FI98637B - Adhesive releasing composition - Google Patents

Description

98637

Release Agent Composition

The invention relates to an adhesive release composition. In particular, the invention relates to a release agent composition having permanent adhesive and tack release properties and excellent weight properties.

It is known that organopolysiloxane-based release agent compositions coated with a desired substrate, such as various papers, synthetic resin films, fibrous materials, etc., have excellent adhesive release properties. These organopolysiloxane release compositions may have a curing mechanism through a condensation reaction (see JP-35-13709 (13.709 / 60) and JP-36-1397 (1,397 / 61)) or a curing mechanism via an addition reaction (see JP). -26798 (26,798 / 71)).

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Although the above release agents provide excellent release properties for a variety of substrates, the coated surfaces are almost non-printable. Thus, it is not possible to write or otherwise mark such surfaces using inks such as printing ink or check ink.

20

The adhesive sheet or tape is generally wound into a roll for use, the adhesive; ·· "layer (a sticky adhesive coating on the sheet or teippialustalla), and separating layer (V opposite to the side of the organopolysiloxane composition in the coating) have overlapping \ and often encounter such infectious.!. sheet must be to write or to make the imprint "·· 25 during operation since this is releasably surface has been poor printing properties. * has been necessary between the adhesive layer and the sheet substrate rear side of the set, for example, printing properties, good and high-quality paper is further to be-in increased revenue. adhesive tape for packaging, e.g. cardboard, things like .. addresses, etc. cannot be overwritten on the tape.

30 • ·. It is an object of the present invention to solve the above problems by providing an adhesive release composition having excellent printability and release properties.

·· 35 The above object, as well as other objects, which are apparent from the following quality requirements and the accompanying requirements, are achieved by an adhesive release composition based on (A) a new oxyalkylene group-containing organopolysiloxane (B 9863737, 2 98) containing at least 3 silicon-linked alkenyl groups in each molecule. ) to an organove-typolysiloxane containing at least 3 silicon-bonded hydrogen atoms in each molecule and (C) a platinum-type catalyst.

More specifically, the invention relates to an adhesive release composition comprising (A) 100 parts by weight of an oxyalkylene group-containing organopolyoloxane having at least 3 silicon-linked alkenyl groups in each molecule, which can be represented by the formula R 2 (R 1 R 2 SiO) x (R 2 SiO 2 SiR 12 R 2 wherein R 1 is a monovalent hydrocarbon group; R 2 is either a hydroxyl group, an R 1 group or an R 3 group; R 3 is a group of the formula - (R 2) a -O- (R 2 O) 2 R 2 in which R 1 and R 2 are alkylene groups having 2 to 6 carbon atoms, R 1> is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, a has values of one or zero, z has an average value of 1 to 100, and x and y are equal to or greater than one, provided that y / x has an average value between 0.1 and 100 and (x + y) has an average value of at least 10; (B) 0.520 parts by weight of an organohydrogenpolysiloxane having at least 3 silicon-15 hydrogen atoms in each molecule, and (C) a catalytic amount of a platinum group metal-containing catalyst.

Component (A) of the invention is new and is central to forming a removable surface with good printability. This component is an oxyalkylene-containing organopolysiloxane of formula R2 (R1R3SiO) x (R12SiO) ySiR1R2.

• ·]; *; In the above formula, R 1 is a monovalent hydrocarbon group, and examples thereof include alkyl groups such as methyl, ethyl, propyl, butyl, octyl, trideltyl and cyclohexyl; aryl groups such as phenyl and tolyl; and alkenyl groups such as vinyl and allyl. It is essential for crosslinking with component (B) that V · at least three of the R1 groups in each molecule are alkenyl groups. From the viewpoint of release properties, it is preferred that the methyl comprises at least SO mole%.

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In the above formula of component (A), R 2 is a hydroxyl group, an R 1 group or an R 3 group, and R 3 is a group of the formula - (R 1) a -O- (R 2 O) 2 R 2. In the formula of R3, R1: V and R5 are alkylene groups having 2 to 6 carbon atoms. Examples of such are the ethylene, propylene, isopropylene, butylene and isobutylene groups. When Zilla, · * · ,. which can have values of 1-100 is a value of two or more is R ^ either the same. ···. 35 qualities or a combination of different qualities. R 1 is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. Examples of this monovalent organic group having 1 to 10 carbon atoms include the following monovalent hydrocarbon groups: 3,98637 methyl, ethyl, propyl, butyl, vinyl and phenyl; and acyl groups such as acetyl and propionyl.

In the formula for R 1, a has a value of one or zero. A value of one is more advantageous in terms of stability against hydrolysis. In the formula for component (A), x and y are integers with a value of at least 1, provided that the ratio y / x is between 0.1 and 100 and (x + y) is at least 10. If (x + y) is not at least 10, is the coatability of the substrate unsatisfactory from a practical point of view. The printability is low when the y / x ratio exceeds 100, and unchanged adhesive release properties 10 are not achieved if the value is less than 0.1.

Component (A) is obtained, for example, by a condensation reaction between an alkenyl group-containing hydroxyl group-terminated diorganopolysiloxane and an oxyalkylene group-containing dichlorosilane.

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Component (B) is a crosslinking agent of component (A) and consists of an organohydrogenpolysiloxane having at least 3 silicon-bonded hydrogen atoms in each molecule and having an average unit formula of R7siO (4_by2- In this formula, each is either a hydrogen atom or a monovalent hydrocarbon group containing no alkyl Examples of such monovalent hydrocarbon groups are those listed in Component (A) with the exception of alkenyl groups In the formula b of Component (B), VI has a value of 1.5 to 3.0, preferably 1.9 to 2.1.

• · · »· • · • · •

The degree of polymerization of component (B), i.e. the number of silicon atoms in the average 25 molecule (B) should be at least 2, while the upper limit is not essential. Its molecular configuration is also not essential and may be straight-chain, branched, branched, cyclic or reticulated.

Concrete examples of the component (B) are: dimetyylivetysiloksipäätteiset 30 dimethylsiloxane-methylhydrogensiloxane copolymers, trimethylsiloxy '· dimethylsiloxane-methylhydrogensiloxane copolymers, dimetyylifenyylisiloksi- X · · · * terminated dimetyylisiloksaanimetyylivetysiloksaam copolymers, trimethylsiloxy methylhydrogenpolysiloxanes, cyclic methylhydrogenpolysiloxanes, and copolymers »copolymers, consisting of dimethylhydrogensiloxane units and SiO 2 units. These. ···, 35 can be used either alone or in combination of two or more types.

4,98637

The amount of component (B) to be used is 0.5 to 20 parts by weight per 100 parts by weight of component (A). If the amount added is less than 0.5 parts, the curing rate is low and productivity decreases. Exceeding 20 parts by weight reduces printability.

Component (C) is a platinum group metal-containing catalyst for the crosslinking reaction between component (A) and component (B). Specific examples of this component are chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid olefin complexes, chloroplatinic acid and vinylsiloxane complexes, chloroplatinic acid and ketone component the composition in question. That is, as long as a catalytic amount is used, the amount to be added can be selected indefinitely without considering the coating conditions, etc. In general, the component is added in an amount corresponding to 10 to 1000 ppm of platinum group metal based on the total of components (A) and (B).

The adhesive release composition of the invention may be used either as such or after mixing with one or more optional ingredients such as organic solvents, organic solvent soluble organopolysiloxane resins, addition retarders, pigments, macromolecular hydrocarbons, etc.

• · ··· «· * # · · \ · * Concrete examples of the above-mentioned organic solvents are aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as heptane, hexane and pentane; halogenated hydrocarbons such as trichlorethylene and ··· J. :: perchlorethylene; as well as ethyl acetate, methyl ethyl ketone and methyl isobutyl-ketone.

The adhesive release composition of the invention can be coated and cured on substrates such as various papers, synthetic resin films, fibers,> aluminum, etc., which are desired to be printable or which can be printed with water-based inks (e.g., fountain pen ink, water-based inks). , 1, ..: pencils) or oil-based inks (eg check inks, printing inks, etc.). It can also be used as a release agent in pressure sensitive tapes, labels * *. * · *. 35, etc.

** ·

The following examples illustrate the invention in more detail, but are not intended to limit the invention. In these examples, parts refer to parts by weight, and viscosity has been measured at 25 ° C. We mean a methyl group and Vi a vinyl group. Peel resistance, residual adhesion and weight properties were measured under the following conditions.

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A certain amount of the adhesive release composition was applied to a sheet-shaped substrate. After the cured film had formed at a certain temperature, after a certain time, the film surface was coated with Oribine BPS-5127 (acyl-based pressure-sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd.) or Oribine BPS-2411. (rubber-based pressure sensitive adhesive manufactured by Toyo Ink Mfg. Co., Ltd.), and this preparation was heated at 70 ° C for 2 minutes. After placed in the back of the paper, and the test material was aged for a period of time (one päivf and 60 days) at 25 ° C of 20 g / cm ^ in under the weight. The aged test piece was cut into 5 cm wide, and the back side of the paper was pulled at an angle of 180 degrees at a speed of 30 cm / min at 15 using a tensile testing machine, and the required separation force was measured in grams.

Residual Adhesion A cured film for peel resistance measurement was formed on the surface of the substrate sheet. . then Nitto Polyester Tape 31B (trade name of Nippon Electric Co., Ltd.) was applied to the surface. A force of 20 g / cm 2 was applied to the sheet and heated for 20 hours at 70 ° C, after which the tape was pulled off and reattached to a stainless steel plate. The force (in grams) J 25 required to peel the treated tape from the stainless steel plate (180 degree peel, speed = 30 cm / min) was then measured. This value is expressed as a percentage of the force V (in grams) required to remove the untreated reference tape from the stainless steel plate.

a • · ... 30 Printability • # · a · a • V A cured film was formed on the surface of the substrate sheet as shown in connection with the measurement of the peel resistance] * ’, and marks were written on this surface with check ink. * (oil-based). The print was visually assessed by looking for creep «· ... 35 or fragmentation and that the writing was clean and well formed.

«6 98637

Reference Example 1

The following substances were placed in a 4-necked flask equipped with a stirred reflux condenser and a thermometer, and the mixture was heated with stirring to 100 ° C: 5,100 parts of a polysiloxane of the formula HO (Me 2 SiO) 4 g (MeViSiO) 2 H, 32 parts of sodium bicarbonate toluene. 118.5 parts of oxyalkylene-containing methyldichlorosilane of the formula MeCl 2 SiCH 2 CH 2 CH 2 O (C 2 H 4 O) 10 CH 3 were then added dropwise over two hours, and the reaction was then allowed to proceed for a further two hours at the same temperature. The mixture was cooled to 70 ° C, 2 parts of water were added, the reaction mixture was filtered, and the solvent was removed under reduced pressure. The product was an oxyalkylene-containing organopolysiloxane (Siloxane A) having the following formula

OH (Me2SiO) 480 (MeViSiO) 200 (MeSiO) i05H 15 I

C3H6O (C2H40) l0CH3

Example 1 100 parts of the oxoalkylene-containing organopolysiloxane (Siloxane A) prepared in Reference Example 1 above, 3 parts of trimethylsiloxy-terminated poly (methylhydrogen) -. * * · Siloxane (viscosity = 20 centipoise), 342 parts of toluene and 801 parts of methyl 1 * 1 r. Of isobutyl ketone was combined and mixed until homogeneous. Then, v. Chloroplatinic acid / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added to give Sample 1.

M · • «· Sample 2, a composition of the present invention, was prepared just as in Sample 1, except that instead of Siloxane A of Sample 1, 100 parts of an oxoalkylene-containing organopolysiloxane (Siloxane B) of formula * ·· · 30

HO (Me2SiO) 46o (MeViSiO) 4o (MeSiO) i oH

S3 C3H60 (C2H40) 5oCH3 9 * 9 «, * 35 Sample 3, which is also a composition of the invention, was prepared exactly as in Sample 1, except that 100 parts of oxoalkylene containing organopolysiloxane were added instead of Siloxane A of Sample 1, having the formula 7 98637

HO (Me2SiO) 48o (MeViSic) 2o (MeSiO) iooH

C3H60 (C2H40) 2o (C3H60) 2oCH3.

In Comparative Example 1, the composition was prepared in exactly the same manner as in Example 1, except that 100 parts of hydroxyl-terminated dimethylsiloxane-methyl vinylsiloxane copolymer rubber (vinyl content 1.0% by weight) were added instead of Siloxane A in Example 1, and 897 parts of toluene were used. toluene and 801 parts of methyl isobutyl ketone instead.

The weight properties, release resistance and residual adhesion of these compositions were evaluated by the methods described above. The conditions were as follows: coating with a solids content of 1 g / m 2 on polyethylene laminated kraft paper, formation of a cured film by heating at 180 ° C for 60 seconds, Oribine BPS-2411 (trade name of Toyo Ink 15 Mfg. Co., Ltd.) was used to measure the peel resistance. pressure sensitive adhesive. The experimental results of the Examples and Comparative Examples are shown in Table 1.

In Samples 1, 2, and 3 (release agent compositions of the invention), no creep of check ink was observed at all, and the written characters were clear and even, indicating that the printability was superior. Likewise, the release resistance and residual adhesion values were excellent. In comparison, in Comparative Example 1, a significant creep of check color was observed, and the marks were smudged and vaguely written.

• · 25 Table 1 • · • · V: Release resistance · 1 ***: Residual adhesion • ·· (g / 5 cm) in time. 30 Printability_1 day 60 days _ (%) • ·. Sample 1 excellent 62 64 91 ./.* Sample 2 excellent 56 57 92 • · • \ * Sample 3 excellent 60 59 90; * · [: 35 Comparative sample 1 bad 16 19 90 ·· »• · · I · • · · • · · • · * ♦ ··· 98637 g

Example 2

The following ingredients were mixed until homogeneous: 100 parts of an oxyalkylene-containing organopolysiloxane (siloxane D) having the structure 5

ViMe2SiO (MeSiO) ioo (Me2SiO) 46o (MeViSiO) 40oSiMe2Vi C3H60 (C2H40) 24 (C3H60) 24CH3 10 5 parts of trimethylsiloxy-terminated methylhydrogenpolysiloxane The chloroplatinic acid-olefin complex was then added in an amount corresponding to a platinum metal content of 200 ppm, and the composition of the invention (Sample 4) was prepared by stirring.

The second composition of the invention, Sample 5, was prepared in exactly the same way as Sample 4 except that 100 parts of oxyalkylene-containing organopolysiloxane (Siloxane E) having the following structure was added instead of the Siloxane D of Example 4.

ViMe2SiO (MeSiO) 2o (Me2SiO) 54o (MeViSiO) 4oSiMe2Vi 20 | C3H60 (C2H40> 24 (C3H60) 24CH3.

As Comparative Example 2, the composition was prepared in exactly the same manner, but using 100 parts of such oxyalkylene instead of the Siloxane D of Example 4. 25 organopolysiloxanes having the following structure m • · ·: V ViMe2SiO (MeSiO) 79o (Me2SiO) i (MeViSiO) 5SiMe2Vi .-. C3H60 (C2H40), 24 (C3H60) 24CH3.

30 • · · l. In Comparative Example 3, the composition was prepared in exactly the same manner, but using 100 parts of an oxyalkylene-containing organopolysiloxane having the following structure instead of the siloxane D of Example 4, ViMe2-SiO (MeSiO) 3 (Me2SiO) 557 ( MeViSiO) 4oSiMe2Vi lv C3H60 (C2H40) 24 (C3H60) 24CH3.

The release resistance, residual adhesion and weight properties of these compositions were evaluated under the following conditions: • · ··· 9 98637 coating with a solids content of 1.2 g / m 2 on polished parchment, heating for 60 seconds at 180 ° C. These results are shown in Table 2. The pressure-sensitive adhesive used to measure the release resistance was Oribine BPS-8170 (trade name of Toyo Ink MFG. Co., Ltd.). The experimental results of the Examples and Comparative Examples are shown in Table 5 2.

Samples 4 and 5 (compositions of the invention) have excellent printability: no check color creep was observed at all, and the characters could be written clearly and evenly. In addition, their release resistance values were unchanged. In comparison, the detachment resistance of ver-10 tail example 2 was too high to be practical, although its printability was excellent (no check color creep, clear and even marks). The peel resistance of Comparative Example 3 was low and thus excellent, but this composition showed a considerable creep of check ink, so that the printability was very poor.

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Table 2 Residual adhesion (g / 5 cm) in time 20 Printability_1 day 60 days (%) Sample 4 excellent 89 90 90 Sample 5 excellent 61 63 90

Comparative Example 2 excellent 598 648 88: ***: 25 Comparative Example 3 bad 24 26 93 • · • · • · · • ·: ***: Example 3 ··· ··· • · »• *»

The following were mixed until homogeneous: 100 parts of oxyalkylene-containing organopoly • · · 30 lysiloxane having the following structure,

F * · * HO (Me2SiO) 66o (MeViSiO) 4o (MeSiO) i4H

: T: I

‘.Λ C3H60 (C2H40) 24 (C3H60) 24CH3 •« ·:. * 35 • ·· 3 parts of trimethylsiloxane-terminated polymethylhydrogensiloxane (viscosity = 20 · * · .. centipoise), 350 parts of toluene and 547 parts of methyl ethyl ketone. The invention co. * · *. The sample, sample 6, was then prepared by adding, with good stirring, 10 μl of chloroplatinic acid / po / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in an amount to give a Platinum metal concentration of 180 ppm.

The second composition of the invention, Sample 7, was prepared in exactly the same manner as Sample 6, 5 except that 6 parts of methyl hydrogen polysiloxane were used instead of 3 parts of methylhydrogenpolysiloxane in Sample 6, and 347 parts of toluene were used instead of 350 parts.

Comparative Example 4 was prepared in the same manner as Sample 6, except that the addition of poly (methylhydroxyoxane) was 0.3 parts instead of 3 parts of Sample 6. Comparative Example 5 10 was further prepared in the same manner as Sample 6, except that the addition of methylhydrogenpolysiloxane was 40 parts instead of 3 parts of Example 6.

These compositions were formed into cured wells by coating polyethylene-laminated kraft paper with a solids content of 0.6 g / m 2 and heating for 60 seconds at 180 ° C, and their peel resistance, residual adhesion and weight properties were evaluated.

The results are shown in Table 3. The pressure-sensitive adhesive used in the release resistance measurement was Oribine BPS-2411 (trade name of Toyo Ink Mfg. Co., Ltd.). The results are shown in Table 3.

Samples 6 and 7, which are compositions of the invention, had superior weight characteristics: no signs of check color creep were written evenly and clearly. Furthermore, they had constant release resistance values.

• ·

In comparison, the composition of Comparative Example 4 could not be cured under the conditions given above, while Comparative Example 5 had poor printability due to check color creep.

··· «· • · ··· _

Table 3 • · »» φ φ m · · • · · * * 30 Release Residual Residual Adhesion • ·; (g / 5 cm) in time * Printability_1 day 60 days (%> ·· · • · · »·. ***; 35 Sample 6 excellent 48 49 92 • · φ .. · Sample 7 excellent 60 66 91 • ♦: ** Comparative Example 4 - ·· »'···' Comparative Example 5 bad 84 96 95 11 98637

Since the release agent of the invention forms a composition containing certain amounts of oxyalkylene-containing organopolysiloxane as component (A), organohydrogenpolysiloxane as component (B) and platinum-type catalyst component (C), it is characterized in that it forms a release pin on various substrate surfaces. has excellent weight properties and constant release force.

• m ·· · • · * »· • · · · · · · · ·» · · · · m · • 1 • · »· * · • • • · · · · · · · · · · 9 • · · • · · ♦ • · · · ·

Claims (4)

98637 An adhesive release composition comprising: (A) 100 parts by weight of an oxoalkylene group-containing organopolysiloxane having at least 3 silicon-linked alkenyl groups in each molecule, which can be represented by the formula R2 (R1R3siO) x (R12SiO) ySiR1R2, wherein R1 is a monovalent hydrocarbon group; R 1 is either a hydroxyl group, an R 1 group or an R 3 group; R 3 is a group of the formula - (R 2) a -O- (R 2 O) 2 R 6, wherein R 1 and R 2 are alkylene groups having 2 to 6 carbon atoms; R *> is a hydrogen atom or a monovalent organic group containing 1 to 10 carbon atoms, a has the values one or zero, z has an average value between 1 and 100; and x and y are equal to or greater than one, provided that y / x has an average value between 0.1 and 100 and (x + y) has an average value of at least 10; (B) 0.5 to 20 parts by weight of an organohydrogenpolysiloxane having at least 3 silicon-bonded hydrogen atoms in each molecule; and (C) a catalytic amount of a platinum hm metal-containing catalyst. 15 Adhesive release composition according to Claim 1, characterized in that component (B) is a trimethylsiloxy-terminated poly (methylhydrogen) siloxane and component (C) is a complex of chloroplatinic acid and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane. . 20 An organopolysiloxane compound containing an oxyalkylene group, characterized in that it has at least 3 silicon-linked alkenyl groups in each molecule and is represented by the formula R 1 (R 1 R 3 SiO 2, R 12 SiO) ySiR 2 2 R 2% wherein R 1 is a monovalent ... * hydrocarbon group; R 1 is one of the group: a hydroxyl group, an R 1 group and an R 3 group; V 25 R 3 is a group of the formula - (R 2) a -O- (R 2 O) ZR 2, wherein R 2 and R 2 are alkylene groups containing 2-6 carbon atom V; R *> is a hydrogen atom or a monovalent organic group containing 1 to 10 carbon atoms, a is one or zero, z is an average value between 1 and 100; ··· and x and y are equal to or greater than one, provided that the ratio y / x has an average value between 0.1 and 100 and the value of (x + y) is on average at least 10. 30 4. Process, characterized in that: · .. ** (I) a coating mixture is prepared from the following components: (A) 100 parts by weight of an organopolysiloxane containing at least 3: * · [: oxyalkylene group-containing organopolysiloxane a silicon-linked alkenyl group in each molecule and which can be represented by the formula i ***: wherein R 1 is a monovalent hydrocarbon group; R 1 is either a hydroxyl group, an R 1 group or an R 3 group; R 3 is a group of the formula - (R 2) a -O- (R 2 O) 2 R 2, wherein R 1 and R 2 are alkylene groups having 2 to 6 carbon atoms; R *> is a hydrogen • · * ··· * atom or a monovalent organic group containing 1 to 10 carbon atoms, a has values of one 98637 or zero, z has an average value of 1 to 100; and x and y are equal to or greater than one, provided that y / x has an average value between 0.1 and 100 and (x + y) has an average value of at least 10; (B) 0.5 to 20 parts by weight of an organohydrogen polysiloxane having at least 3 silicon-bonded hydrogen atoms in each molecule; and (C) a catalytic amount of a platinum group metal-containing catalyst; (U) the substrate material is coated with the mixture (I); and (III) curing the coating composition to a solid.