FI98637C - Release Agent 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 as well as excellent weight properties.

It is known that organopolysiloxane-based release agent compositions coated with a desired substrate, such as various papers, synthetic resin films, fibers, aluminum, etc., have excellent adhesive release properties. These organopolysiloxane release agent 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 through an addition reaction (see JP). -26798 (26,798 / 71)).

15

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 in the adhesive layer (tacky adhesive coating on the sheet or teippialustalla), and separating layer (the opposite side of the organopolysiloxane coating) become superposed and meet. Often such an adhesive sheet must be printed or printed during use. Since this surface has been releasably poor printing properties, it has been necessary between the adhesive layer and the back side of the substrate sheet, for example, set the weight of the characteristics of good and high-quality paper. Furthermore, when adhesive tape is used for packaging, e.g., cardboard, things such as addresses, etc. cannot be pinned over the tape.

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 and 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 having at least 3 silicon-linked alkenyl groups in each molecule, 2,98637 (B) a hydrogen atom in each molecule to an organove-typolysiloxane 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 organopolyloxane having at least 3 silicon-linked alkenyl groups in each molecule, which can be represented by the formula R 1, R 2, SiO 2, R 2, SiCO 2 R 1, wherein R 1 is a monovalent hydrocarbon group; R 1 is either a hydroxyl group, an R 1 group or an R 1 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 1 is a hydrogen atom or a monovalent organic group containing 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-bonded 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, tridecyl and cyclohexyl; aryl groups such as phenyl and tolyl; and alkenyl groups such as vinyl and allyl. It is essential for cross-linking with component (B) that at least three of the R1 groups in each molecule are alkenyl groups. From the karma of the release properties, it is preferred that the methyl comprises at least 80 mole% of R1.

In the above formula of component (A), R 1 is a hydroxyl group, an R 1 group or an R 3 group, and R 3 is a group of the formula - (R 2) a -O- (R 2 O) 2 R 2. In the formula for R 1, R 1 and R 2 are alkylene groups having 2 to 6 carbon atoms. Examples of such are ethylene, propylene, isopropylene, butylene and isobutylene groups. When z, which can have values from 1 to 100, has a value of two or more, R 1 has either the same grade or a combination of different grades. 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 are the following monovalent hydrocarbon groups:

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3,98637 methyl, ethyl, propyl, butyl, vinyl and phenyl; and acyl groups such as acetyl and propionyl.

In the formula of R.3, a has the value 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 a hydroxyl group-terminated diorganopolysiloxane containing an alkenyl group and a dichlorosilane containing an oxyalkylene group.

15

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 R 1 SiO (4_b) / 2 In this formula, each R 7 is either a hydrogen atom or a monovalent hydrocarbon group , which does not contain alkenyl groups. Examples of such monovalent hydrocarbon groups are those listed for R * of component (A) with the exception of alkenyl groups. In the formula of component (B), b has a value of 1.5-3.0, preferably 1.9-2.1.

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 chain, branched, cyclic or reticulated.

Concrete examples of the component (B) are: dimetyylivetysiloksipäätteiset 30 dimetyylisiloksaanimetyylivetysiloksaani copolymers, trimethylsiloxy dimetyylisiloksaanimetyylivetysiloksaani copolymers, dimetyylifenyylisiloksi-terminated dimetyylisiloksaanimetyylivetysiloksaani copolymers, trimethylsiloxy methylhydrogenpolysiloxanes, cyclic methylhydrogenpolysiloxanes, and copolymers consisting of dimetyylivetysiloksaaniyksiköistä and Si02 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 complexes, alumina and rhodium-plated platinum, alumina or silicon-bonded, 10 This component is added in an amount sufficient to cure the composition in question. That is, as long as a catalytic amount is used, the amount to be added can be selected without limitation 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.

Specific examples of the above-mentioned organic solvents include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as heptane, hexane and pentane; halogenated hydrocarbons such as trichlorethylene and perchlorethylene; as well as ethyl acetate, methyl ethyl ketone and methyl isobutyl ketone.

The adhesive release composition of the invention may 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 written with water-based inks (e.g., fountain pen, water-based pens, 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 a viscosity of 5,98637 is 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.

Disconnection resistor 5

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 (acrylic-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 day and 60 days) at 25 ° C of 20 g / cm ^ 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 was formed on the surface of the substrate sheet as shown in the release resistance measurement, then Nitto Polyester Tape 31B (trade name of Nippon Electric Co., Ltd.) was applied to the surface. The sheet was subjected to a force of 20 g / cm 2 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) 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 (in grams) required to remove the untreated reference tape from the stainless steel plate.

30 Printability

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 no creep 3 5 or fragmentation and that the writing was clean and well formed.

6,98637

Reference Example 1

The following substances were placed in a four-necked flask equipped with a stirrer, reflux condenser and 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 (Me 2 SiO) 4go (Me ViSiO) 200 (MeSiO) 105H

15 I

C3H60 (C2H40) 10CH3

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 isobutyl were mixed. gay sex gene. Chloroplatinic acid / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was then added to give Sample 1.

Sample 2, a composition of the present invention, was prepared just as in Sample 1, except that 100 parts of oxyalkylene-containing organopolysiloxane (Siloxane B) of formula 30 was added instead of Sample 1 Siloxane A.

HO (Me2SiO) 46o (MeViSiO) 4o (MeSiO) IOH

C3H60 (C2H40) 50CH3 35 Sample 3, which is also a composition of the invention, was prepared exactly as in Sample 1, except that 100 parts of oxyalkylene-containing organopolysiloxane of formula HO (Me2SiO) 480 (Me ViSio) were added instead of Sample 1 Siloxane A. 20 (MeSiO) + 00 ^ 7 98637 C3H6O (C2H4O) 2O (C3H6O) 20CH3.

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

Peel resistance 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 poor 16 19 90 8 98637

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 an oxyalkylene-containing organopolysiloxane having the following structure instead of the Siloxane D of Example 4.

ViMe2SiO (MeSiO) 79o (Me2SiO) 1 (MeViSiO) 5SiMe2Vi C3H60 (C2H40) 24 (C3H60) 24CH3.

30

In Comparative Example 3, the composition was prepared in exactly the same manner, but using 100 parts of oxyalkylene-containing organopolysiloxane having the following structure instead of the Siloxane D of Example 4. ViMe2SiO (MeSiO) 3 (Me2SiO) 557 (MeViSiO) 40SiMe2Vi C3 H60 (C2 24CH3 The release resistance, residual adhesion and weight properties of these compositions were evaluated under the following conditions: 9 98637 coating at 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 release 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 poor 24 26 93

Example 3

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

HO (Me2SiO) 660 (MeViSiO) 4o (MeSiO) i4H

C3H60 (C2H40) 24 (C3H60) 24CH3 3 parts of trimethylsiloxane-terminated polymethylhydrogensiloxane (viscosity = 20 centipoise), 350 parts of toluene and 547 parts of methyl ethyl ketone. The composition of the invention, Sample 6, was then prepared by adding, with good stirring, 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 way as sample 6, 5 except that 6 parts of methylhydrogenpolysiloxane 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 (methylhydrogensiloxane was 0.3 parts instead of 3 parts of Sample 6. Comparative Example 5 was further prepared in the same manner as Sample 6 except that the addition of methylhydrogenpolysiloxane was 40 parts of Part 3 of Example 6. instead of.

These compositions were formed into cured films 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 check creep was observed and the characters 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 30 Release resistance Residual adhesion (g / 5 cm) over time

Printability_1 day 60 days (%) 35 Sample 6 excellent 48 49 92 Sample 7 excellent 60 66 91

Comparison example. 4 - -

Comparison example. 5 bad 84 96 95

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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.

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 1 is a hydrogen atom or a monovalent organic group containing 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) 0.5 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 group 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-bonded alkenyl groups in each molecule and is represented by the formula R 1, R 1, R 5, O 2, R 1, Si, N, 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; R 3 is a group of the formula - (R 2) a -O- (R 2 O) 2 R 2, wherein R 1 and R 3 are alkylene groups having 2 to 6 carbon atoms; R 1 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) averages at least 10. 30 A process characterized in that: (I) a coating composition is prepared from the following components: (A) 100 parts by weight of an oxoalkylene group-containing organopolysiloxane having at least 3 silicon-linked alkenyl groups in each molecule and which can be represented by the formula 35 R 2 (R 1 R 3 s) x (R (2SiO) ySiR12R2, 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 30) 2 R 6, wherein R 1 and R 3 are alkylene groups having 2 to 6 carbon atoms; R 1 is a hydrogen atom or a monovalent organic group containing 1 to 10 carbon atoms, a has values of one II 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; (II) the substrate material is coated with the mixture (I); and (III) curing the coating composition to a solid.