/100 g (organopolyoxyalkylene A-ii) and a viscosity of 430 mPa. s.

[Synthesis Example 3: Preparation of component (A)]

Except that 850 g of the dimethyl polyoxyalkylene of the formula (1) is used, wherein R ¹ represents a methyl group, R ² represents a vinyl group, a = 177, b = 1, a vinyl content of 0.022 mol / 100 g, and a viscosity of 500mPa. s, that is, a dimethylpolysiloxane represented by an average composition formula (1-2) as a component (A1),

An organopolyoxane A was prepared in the same manner as in Synthesis Example 1, except that 214 g of the same 70% toluene solution (active component: 150 g) of the MQ resin used in Synthesis Example 1 was used as the component (A2). -iii. The organic polyoxane has a vinyl content of 0.019 mol/100 g (organopolyoxyalkylene A-iii) and a viscosity of 560 mPa. s.

[Reference Example 1]

100 parts of the organopolysiloxane Ai obtained in Synthesis Example 1 as component (A) and 2.2 parts of methylhydropolyoxyl represented by the average composition formula (3-1) shown below Alkane as component (B) [SiH/(SiCH=CH ₂ )=2.0]

To the mixture was added 0.2 part of 1-ethynyl-1-cyclohexanol as component (C), and stirring was continued until a homogeneous mixture was obtained. To the obtained mixture, a sufficient amount of a complex of platinum and vinyl siloxane represented by the structural formula Pt/[H ₂ C=C(CH ₃ ) ₂ Si] ₂ O is added as component (D), To provide an equivalent of 100 ppm of platinum relative to the organopolyoxane Ai, thereby producing a viscosity of 406 mPa.聚聚矽 oxygen composition.

Subsequently, the prepared polyfluorene oxide composition was applied to a polyester film having a thickness of 25 μm using a coating amount of 0.4 to 0.5 g/m ² (product name: Lumirror No. 25, S10, by Kimoto Co., Ltd.) On the manufacturing, and then by heating at 120 ° C for 20 seconds to form a cured film. The adhesion, peeling strength and residual adhesion ratio of the cured film were measured. The results of these measurements are shown in Table 2.

[Reference Example 2]

The viscosity was determined to be 400 mPa using the same procedure as in Reference Example 1, except that 100 parts of the organopolyoxane A-ii obtained in Synthesis Example 2 was used as the component (A). The polyfluorene composition of s, followed by formation of a cured film, and then evaluation of the effectiveness of the cured film. The results are shown in Table 2.

[Reference Example 3]

Except that 100 parts of the organopolysiloxane A-iii obtained in Synthesis Example 3 was used as the component (A), and 2.6 parts of the methylhydrogenpolysiloxane represented by the average composition formula (3-1) was used [ SiH / (SiCH = CH ₂ ) = 2.0] As the component (B), the viscosity was 505 mPa using the same procedure as in Reference Example 1. The polyoxygen composition of s, followed by formation of a cured film, and then evaluation of the effectiveness of the cured film. The results are shown in Table 2.

[Example 1]

Except that 2.8 parts of methylhydropolysiloxane (SiH/(SiCH=CH ₂ )=2.5) used as the component (B) in Reference Example 1 was used, and 15 parts of the structural formula shown below were added ( 2-1) A double-chain olefin (Linealene Dimer A-20, manufactured by Idemitsu Kosan Co., Ltd.) was used as the component (E), and the viscosity was 220 mPa using the same procedure as in Reference Example 1. The polyoxygen composition of s, followed by formation of a cured film, and then evaluation of the effectiveness of the cured film. The results are shown in Table 2.

[Comparative Examples 1 to 4]

The compositions of Comparative Examples 1 to 4 were prepared in the same manner as in Reference Example 1 using the components shown in Table 1 and the blend ratio.

The various components used, the blending amount of each of the components, and the viscosity of each of the compositions of Reference Examples 1 to 3, Example 1 and Comparative Examples 1 to 4 are shown in Table 1.

The component (A2) of Comparative Example 3 is a unit containing R ₃ SiO _1/2 (wherein R represents a methyl group, a vinyl group or a hydroxyl group) and a SiO _4/2 unit, wherein R ₃ SiO _1/2 unit / SiO _{4 / The} unit _{2 had} a molar ratio of 0.85, a vinyl content of 0.07 mol/100 g [component (A2)], and a hydroxyl group content of 0.03 mol/100 g [component (A2)] of a 70% toluene solution of MQ resin. The component (A1) of Comparative Example 4 is a dimethylpolyoxane of the above formula (1) wherein R ¹ represents a methyl group, R ² represents a vinyl group, a = 10, b = 0, and a vinyl content. It is 0.21 mol/100 g [component (Al)] and has a viscosity of 10 mPa. s.

Using the respective polyfluorene oxide compositions of Comparative Examples 1 to 4, the same procedure as in Reference Example 1 was employed to form a cured film and then the efficacy of the cured film was evaluated. The results are shown in Table 2.

[Comparative Example 5]

56 parts of the organic polyoxoxane having the average composition formula (4) shown below, having a vinyl content of 0.57 mol/100 g and a viscosity of 25 mPa. s,

34 parts of dimethylorganopolysiloxane having a vinyl group bonded to a ruthenium atom at the end of two molecular chains represented by the above average composition formula (1-1), 10 parts being composed of the average composition shown below The organopolysiloxane having the formula (5) has a vinyl content of 0.07 mol/100 g and a viscosity of 1,000,000 mPa. s,

39 parts of methylhydropolysiloxane (SiH/(SiCH=CH ₂ )=1.8] represented by the above average composition formula (3-1), and 1.0 part of 1-ethynyl-1-cyclohexanol are combined and Stirring is then continued until a homogeneous mixture is obtained. To the resulting mixture, a sufficient amount of a complex of platinum and vinyl oxane represented by the structural formula Pt/[H ₂ C=C(CH ₃ ) ₂ Si] ₂ O is added to provide an average of the combined masses. The composition of the dimethylorganopolysiloxane of the formula (1-1) and the equivalent of 100 ppm of the platinum of the organopolysiloxane represented by the formula (5), thereby producing a viscosity of 400 mPa.聚聚矽 oxygen composition. Using this polyoxymethylene composition, a cured film was formed using the same procedure as in Reference Example 1 and then the efficacy of the cured film was evaluated. The results are shown in Table 2.

[Table 2]

From the results of Table 2, it is clear that the solventless polyxanthene composition of the present invention produces a cured film which exhibits not only long-term adhesion to the plastic film but also good peeling performance.

Claims (4)

A solvent-free curable polyxanthoxy stripper composition for a plastic film having a temperature of 100 to 1,500 mPa at 25 ° C. The viscosity in the range of s, and it comprises: (A) 100 parts by mass of the product obtained by the reaction between the component (A1) and the component (A2) described below by using a basic catalyst under heating. : (A1) 97 to 80 parts by mass of a linear diorganopolysiloxane having at least two alkenyl groups bonded to a ruthenium atom in each molecule, wherein the amount of the alkenyl group is 0.01 to 0.05 mol/100 g. Within the range, and the viscosity at 25 ° C is between 100 and 1,500 mPa. In the range of s, (A2) 3 to 20 parts by mass of a polyorganosiloxane containing R ₃ SiO _1/2 units and SiO _4/2 units, wherein R represents the same or different from 1 to 10 carbon atoms and contains no fat. a monovalent hydrocarbon group of a group unsaturated bond, or a hydroxyl group, wherein the molar ratio of the R ₃ SiO _1/2 unit to the SiO _4/2 unit is in the range of 0.6 to 1.5, wherein the component (A1) and the component (A2) The combined amount is 100 parts by mass, (B) 0.5 to 10 parts by mass of the organohydrogenpolysiloxane having at least three hydrogen atoms bonded to the ruthenium atom in each molecule, and the viscosity at 25 ° C At 5 to 1,000 mPa. Within the range of s, (C) an effective amount of an addition reaction retarder, (D) an effective amount of a platinum group metal-based catalyst, and (E) 0.1 to 100 parts per 100 parts by mass of the component (A) 30 parts by mass of the double-chain olefin represented by the following formula (2): Where p and q are integers satisfying 0≦p≦20 and 0≦q≦20, respectively, and the constraint condition is 14≦p+q≦20. The solvent-free curable polydecane oxygen stripper composition according to claim 1, wherein the component (A1) of the alkenyl group-containing diorganopolysiloxane is represented by the formula (1) shown below. Linear diorganopolyoxy siloxane: (R ² R ¹ ₂ SiO _1/2 ) ₂ (R ¹ ₂ SiO _2/2 ) _a (R ² R ¹ SiO _2/2 ) _b (1) wherein R ² is -(CH ₂ ) _c -CH=CH ₂ represents an alkenyl group, wherein c is an integer of 0 to 8, and R ¹ represents the same or different monovalent hydrocarbon group having 1 to 10 carbon atoms which does not contain an aliphatic unsaturated bond, And a and b are integers satisfying 60≦a≦280 and 0≦b≦10, respectively. The solvent-free curable polyfluorene stripper composition according to claim 1, wherein 100 parts by mass of the linear diorganopolyoxyalkylene of the component (A1) and the component (A2) are used. a combination of polyorganosiloxanes in the presence of 0.001 to 2.0 parts by mass of a basic catalyst at a temperature of 80 to 180 ° C for 0.5 to 24 hours to produce a reaction mixture, followed by neutralization of 0.005 to 3.0 parts by mass The agent is added to the obtained reaction mixture, and a neutralization reaction is carried out at a temperature of 40 to 160 ° C to obtain a product of the component (A). A peelable plastic film comprising a plastic film substrate and a cured film of the solvent-free curable polyfluorene stripper composition according to claim 1 of at least one surface of the plastic film substrate.